IGCP/SIDA Project 594, Annual Workshop, Windhoek, Namibia, 2012, © Czech Geological Survey, ISBN 978-80-7075

-781-9

3.4 Contents of metals and arsenic in cassava parts The sampling of crops was mainly focused on those parts of cassava that are used for preparation of food (leaves and tubers). In order to assess the distribution of metals also in other parts of cassava a few samples of the same plant were taken in uncontaminated parts of the Copperbelt, from which leaf stalks, stems and roots were analyzed for metals and arsenic in addition to their leaves and tubers (Fig. 2). The results revealed that the contents of zinc in cassava leaves (median 133 mg kg-1 dw) are very high and even higher than contents of this element in soil (55 mg kg-1). The contents of copper and zinc in the aboveground parts of cassava were found to be higher relative to their contents in their peeled tubers whereas the contents of As and Pb in the aboveground and underground parts of cassava are more or less the same. The content of cobalt was below the detection limit of the given analytical method.
Leaf: As 0.14 Co <0.5 Cu 11.7 Pb 3 Zn 133 Leaf stalk: As 0.43 Co <0.5 Cu 7.7 Pb 2 Zn 76

Pb in the contaminated area and the uncontaminated area (2.2 and 2.4 mg kg-1 dw respectively) do not differ significantly. Median values for individual data sets of cassava tubers are significantly lower in relation to the same median values for leaves, except for arsenic (Table 3). 3.6 Correlation of chemical elements in soils and in cassava Significant values of Spearman’s coefficients of correlation at the significance level p<0.001 (99.9%) were found in the case of cassava between contents of Co in soil and leaves (r = 0.49), Cu in soil and leaves (0.57), Zn in soil and leaves (0.53) and between content of Cu in soil and in tubers (r = 0.61). Significant correlation at the level p<0.05 (99%) was found between content of lead in soil and leaves (r = 0.37) and As in soil and leaves (r = 0.39). 3.7 Dietary risk assessment Although cassava tubers are decreasing in use as foodstuffs among the urban population and gradually being replaced by cornflour, the cassava in the Copperbelt countryside still represent a very substantial part of the food intake. In the risk assessment of Cu, Pb and As, their intake through cassava consumption by the rural population of the Copperbelt was taken into account. The flour made from cassava tubers in Zambia is mostly used for preparation of cassava mush that is locally called “nshima”. Daily intake of cassava mush or is estimated at 300 g (single meal). Leaves of cassava are stewed in oil and prepared as a vegetable salad. The daily intake can be estimated at 70 g/day (single meal). The highest tolerable weekly or daily intake limits established by the Joint FAO/WHO Expert Committee on Food Additives (JECFA, 2007) were used when assessing the health risk linked with the intake of metals and arsenic through consumption of cassava cultivated in contaminated areas of the Copperbelt. The daily maximum tolerable limit for copper is 0.5 mg.kg1 /human body weight (HBW), for lead the weekly tolerable limit corresponds to 0.025 mg kg-1/HBW and for arsenic the highest tolerable weekly intake limit is 0.015 mg kg-1/HBW). The highest tolerable limit for cobalt was not established as yet. Because these intake limits apply to fresh vegetables, the contents of metals and arsenic referred to in this study referring to dry weight (dw) were recalculated to fresh weight (fw). Mean contents of water in leaves and tubers of cassava were used in the recalculation. The average weight (HBW) of Zambian rural population (adults) was estimated at 70 kg. The values of daily or weekly dietary copper uptake in relation to 70 kg HBW in the contaminated area of the Copperbelt show that the daily dietary uptake of copper in the contaminated area does not exceed the limit established by JECFA (2007). As far as lead and arsenic are concerned, their weekly tolerable limits are exceeded only rarely, particularly in the neighborhood of smelters. However, the limits for As and Pb were slightly exceeded in some samples even in the uncontaminated area. This is likely to be due to
31

Root: As 0.37 Co <0.5 Cu 6.5 Pb 1.8 Zn 23 Stem: As 0.27 Co <0.5 Cu 14.1 Pb 1.3 Zn 51

Peeled tuber: As 0.11 Co <0.5 Cu 1.7 Pb 0.7 Zn 11

Peel: As 0.81 Co <0.5 Cu 6,7 Pb 1.8 Zn 36

Concentration in soil: As: 0.90, Co: 17, Cu: 48, Pb: 10,6, Zn: 55 mg kg -1

Figure 2. Contents of metals and arsenic (median values, mg kg-1, dw) in cassava components from the same sampling site in the uncontaminated part of the Zambian Copperbelt. Median values in soil are given for comparison. Number of samples taken: 5.

3.5 Metals and arsenic in cassava leaves and tubers in uncontamited and contamited areas These basic statistical data on the content of metals and arsenic in cassava leaves and tubers in uncontaminated (EI< 1) and contaminated (EI>1) areas of the Copperbelt are summarized in Table 2 and 3. For cassava leaves, median values for Zn (107.1 mg kg-1 dw) Cu (131 mg kg-1 dw) Co (5.2 mg kg-1 dw) and As (0.58 mg kg-1 dw) are significantly higher compared with cassava leaves in the uncontaminated area (Zn: 50.4; Cu: 20; Co: 1.1; As: 0.23, all in mg kg-1 dw, respectively). Median values for

IGCP/SIDA Project 594, Annual Workshop, Windhoek, Namibia, 2012, © Czech Geological Survey, ISBN 978-80-7075-781-9

natural high contents of both elements in some soils of the Copperbelt (Kříbek et al. 2010). Therefore, based on the risk analysis, it is concluded that the health risk associated with the consumption of cassava grown in the contaminated area of the Copperbelt is, in general, low. Moreover, both vegetables sold in local markets mostly do not come from the most contaminated areas but are imported from less contaminated areas. 3.8 Surface contamination of cassava leaves Although the health risk linked with the intake of metals and arsenic from cassava by human beings is low in contaminated area, it might be substantially higher when poorly washed leaves of cassava are used for preparation of salads. The leaves of cassava cultivated in the immediate vicinity of smelters in the Copperbelt are covered with tiny particles of dust consisting commonly of fragments of quartz, feldspars and clay minerals. The dust, however, also comprises tiny fragments of silicate slag containing enhanced contents of metals – iron and copper in particular (Vítková et al. 2010) (Fig. 3A, B). Some slag particles also contain other potentially toxic elements such as for example Bi and Pb. Microspherules of intermediate solid solution (ISS) of Cu, Fe and S were also identified on the leaves of cassava (Fig. 3C). The dust fallout near smelters also contains spherules of easily soluble chalcanthite (CuSO4.5H2O) that is a reaction product of molten copper with escaping sulfur dioxide (Fig. 3D). Strong contamination of the surface of leaves of cassava grown near the smelters is best observed when comparing the contents of metals and arsenic in unwashed and carefully cleaned cassava leaves collected from crops cultivated in contaminated and uncontaminated areas of the Copperbelt region (Table 4). The table shows clearly that the contents of metals and arsenic in unwashed leaves of cassava cultivated in the contaminated area close to the smelter can be significantly reduced simply by washing them. It is obvious that the washing results chiefly in reduction of the contents of Cu, Co and Fe, which are the major components of the dust fallout emitted by local smelters.

Cht ISS

A

SL Gy Qtz
100 m

B ALS Sl

50 m

C

D

80 m

60 m

4 Conclusions
Because of strong contamination of some parts of the Zambian Copperbelt mining district caused by the extraction and processing of copper ores, the local soils and cassava plants in contaminated areas contain high contents of this metal. The contents of Cu in cassava leaves were found to be the highest ever recorded. The leaves of cassava in the contaminated area also contain higher contents of zinc, cobalt and arsenic whereas the content of lead is low and more or less the same in plants from both contaminated and uncontaminated areas. The contents of metals in the tubers of both plants are much lower than the contents in their leaves. The dietary risk assessment has not indicated any excessive intake of copper, but excessive intake of Pb and As was occasionally recorded in contaminated as well as uncontaminated areas of the Zambian

Figure 3. Dust fallout particles on the surface of cassava leaves from contaminated area of the Zambian Copperbelt. A: Cassava leaves collected 1 km downwind of the Mufulira Smelter. Dust particles are composed of angular and subangular grains of quartz (Qtz), spherical grains of Cu-Fe-S intermediate solid solution (ISS), chalcanthite (Cht), gypsum (Gy) and clusters of fine-grained slag particles (Sl). B: cassava leaves taken 4 km downwind of the smelter. Dust particles consist of clusters of very fine alumosilicate particles (ALS) and particles of slag (Sl) with detectable amount of copper, bismuth, zinc and lead. C. Close up photograph of intermediate solid solution of Cu-Fe-S (ISS) on the surface of cassava leaf. D. A particle of chalcanthite (CaSO4 .2H2O) on the surface of cassava leaf. Back-scattered electron images.

Copperbelt. This means that the enhanced contents of Pb and As could have been caused both by anthropogenic contamination and also by naturally high contents in some soils. The surface of the leaves of vegetables growing near the smelters is covered by abundant small particles of slag and even by tiny metallic grains. As a consequence, the preparation of vegetable salads from poorly washed
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IGCP/SIDA Project 594, Annual Workshop, Windhoek, Namibia, 2012, © Czech Geological Survey, ISBN 978-80-7075-781-9

cassava and sweet potato leaves is a risk to the health of the local population. This applies not only to the food plants studied, but to all other leafy vegetables like cabbage or giant rape cultivated in contaminated areas. This study has shown that cassava can, to large degree, tolerate high contents of copper and cobalt in the soils on which they are grown. However, such high contents may cause lower yields in crops cultivated in contaminated areas. In future, the effects of uptake of both metals on the crop yields of these food plants in contaminated areas of the Zambian Copperbelt should be studied in greater detail.

References
Joint FAO/WHO Expert Committee on Food (JECFA) (2007): Database of food additives and pollutants. http://jecfa.ilsi.org/search.cfm, visited 10-10-2011 Kříbek B, Majer V, Nyambe IA (2007) Environmental– Geochemical Atlas of the Central-Northern Part of the Copperbelt Province of Zambia. Czech Geological Survey, Prague Kříbek B, Majer V, Veselovský F, Nyambe IA (2010) Discrimination of lithogenic and anthropogenic sources of metals and sulfur in soils of the central-northern part of the Zambian Copperbelt Mining District: A topsoil vs. Subsurface soil concept. J. Geochem. Explor. 104:69–86 Vítková M, Ettler V, Johan Z, Kříbek B, Šebek O, Mihaljevič M (2010) Primary and secondary phases in copper-cobalt smelting slags from the Copperbelt Province, Zambia. Min. Mag. 74:581–600

Acknowledgements
This study was carried out within the framework of the IGCP/SIDA Project No. 594, Assessment of the impact of mining and mineral processing on the environment and human health in Africa. The work was supported by the Czech Science Foundation (project GA ČR P210/12/1413).

Table 1. Statistical summary of parameters of soils from uncontaminated and contaminated (in parenthesis) area of the Zambian Copperbelt. Number of analyzed samples: uncontaminated area: 41, contaminated area: 30. Fe (g kg-1) 0.12 (0.15) 0.17 (0.21) 0.31 (0.72) 0.58 (1.38) 1.27 (2.14) 2.03 (3.95) 3.95 (4.82) As (mg kg-1) <0.10 (<0.10) <0.10 (<0.10) <0.10 (0.24) 0.27 (0.57) 0.64 (0.91) 1.91 (3.72) 2.28 (3.81) Co (mg kg-1) <5.0 (<5.0) <5.0 (<5.0) <5.0 (7.0) 5.1 (11.2) 9.2 (35.3) 20.6 (82.0) 35.4 (84.2) Cu (mg kg-1) 16.1 (43) 24.1 (108.5) 45.1 (192.3) 85.5 (370.5) 152.3 (694.8) 484.1 (1661.4) 768.2 (3067.1) Pb (mg kg-1) <10 (<10) <10 (<10) <10 (<10) <10 (<10) 10.2 (17.3) 36.4 (25.3) 107 (50) Zn (mg kg-1) <5 (<5) 5.0 (5) 6.1 (10.5) 11.2 (18) 17.2 (35.5) 52.9 (118.2) 72.0 (280.1)

Min. value Percentiles 5% 25% 50% (median) 75% 95% Max. value

Table 2. Statistical summary of contents of metals and arsenic (mg kg-1 dw) in cassava leaves from uncontaminated and contaminated (in parentheses) areas of the Zambian Copperbelt. Number of analyzed samples: n = 31, (n) = 23. As 0.04 (0.21) 0.08 (0.31) 0.19 (0.62) 0.33 (0.79) 0.73 (0.97) 1.68 (0.99) 2.23 (1.00) Co <0.5 (2.7) <0.5 (2.9) <0.5 (3.5) 0.7 (4.3) 0.9 (13.4) 5.4 (17.9) 6.6 (19.7) Cu 15.6 (65.2) 17.5 (67) 24.2 (134.3) 28.0 (233.2) 42.2 (242.9) 134.6 (337.3) 197.5 (376.9) Pb <0.5 (1.7) 0.5 (1.8) 1.1 (1.9) 2.2 (4.0) 4.5 (6.3) 7 (6.8) 7.0 (13.1) Zn 22.9 (21.7) 23.1 (22.4) 24.1 (26.5) 28.2 (33.5) 31.1 (36.5) 41.5 (40.0) 48.0 (41.3)

Min. value Percentiles 5% 25% 50% (Median) 75% 95% Max. value

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IGCP/SIDA Project 594, Annual Workshop, Windhoek, Namibia, 2012, © Czech Geological Survey, ISBN 978-80-7075-781-9 Table 3. Statistical summary of contents of metals and arsenic (mg kg-1 dw) in cassava tubers from uncontaminated and contaminated (in parentheses) areas of the Zambian Copperbelt. Number of analyzed samples: n = 31, (n) = 19. As 0.04 (0.04) 0.04 (0.10) 0.10 (0.32) 0.26 (0.50) 0.43 (0.72) 0.69 (1.26) 0.84 (2.30) Co <0.5 (<0.5) <0.5 (<0.5) <0.5 (<0.5) <0.5 (<0.5) <0.5 (0.8) 1.6 (5.7) 3.2 (12.3) Cu 1.7 (2.3) 2.0 (2.9) 2.9 (4.3) 3.9 (8.4) 5.3 (21.5) 12.5 (64.7) 17.1 (92.9) Pb <0.5 (<0.5) <0.5 (<0.5) <0.5 (<0.5) 0.8 (0.6) 2.1 (1.1) 5.7 (1.3) 8.8 (2.3) Zn 7.9 (9.9) 9.9 (10.1) 12.1 (14.8) 15.4 (21.6) 20.0 (25.9) 49.3 (34.0) 93.9 (35.7)

Min. value Percentiles 5% 25% 50% (Median) 75% 95% Max. value

Table 4. Contents (mg kg-1, dw) of metals and arsenic in unwashed and thoroughly washed cassava leaves from uncontaminated and contaminated area of the Copperbelt region and the amount of chemical elements removed by washing (in % of contents in unwashed leaves). MED = median value, MAD = median absolute deviation, number of samples: 5. Unncontaminated area Unwashed leaves Washed leaves MED ± MAD MED ± MAD 0.10 ± 0.01 0.95 ± 0.05 8.25 ± 1.33 140.6 ± 50.01 0.35 ± 0.05 72.07 ± 1.27 0.10 ± 0.01 0.90 ± 0.08 7.12 ± 1.09 136.2 ± 0.60 0.30 ± 0.00 68.14 ± 0.73 Contaminated area Unwashed leaves Washed leaves MED ± MAD MED ± MAD 0.08 ± 0.01 1.30 ± 0.05 35.95 ± 5.74 800.20 ± 51.0 0.71 ± 0.11 345.20 ± 6.16 0.07 ± 0.01 0.60 ± 0.03 20.12 ± 1.12 183.00 ± 0.0 0.61 ± 0.11 316.27 ± 4.43

Element As Co Cu Fe Pb Zn

% of element removed 4.8 5.3 13.7 3.1 14.3 5.5

% of element removed 12.0 53.8 44.0 77.1 14.3 8.4

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IGCP/SIDA Project 594, Annual Workshop, Windhoek, Namibia, 2012, © Czech Geological Survey, ISBN 978-80-7075-781-9

Dendrogeochemical Record of Pollution from Mining and Smelting in Copperbelt, Zambia
Martin Mihaljevič and Vojtěch Ettler Institute of Geochemistry, Mineralogy and Mineral Resources, Faculty of Science, Charles University, Albertov 6, 128 43 Praha 2, Czech Republic, mihal@natur.cuni.cz Ondřej Šebek Laboratories of Geological Institutes, Faculty of Science, Charles University, Albertov 6, 128 43 Praha 2, Czech Republic Ondra Sracek Department of Geology, Faculty of Science, Palacký University, 17. listopadu 12, 771 46 Olomouc, Czech Republic Bohdan Kříbek, Vladimír Majer and František Veselovský Czech Geological Survey, Klárov 3, 118 21 Praha 1, Czech Republic Tomáš Kyncl DendroLab, Eliášova 37, 616 00 Brno, Czech Republic Abstract. The composition of tree rings and soils was studied at several locations affected by smelting and transportation in the vicinity of Kitwe (Copperbelt, Zambia). The contents of cobalt (Co), copper (Cu), manganese (Mn) and lead (Pb) and the 206Pb/207Pb, isotope ratios in the tree rings were interpreted in relation to potential sources of contamination. The highest Co contents in the tree rings correspond to maximum ore production in the mid-1970´s. Acidification through SO2 emissions is documented in the increased Mn contents from the mid-1980´s. The isotopic composition of the tree 206 207 rings ( Pb/ Pb) of the studied tree species varies in the interval 1.16–1.34. The soil isotope composition varies in the range 1.18–1.35. The Pb isotope composition in the soils and tree rings was formed by a combination of lithogenic Pb, Pb in processed ores and automobile Pb. Keywords. Zambia, tree rings, soils, lead, copper, cobalt, Pb isotopes

This work was performed in order to determine, through comparison of dendrochemistry and the soil composition, whether the source of these substances in the pine-tree xylem is interception or root uptake and the degree to which the studied tree species are affected by industrial activities, transportation or natural processes.

2 Material and methods
Tree rings were sampled at four sites i) close to the smelter (smelter samples I), ii) close to a busy roadway (road samples II and III) and in a remote area (remote samples IV) using a Haglof Incremental Borer (diameter 5 mm). Soils were sampled in 1×1-m-wide pit at site close to the smelter and at a remote (baseline) site. According to the FAO classification (FAO 1997), the studied soils are ferralsols. Details of the rings and soil sample treatment are given elsewhere, e.g., in Mihaljevič et al. (2011). The total content of Pb, Cu, Co and Mn and the isotopic composition of Pb in the mineralizates were determined using inductively coupled plasma mass spectrometry. The locations of the tree ring and soil samples are depicted in Figure 1.

1 Introduction
The contents of a number of substances in wood are proportional in quantity to those in the environment. Tree rings form a geochemical archive and discussions are emerging on their suitability for monitoring historical pollution of the atmosphere (Watmough and Hutchinson 2003). Compounds and ions can enter trees from the soil or directly through capture from the atmosphere by aboveground components (bark, foliage). At sites with important local sources of air pollution, metal uptake occurs through the above-ground parts of the tree (eg. Lageard et al. 2008). The concentrations of the individual elements provide suitable supplementary information to that based on Pb isotopes (Savard et al. 2006). The contents of 206Pb, 207Pb and 208Pb permit differentiation of pollutants of lithogenic, ore and automobile origin and, where appropriate, Pb derived from fossil fuels. Extraction and processing of Cu ores in the Zambian part of the Copperbelt is accompanied by significant emissions of Cu, Co, Pb and SO2. Air-borne dust released from the mines, smelters and transport of concentrates and SO2 from the smelter cause contamination, especially of the surface layers of the soils, plants and biomass (Kříbek et al. 2010).
35

3 Results and discussion
The soils in the contaminated profiles (I, II, III) have lower pH (range 5.8–4.2), higher TS contents (69–3,633 mg kg-1) and higher contents of metals, especially Cu (205–37,770 mg kg-1), Co (8.4–676 mg kg-1), Zn (12.5– 549 mg kg-1) and Pb (32–418 mg kg-1). The 206Pb/207Pb ratio varies in the range 1.175–1.35 in soils from profiles in the contaminated area. The surface layers at the location close to the metallurgy plant (I) and close to the roadway (II and III) have low 206Pb/207Pb ratios (<1.19). The soil profiles at the uncontaminated site (IV) have slightly higher pH values (range 6.1–4.5), lower TS contents (45–179 mg kg-1) and lower metal content, especially Cu (26–134 mg kg-1), Co (3.9–5.65 mg kg-1), Zn (13.7–21.9 mg kg-1) and Pb (8.6–11.2 mg kg-1). The 206 Pb/207Pb ratio in the remote profile (IV) varies in the range 1.33–1.38. The ore concentrates processed at Kitwe have 206Pb/207Pb = 1.21–1.28 (Mihaljevič et al. 2011).

IGCP/SIDA Project 594, Annual Workshop, Windhoek, Namibia, 2012, © Czech Geological Survey, ISBN 978-80-7075-781-9

Copper in the tree rings varies in the range 2–40 mg kg-1 and is clearly higher in the tree rings in the vicinity of the smelter, showing an increase after 1975. In contrast, the Cu content in the tree rings in the remote area and in the vicinity of the highway does not exceed 5 mg kg-1. Cobalt in the tree rings varied in the range 0.05– 0.07 mg kg-1, is highest close to the smelter, lower close to the highway and lowest in the remote area.

decreased rapidly after 1999 and even fell to a value of 1.17. Soils from the profile in the vicinity of the smelter have a low 206Pb/207Pb ratio (approx. 1.17). In the lower part of the profile (depth > 10 cm), the 206Pb/207Pb ratio is higher (approx. 1.34). Concentrates processed in the smelter and dust collected from the inert surfaces in the vicinity of the smelter have a higher 206Pb/207Pb ratio (1.21–1.28). This indicates that the Pb with low isotopic ratio found in the surface layer of soils in the vicinity of the smelter and in the youngest tree rings (206Pb/207Pb = 1.16–1.17) at all the locations is derived from combustion of leaded petrol. The 206Pb/207Pb ratios in the soils in the remote profiles (206Pb/207Pb > 1.32, Fig. 2) indicate very limited impact on the soil by dust from the smelter, concentrates or combustion products of leaded petrol (206Pb/207Pb < 1.1). In contrast, the isotopic composition of the youngest parts of the tree rings (206Pb/207Pb = 1.16–1.17) at the remote site are most probably affected by the leaded gasoline aerosol fingerprint with low 206Pb/207Pb ratio, which is not found in the soils.

Figure 1. Scheme of sampling sites for the tree species and soil samples (smelter samples – I, road samples – II, III and remote samples – IV).

Manganese in the pine tree rings varies in the range 5– 125 mg kg-1. Maxima in the Mn contents in the composition of the tree rings are apparent close to the smelter from the 1970’s to the 1980’s and close to the highway in the second half of the 1980’s. The Mn contents in the tree rings document changes in the soil pH values The Pb content in the tree rings is very low and varies in the range 0.02–0.7 mg kg-1. Lead has random peaks in the 1970’s, at the end of the 1980’s, 1990´s and in the youngest tree rings, formed after 2000. The isotopic composition in the tree rings varies in the range 206Pb/207Pb = 1.16 – 1.34 (average 206Pb/207Pb = 1.23, n = 90) in the vicinity of the metallurgy plant (samples I), 206Pb/207Pb = 1.16–1.29 (average 206Pb/207Pb = 1.20, n = 38) close to the roadway (samples II and III) and 206Pb/207Pb = 1.16–1.33 in the remote area (samples IV). The variation in the Pb isotopic composition in the studied tree rings is depicted in Figure 2. The average values of the 206Pb/207Pb ratio at the site in the vicinity of the smelter (I) and close to the highway (II and III) have a similar course. Up to the mid-1980’s, the 206Pb/207Pb ratio varied in the range 1.23–1.26. In 1984, the 206 Pb/207Pb ratio decreased rapidly to a value of 1.21, after which it decreased slowly to 1.17. The average isotope composition of the tree rings in the remote area is higher (206Pb/207Pb equal to 1.17–1.29); this ratio
36

Figure 2. 206Pb/207Pb ratio in the tree rings of the studied trees, soils, concentrates and dust.

Acknowledgements
This work was performed with financial support from the project of the Ministry of Education, Youth and Sports (MSM 0021620855), IGCP 594 and the Czech Science Foundation (GA ČR 205/08/0321/1).

References
Kříbek B, Majer V, Veselovský F, Nyambe I (2010) Discrimination of lithogenic and anthropogenic sources of metals and sulphur in soils of the Zambian Copperbelt Mining District: A topsoil vs. subsurface soil. Journal of Geochemical Exploration 104: 69–86 Lageard JGA, Howell JA, Rothwell JJ, Drew IB (2008) The utility of Pinus sylvestris L. in dendrochemical investigations: Pollution impact of lead mining and smelting in Darley Dale, Derbyshire, UK. Environmental Pollution 153:284–294 Mihaljevič M, Ettler V, Šebek O, Sracek O, Kříbek B, Kyncl T, Majer V, Veselovský F (2011) Lead isotopic and metallic pollution record in tree rings from the Copperbelt mining-smelting area, Zambia. Water Air and Soil Pollution 216: 657–668 Savard MM, Bégin C, Parent M, Marion J, Smirnoff A (2006) Dendrogeochemical distinction between geogenic and anthropogenic emissions of metals and gases near a copper smelter. Geochemistry-Exploration Environment Analysis 6: 237– 247 Watmough SA, Hutchinson TC (2003) A comparison of temporal patterns in trace metal concentration in tree rings of four common European tree species adjacent to Cu-Cd refinery. Water Air and Soil Pollution 146: 225–241

IGCP/SIDA Project 594, Annual Workshop, Windhoek, Namibia, 2012, © Czech Geological Survey, ISBN 978-80-7075-781-9

Trace elements dispersion from a tailings dam and speciation study in surrounding agricultural soils: A Case study from Kombat Mine area, Otavi Mountainland, Namibia
Marta Mileusnić and Stanko Ružičić University of Zagreb, Faculty of Mining, Geology and Petroleum Engineering, Department of Mineralogy, Petrology and Mineral Resources, Pierottijeva 6, HR-10000 Zagreb, Croatia, e-mail marta.mileusnic@rgn.hr Benjamin Siyowi Mapani and Akalemwa Fred Kamona University of Namibia, Faculty of Earth Science, Department of Geology, Private Bag 13301, Windhoek, Namibia Isaac Mapaure and Percy Maruwa Chimwamurombe Department of Biological Sciences, Faculty of Science

Abstract. Kombat tailings dam (impoundment) has been exposed to water and wind erosion over a long period of time. In this study, the tailings, as well as surrounding arable soils, were characterised with respect to mineral and trace element composition. Sequential leaching procedure was used to determine binding mechanisms involved in the retention of metals in soils, which indicate trace metals bioavailability, threat to groundwater pollution, as well as dominant type of dispersion (hydromorphic or mechanical). Among seven analysed elements, copper and lead showed significantly high concentration in tailings and exceed maximal allowed values in farmland soils. Seasonal variations in metal concentrations are not observed. The main binding phase for Cu and Pb is the oxide fraction. Similar metal distribution in sequential leaching fractions of tailings and soils are in agreement with the assumption that wind and water are the main mechanical dispersal agents of the tailings to the surrounding farmlands. Although farmland soils are contaminated with Pb and Cu, these metals are relatively strongly bound to the soils and there is probably a small risk for their release in soil, water and later to the groundwater, although lead possesses a risk of intermediate bioavailability to plants and humans if it is ingested via dust. Keywords. Soil pollution, potentially toxic metals, tailings, mining, sequential leaching (extraction), bioavailability, environment, Kombat, Namibia

identify dominant type of metal dispersion from the tailings impoundment (water and/or wind); (3) to carry out preliminary assessment of environmental risk associated with tailings impoundment. The results are to be used for decisions about soil remediation and tailings impoundment reclamation methods.

2 Materials and methods
2.1 Site characterization The mining town of Kombat is located in Grootfontein district. The tailings impoundment is situated 1 km to the south of the town of Kombat, close to the B8 road (19o43’S; 17o42’E) and it is surrounded by the farming lands (Fig. 1). The tailings impoundment spreads over circa. 10 ha and has a height of 3–4 m. The total population of Kombat is estimated at 2,000 inhabitants. The district’s agricultural activities are dominated by livestock production, crop farming and accounts for a major source of local farmers’ income. Phreatic water sources accessible through boreholes as well as mine water are used as drinking water. Carbonates (with karst phenomena) and phyllites are the dominant bedrock in the area. Ore minerals associated with the tailings are chalcopyrite, galena, sphalerite, chalcocite and bornite, with minor tennantite as primary phases, and malachite, azurite, arsenates, cerussite, chrysocola, cuprite and native copper as secondary minerals (Innes and Chaplin 1986, Changara 2009). Soils can be classified as calcic regosols, calcic cambisols and pelitic vertisols according to the FAOUnesco (1997) classification. Kombat town has a sub tropical climate, with very hot summers and mild winters. Mean monthly temperatures vary from 16oC to 35oC (Changara 2009; MET DEPT 2004). The annual average rainfall is 470 mm. Most of the rainfall occurs between December and February (summer). The period between May and June is characteristic of the dry winter months with little or no rain (MET DEPT 2004). All watercourses are dry for the most part of the year.

1 Introduction
Extensive mining and ore processing activities in the Kombat district left significant amounts of mining waste materials that can be considered as a serious problem in relation to environmental contamination. Approximately 24,550,280 t of copper ore were mined out during 46 years and it has been estimated that 300 million of tons of waste are stored in the tailings impoundment (Kříbek and Kamona 2005), which is located within the farming area (Fig. 1). The subject of investigation is agricultural soil around Kombat tailings impoundment (Fig. 1). The objectives of this research are: (1) to determine lateral distribution and seasonal variability of trace metals, as well as dominant metal binding mechanisms in the agricultural soil polluted by mining activity; (2) to
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IGCP/SIDA Project 594, Annual Workshop, Windhoek, Namibia, 2012, © Czech Geological Survey, ISBN 978-80-7075-781-9

Figure 2. Wind erosion of the tailings impoundment during winter.

.
Figure 1. Topographic map of the Kombat area showing the location of town and tailings impoundment as well as sampling location.

Winds have an average wind speed between 3 and 5 m/s and they occur 40 % of the time. During summer and autumn, north-easterly winds are more frequent, while winter months are characterized by the highest frequency of easterly winds (MET DEPT 2004). Comprehensive assessment of the pollution from the tailings impoundment into the surrounding area was done after the assumption that the main agents of material transfer from tailings impoundment into surrounding areas are wind (Fig. 2) and rain water which comes as run-off in episodes of heavy downpours (Fig. 3). 2.2 Sampling Sampling procedure was created after preliminary investigation in which sampling was done at 500 m intervals to gauge the potential for presence of toxic elements, mainly on the tailings impoundment following up an earlier campaign where samples were taken at 1 km intervals (Kribek et al. 2006). Three types of samples were collected: (1) tailings samples; (2) soil samples from areas in the windward direction from the tailings impoundment assumed as polluted; and (3) soil control samples, obtained several kilometres to the south from the tailings impoundment and assumed to have background concentration of analysed elements. The sampling (uppermost 4 cm of the profile) was done at intervals of 250 m between soil sampling locations in the rangeland and farm lands, and 100 m intervals within the tailings impoundment (Fig. 1). All sample locations were sampled twice, once in the wet season and secondly in the dry season. Apart from the usual
38

Figure 3. Water erosion of the tailings impoundment during summer.

tailings samples, salt crust was sampled on some locations in dry season. 2.3 Analytical methods Mineral composition of all samples was determined by means of powder material with X-ray diffraction (XRD) using a Philips diffractometer PW1710 (CuKα radiation). The pH values (in KCl) were determined on a few soil and tailings samples selected on the basis of their spatial distribution using the PHM 201 pH-meter. Pseudo total concentrations of trace element (Cu, Pb, Zn, Cr, Ni, Co, Cd) were obtained in all samples from both seasons, after aqua regia digestion, by flame atomic absorption spectrometry (AAnalyst 700, Perkin Elmer). Different forms of metals in selected soil and tailings samples were analysed using sequential extraction, whereby a series of single reagents is used to extract operationally defined phases in a defined sequence. As Kombat soils and tailings have a high content of carbonates and are highly contaminated with copper and lead, to avoid possible problems with the selectivity and re-adsorption, a combination of the Tessier extraction scheme (Tessier et al. 1979) and procedure optimised for

IGCP/SIDA Project 594, Annual Workshop, Windhoek, Namibia, 2012, © Czech Geological Survey, ISBN 978-80-7075-781-9

pp mg/kg

carbonate-rich sediments (Sulkovski and Hirner 2006) was used to give following four fractions: adsorbed (ADS/EXC), bound to carbonate (CARB), bound to iron and manganese oxides (FEMN) and bound to organic matter and sulphides (OR/SUL).

150 130 110 90 70
MAC Cu

3 Results
Mineral content of the tailings is dominated by carbonates (calcite and dolomite). Quartz and micaceous material are present in all analysed samples. In some samples gypsum is detected as well. There are indications of some primary and secondary Cu and Pb minerals. The mineral content of soil samples is dominated by quartz and different amounts of carbonate minerals (calcite and dolomite). Other minerals present are: K-feldspar, plagioclase and clay minerals. The pH of analysed tailings samples are circumneutral (7.0–7.7), while soil samples are alkaline (8.1– 8.6). Near total (aqua regia digested) metal concentrations in soils do not differ significantly considering different seasons. Metal concentrations in tailings samples for Cu and Pb are very variable (range: Cu 429–9086 mg/kg and Pb 388–5589 mg/kg) even between samples taken at the same time. Therefore, median values of metal concentrations presented in Table 1 refer to the values obtained for both seasons. Comparing median values of control soils and affected agricultural soils, while Cr, Ni, Co and Cd do not show any enrichment, zinc concentration are 2 times higher, lead concentrations 8 times higher and, copper concentrations 12 times higher. Fig. 4 and 5 represent concentrations of copper and lead in agricultural soil in vicinity of tailings impoundment, respectively. Concentrations of lead and copper in all analysed samples exceed maximal permissible values for agricultural soils compared with Canadian soil quality guidelines (CECME 1999). Zinc concentrations, although elevated, do not pose a threat. A relation between concentrations of these three elements is in agreement with abundance of their minerals. Cu and Pb ore minerals far outweigh sphalerite (Innes and Chaplin 1986).
Table 1. Median values of metal concentrations (in mg/kg) in tailings and soils of Kombat area (BDL – below detection limit). Element Tailings Polluted farmland soil 112 117 49 20 9 5 BDL Unpolluted (control) soils 18 17 27 27 12 5 BDL

50 1 2 3 4 5 6 7

Figure 4. Aqua regia extractable copper concentrations (near total concentrations) in agricultural soil in vicinity of tailings impoundment (red – wet season; blue – dry season). Horizontal line indicates maximal permissible copper concentration (MAC Cu = 63 mg/kg) in agricultural soils (CECME 1999).
170 150 130 110 90 70 50 1 2 3 4 5 6
mg/kg

MAC Pb

7

Figure 5. Aqua regia extractable lead concentrations (near total concentrations) in agricultural soil in vicinity of tailings impoundment (red – wet season; blue – dry season). Horizontal line indicates maximal permissible lead concentration (MAC Pb = 70 mg/kg) in agricultural soils (CECME 1999).

The importance of the soil fractions as binding sites for trace metals, determined by sequential extraction analysis of polluted soil samples, follows this sequence: COPPER: CRFE >> RES> OR> ADS-EXC> CARB (Fig. 6) and LEAD: CRFE >> CARB> OR> RES> ADS-EXC (Fig. 7).
500 450 400 350 mg/kg 300 250 200 150 100 50 0 ADS-EXC CARB FEMN soil fraction OR/SUL RES

Cu Pb Zn Cr Ni Co Cd

1328 946 107 16 3 6 3

Figure 6. Copper in sequential extraction fractions of polluted soil samples.

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IGCP/SIDA Project 594, Annual Workshop, Windhoek, Namibia, 2012, © Czech Geological Survey, ISBN 978-80-7075-781-9

600 500 400 mg/kg 300 200 100 0 ADS-EXC CARB FEMN soil fraction OR/SULF RES

study by Casteel et al. (2006), which documented significant mineralogical controls on the relative bioavailability of ingested lead, showed that lead associated with iron oxide shows intermediate bioavailability. Rehabilitation of tailings impoundment, i.e. its return to a state allowing future land use of surrounding soils, is necessary. An effective strategy for isolating tailings is covering of impoundment with a thick layer of solid, inert material and planting vegetation which would protect it against erosion and transpire infiltrated water.

Acknowledgements
This study was carried out within the framework of the IGCP/SIDA Project No. 594, Assessment of the impact of mining and mineral processing on the environment and human health in Africa.

Figure 7. Lead in sequential extraction fractions of polluted soil samples.

4 Conclusions
Among seven analysed elements, copper and lead showed significantly high concentration in tailings and they are of environmental concern in Kombat area. Concentrations of these elements in all analysed samples of farmland soils west of the tailings impoundment exceed maximal allowed values for agricultural soils. Seasonal variations in metal concentrations are not observed. The main binding site for Cu and Pb is the oxide fraction. Due to long periods of drought during winter months and short heavy downpours during summer, mechanical weathering of Kombat tailings impoundment prevails over chemical weathering. Similar metal distribution in sequential leaching fractions of tailings and soils are in agreement with the assumption that wind and short term but strong torrents are dispersing tailings to the surroundings farmland. Given the fact that carbonate minerals dominate in tailings, the drainage is neutralized and lead and copper immobile. But, some potentially toxic elements, such as arsenic, which is associated with lead and copper in sulphide ore minerals of Kombat, may still be present in relatively high concentrations in these waters. Hence, there is a need for speciation study of arsenic in Kombat soil. Although farmland soils are contaminated with Pb and Cu, these metals are relatively strongly bound to the soils and there is probably small risk for their release in soil water and later to groundwater. In the case of mobilisation, relatively high pH of soil would cause reprecipitation. However, it should be emphasised that a

References
CECME (1999) Soil Quality Guidelines for the Protection of Environmental and Human Health. Canadian Environmental Council of Ministers of the Environment, 2006. Casteel SW, Weis CP, Henningsen GM, Brattin WJ (2006) Estimation of relative bioavailability of lead in sol and soillike materials using young swine. Environmental Health Perspectives 114:1162–1171 FAO – Unesco (1997) Soil map of the world 1:500 000. Volume VI. Africa. – Unesco, Paris Innes J, Chaplin RC (1986) Ore bodies of the Kombat mine, South West Africa/Namibia. In: Mineral Deposits of Southern Africa (C.R. Anhaeusser and S. Maske, editors). Geological Society of South Africa, Johannesburg, Republic of South Africa, 1789–1805 Kříbek B, Kamona F (2005) Assessment of the mining and processing of ores on the environment in mining districts of Namibia. Final report of the project of the development assistance programme of the Czech Republic to the Republic of Namibia for the year 2004 – Tsumeb area. MS Czech Geol. Surv., Record Office – File Report No. 2/2005, Prague, Czech Republic. Metereology department, Windhoek. (2004) Climate Bulletins for 2004. Republic of Namibia Sulkowski M, Hirner AV (2006) Element fractionatin by sequential extraction in a soil with hight carbonate content: Applied Geochemistry 21:16–28 Tessier A, Campbell PGC, Bisson, M (1979) Sequential extraction procedure for the speciation of particulate trace metals. Analytical Chemistry 51:844–851

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IGCP/SIDA Project 594, Annual Workshop, Windhoek, Namibia, 2012, © Czech Geological Survey, ISBN 978-80-7075-781-9

Discrimination of three geologies on the Witwatersrand Basin gold fields, South Africa, using remote-sensing of tree canopy spectral reflectance
Miranda H. Muller School of Geography, Archaeology and Environmental Sciences School of Animal, Plant & Environmental Sciences University of the Witwatersrand, Johannesburg, South Africa Isabel M. Weiersbye School of Animal, Plant & Environmental Sciences Author for correspondence: iweiersbye@gmail.com David J. Tongway Australian National University, Canberra, Australia Devlyn Hardwick School of Geography, Archaeology and Environmental Sciences

Abstract. Conventional grid soil-sampling approaches to explore for shallow ore-bodies are time-consuming and costly, and can result in surface disturbance and negative socio-ecological impacts. The mapping of groundwater pollution using geophysical methods and monitoring boreholes suffers from similar constraints, and is spatially imprecise. Remote-sensing of indicator minerals and vegetation pattern is a non-invasive approach to identifying anomalies on which to focus subsequent sampling, but is constrained both when the substrate is completely concealed by vegetation, and when vegetation pattern has been highly disturbed. However, remote-sensing of the vegetation itself can be used as a surrogate through identifying soil toxicities and nutrient availability to plants, as well as changes in the depth and salinity of water. To use vegetation response as a reliable geological or pollution mapping tool, it is however necessary to consider plant functional groups, taxa, phenology, seasonality and landscape. In this report, we show that the canopy reflectance signatures of two evergreen phreatophyte tree species (Searsia lancea and Euclea crispa), with a continuous distribution across three contrasting geologies at the same location on the Witwatersrand Basin gold fields, can be used to distinguish Black Reef quartzite and sulphide ore-body, from Malmani Dolomite and Ventersdorp Lava. Tree canopy spectral reflectance indices (NDVI, PSRI, NDWI & Red-Edge NDVI), the red edge wavelength and inflection point, and the 725/702 ratios of the first and second derivatives of the reflectance spectra were evaluated for disjunct patterns. Differences (p < 0.001) between the geologies were found for the NDVI, PSRI and Red-Edge NDVI, as well as for the Red edge wavelength and inflection point, and the 725/702 ratio of the 1st derivative. Paired groupings between Landscape Functional Types within these geologies indicate that topography and landscape factors played a lesser role in determining tree signatures than substrate parent geology. The approach therefore holds potential for the spatial mapping of substrata polluted by natural ore bodies or anthropogenic activities. Current research involves assessing variation in the spectral response of different trees to anomalies in semi-arid as opposed to humid tropical locations, and understanding the relationship between growing conditions and physiological response.
41

Keywords. Hyperspectral remote-sensing, geobotany, vegetation indices, gold, pyrite, acid rock drainage (ARD)

1 Introduction
Globally, there is pressure on mining companies to conduct environmentally acceptable operations. In an increasing number of countries, including South Africa, companies are liable for any environmental and social damage that may be caused by their operations and must provision accordingly (DME 2002, Sutton and Weiersbye 2007). Traditional methods of resource exploration prior to mining, as well as delineation of subsequent polluted land or groundwater, are labour and energy-intensive, and intrusive (Reid 2008). Intrusive exploration can also expose environments to the increased exploitation and exportation of all natural resources, with negative impacts on the livelihoods of local people (Garrett et al. 2010). The development of rapid, low-cost remote-sensing methods for preliminary mapping of resources or pollutants can therefore facilitate a more strategic approach to sampling. Hyperspectral remote sensing of surface minerals is a widely used exploration technique, but its utility is limited where cloud, mist or vegetation masks the earth’s surface (King et al. 2010). In such cases groundbased surveys are undertaken, with sampling of rocks and soils at intervals to identify sites suitable for trenching or drilling. However, one less invasive approach is phytogeochemical exploration. This involves statistical interpretation of disjunct vegetation patterns, presence of diagnostic vegetation forms or indicator species, and the actual elemental composition of plant matter – especially leaves, to determine information about the underlying substrata (Brooks et al. 1995, Dunn 2007). Although relatively non-invasive, this approach requires extensive foliar sampling, and so could be improved and rendered more generic through the use of remote-sensing associated with representative `ground-truth’ validation (Reid et al. 2005, Reid et al. 2009, Reid and Hill 2010). Leaves contain light-

IGCP/SIDA Project 594, Annual Workshop, Windhoek, Namibia, 2012, © Czech Geological Survey, ISBN 978-80-7075-781-9

harvesting and photoprotective pigments that are sensitive indicators of growing conditions. Anomalous plant water content is also detectable from the reflectance characteristics of foliage (Govender et al. 2009). Remotely-sensed decreases in leaf water content and stress indices were used to determine where trees lacked access to groundwater, and where groundwater was contaminated by AMD (Govender 2011). In contrast, tree clusters and elevated leaf water indices in a dolomitic grassland during the dry season were used to identify probable dolines where roots access groundwater (Muller et al. 2012). It is established that growth in elevated concentrations of metals or metalloids, as well as osmotic stressors, results in biochemical and structural changes to leaves (Marschner 1995). Hyperspectral remote-sensing of phreatophyte tree leaves was found to be a quick method for determining plant physiological status and the nature of the substrate. Changes in canopy spectral signatures occurred in response to seasonal drought, acid mine drainage (AMD), and high osmolality of groundwater (Weiersbye et al. 2006, Govender 2011). That these spectral responses were a consequence of stressful substrate conditions was supported by the findings that AMD-contaminated groundwater directly impaired viable seed production – a measure of fitness, in a range of phreatophyte species in a dose-dependent fashion (Weiersbye and Witkowski, 2003, 2007). Furthermore, derived VIs can be useful in indicating substrate mineralisation and metal contamination by causing a shift in the typical leaf pigment signature towards the ultraviolet portion of the electromagnetic spectrum, known as a blue shift (Sims and Gamon 2002). Detection of this shift has potential use in geobotanical exploration and pollution mapping. For example, of a metal-polluted grassland (Kooistra et al. 2004), and, used in combination with the Red Edge stress signature to discriminate between plants grown in differing concentrations of CuSO4 (Schellekens et al. 2005). The aim of this study was to determine whether tree canopy spectral reflectance can be used to discriminate between Ventersdorp Lava, Black Reef quartzite with pyrite, and Malmani Dolomite.

2.1 Study site and delineation of LFTs The site is situated at AngloGold Ashanti Ltd's Vaal River Mining Operations in the North West Province of South Africa. The region is semi-arid with seasonal rainfall (Mean Annual Precipitation (MAP) of < 600 mm, and Mean Annual Potential Evapotranspiration of more than twice MAP). A shallow ore body (`Black Reef’) is situated in between soils derived from Ventersdorp Lavas on the one side, and Malmani Dolomites on the other (Figure 1). The reef is a narrow outcrop at surface, but is estimated to be 200-300m in width below the surface. The reef is enriched in S, Fe, Au, Co, Mn and U, whereas the adjacent Malmani dolomites contain more Ca and Mg (AGA, 2009). The study site was intentionally situated up-gradient (i.e. beyond the influence) of groundwater pollution plumes.Use an empty line to separate headings from the text. The whole abstract must be no more than three pages long. The main vegetation unit is Vaal Reefs Dolomite Sinkhole Woodlands (Gh12) with a small area of Klerksdorp Thornveld (Gh13), rocky outcrops supporting trees and shrubs along the Black Reef (Mucina and Rutherford, 2006). The Vaal Reef Dolomite Sinkhole Woodlands are characterised by clumps of phreatophyte trees which may indicate dolines or sinkholes (Muller et al. 2012). The site was characterised in terms of geological maps and soils, surface run-off pathways, vegetation structure, location within the catena, slope and soil characteristics, into the six LFTs (Figure 1). Subsequent soil mapping verified the distinction between LFTs (McLeroth 2012 unpublished).

3 Spectral data acquisition and sampling
By defining LFTs, it is possible to account for some of the landscape variables which could influence the spectral findings. For each LFT (2 per geology), four sampling blocks of approximately 50m x 50m were selected. At each sampling point (i.e. individual tree) spectral reflectance of leaves was acquired using a handheld spectroradiometer (Field Spec-Pro Analytical Spectral Devices, ASD Inc., Boulder Colorado, U.S.A. with a spectral range of 350 nm to 2500 nm at 1 nm intervals). Leafy branches were cut from each tree and measured immediately using the Fieldspec internal light source. For each tree (N=8 per species per geology) 10 spectral readings were taken from the abaxial surface of approximately 20 leaves per reading. After measurement the sampled leaves were washed in distilled water, then frozen and lyophilised in preparation for elemental analysis together with composite site soil samples from the tree fine-root zone (0–50 cm) (data not shown). Vegetation indices derived from the reflectance data were used to determine the Red Edge stress signature and to measure the blue shift of the plant spectrum.

2 Methodology
Whether there is a difference in canopy spectral signatures was assessed for two phreatophyte species (Searsia lancea (L.f.) Moffet (Anacardiaceae) and Euclea sp. (E. crispa (Thunb.) Gürke and/or E. undulata Thunb, Ebenaceae) growing at the same locality. Two fundamental questions, vis whether there is a difference in spectral response between trees growing on different soils, and whether the red edge and blue shift are reliable indicators for growth on contrasting geologies, cannot not be answered without ascertaining the effects of topography. To account for variation in foliar spectral signatures due to localized topography and associated effects, trees were sampled from six Landscape Functional Types (LFTs, sensu D.J. Tongway 2011) on the three substrate geologies.
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IGCP/SIDA Project 594, Annual Workshop, Windhoek, Namibia, 2012, © Czech Geological Survey, ISBN 978-80-7075-781-9

Figure 1. Sampling points shown by six landscape function types (LFT) in relation to surface geology at the study site in the Vaal River Mining Operations (geology after AngloGold Ashanti Ltd, 2011). The inset maps show (top) the location of the study site in South Africa (Google maps), and (bottom) the distribution of jarosite, an indication of ARD, along the Black Reef (after Weiersbye et al. 2006).

The 725/702 ratio of the 1st and 2nd order derivatives of the reflectance data were used to detect a blue shift that has been found to be associated with metal-related plant stress (Smith et al., 2004). In addition, the Normalised Difference Vegetation Index (Tucker, 1979): (NDVI =
),

types (Bonferroni 1936, Kruskal and Wallis 1952, Dunn 1964).

4 Results and Discussion
Significant differences between the geologies were found for the three vegetation stress indices (Table 1, p<0.001). The NDWI did not differ across LFTs, which suggests that the observed stress spectral signature is not related to low water availability or physiological (osmotic) drought. There was significant variation in red-edge inflection point and red-edge wavelength between the geologies (Table 1, p < 0.0001). Determining the red-edge wavelength and inflection point is one method of measuring the blue shift, and these features may be used as indicators of plant stress. The Red-Edge wavelength range for S. lancea growing on the Black Reef indicated a strong blue shift when compared to the Dolomite and Ventersdorp Lava (p < 0.0001). Similar differences have been found for S. lancea growing on AMD-polluted versus unpolluted groundwater on the same geology (dolomites) (Govender 2011), and between ARD-tolerant versus sensitive ecotypes of S. lancea grown together in plots on polluted groundwater underlying doleritic soils (Weiersbye et al. 2006). In contrast there were no differences for Euclea sp. between the Black Reef and the Dolomite for the Red-

the Plant Senescence Reflectance Index (Merzylak et al. 1999): (PSRI = ),

the Normalised Difference Water Index (Gao 1996): (NDWI = )

and the Red Edge NDVI (Gitelson and Mezylak 1994): (Red Edge = were derived. A Kruskal-Wallis non-parametric test with a Dunn’s Post Test with a Bonferroni correction was used to detect significant differences between species, initially across the three geologies, and then across landscape functional
)

43

IGCP/SIDA Project 594, Annual Workshop, Windhoek, Namibia, 2012, © Czech Geological Survey, ISBN 978-80-7075-781-9 Table 1. Vegetation Indices (VI) for leaves of the two tree species. Data are ranges and mean of ranks and groups from the Dunn’s procedure based on the mean of ranks. Significant differences between the three geologies (VL – Ventersdorp Lavas, BR – Black Reef, D – Dolomite) combined are indicated in bold. P-values and the observed Kvalue are given. The critical K-value is 5.991. (Kruskal-Wallis non-parametric test)
Euclea sp (n=209 D.f. = 2) Range VL NDVI K (observed) VL Red Edge NDVI Vegetation Indices Red Edge inflection point and wavelength 702/725 ratios of the 1st and 2nd derivatives K (observed) VL NDWI K (observed) VL PSRI K (observed) VL Red-edge inflection point K (observed) VL BR D p-value K (observed) VL 1st Derivative ratio K (observed) VL 2 derivative ratio K (observed)
nd

S. lancea (n=250, D.f. =2 ) Range 0.666 - 0.908 0.752 – 0.908 0.660 – 0.896 0.0003 0.383 – 0.635 0.342 – 0.637 0.430 – 0.654 < 0.0001 -0.003 – 0.154 0.020 – 0.080 0.026 – 0.073 0.015 -0.019 – 0.014 -0.009 – 0.032 -0.022 – 0.017 < 0.0001 0.106 – 0.416 0.272 – 0.364 0.298 – 0.416 <0.0001 718.283-723.467 715.324-724.498 719.954-724.754 <0.0001 0.626 - 1.558 0.557 – 1.723 0.879 – 1.758 <0.0001 -9.335 – -0.495 -4.297 – 1.201 -2.168 - -0.352 <0.0001 Mean of ranks (Group) 108.602 (a) 118.159 (a) 151.613 (b) 16.082 99.784 (a) 117.524 (a) 161.963 (b) 32.466 125.75 (ab) 109.146 (a) 141.988 (b) 8.354 101.330 (a) 157.854 (b) 118.925 (a) 26.907 132.682 (b) 80.537 (a) 163.688 (b) 54.881 97.705 (a) 114.707 (a) 167.138 (b) 41.351 99.205 (a) 116.707 (a) 163.438 (b) 34.867 97.943(a) 125.049 (b) 156.275(c) 27.272

Combined (n=459, D.f. = 2) Range 0.666 – 0.908 0.708 – 0.908 0.660 – 0.896 <0.0001 0.353 – 0.635 0.335 – 0.637 0.407 – 0.654 <0.0001 -0.003 – 0.154 0.020 – 0.098 0.026 – 0.094 0.881 -0.036 – 0.026 -0.011 – 0.032 Mean of ranks (Group) 205.839 (a) 199.429 (a) 305.303 (b) 53.749 182.414 (a) 220.577 (b) 310.459 (c) 68.103 230.310 (a) 226.405 (a) 234.361 (a) 0.253 201.282(a) 228.197 (b)

Mean of ranks (Group) 106.942 (a) 75.160 (b) 158.571 (c) 52.763 80.616(a) 108.901 (b) 147.405 (c) 34.966 101.012 (a) 113.210 (a) 97.333 (a) 2.542 98.651 (a) 107.765 (a) 112.667 (a) 1.792 98.698 (a) 105.210 (a) 117.500(a) 2.729 78.186 (a) 119.321(b) 132.286(b) 29.997 78.279 (a) 118.160 (b) 134.333 (b) 30.505 85.118 (a) 114.728 (b) 124.000(b) 15.562

0.668- 0.839 0.708- 0.843 0.752 – 0.860 <0.0001 0.353 – 0.540 0.335 – 0.574 0.407 – 0.583 <0.0001 0.033 – 0.122 0.036 – 0.098 0.026 – 0.094 0.281 -0.036 – 0.026 -0.011 – 0.021 -0.005 – 0.014 0.408 0.241 – 0.446 0.292 – 0.441 0.304 – 0.430 0.255 715.834-722.767 716.270-723.903 717.227-724.244 <0.0001 0.351 – 1.388 0.591 – 1.524 0.643 – 1.586 <0.0001 -20.513 – 17.145 -21.165 – 6.386 -19.213 - -0.432 0.0004

BR D

p-value

BR D

p-value

BR D

p-value

BR D

-0.022 – 0.017 261.423 (ab) 0.0002 17.019

p-value

BR D

0.106 – 0.446 234.552 (ab) 0.272 – 430 199.945 (a) 0.298 - 0.430 0.0002 715.834-723.467 715.324-724.498 717.227-724.754 <0.0001 0.351 – 1.558 0.557 – 1.723 0.643 – 1.758 <0.0001 -20.513 – 17.145 -21.165 – 6.386 -19.213 - -0.352 <0.0001 263.664 (b) 16.431 176.126 (a) 230.423 (b) 306.270 (c) 69.039 177.448 (a) 231.374 (b) 303.115 (c) 64.395 186.642(a) 232.471 (b) 286.303 (c) 40.692

p-value

Red-Edge Wavelength

BR D

p-value

BR

D
p-value

-Edge wavelength calculations and the derivative ratios. Euclea sp. on both these geologies were however significantly different to the Ventersdorp Lavas. The features most likely to influence plant growth on soils derived from Dolomites include their higher Ca and Mg status and neutral to slightly basic pH, and on the Black Reef, factors associated with ARD and elevated metal concentrations, including lower pH and fertility, and increased osmolality. However no differences in the NDWI were found to support an osmotic effect.

It is established that saline or acidic conditions associated with ARD in the study region inhibit nutrient cycling, in particular the mineralisation of nitrogen and phosphorus. A linear decline in tree seed production, mass and viability was observed for phreatophyte and riparian tree species (Weiersbye and Wikowski 2007).

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IGCP/SIDA Project 594, Annual Workshop, Windhoek, Namibia, 2012, © Czech Geological Survey, ISBN 978-80-7075-781-9

Table 2. Comparisons between groups obtained using the Dunn’s procedure for the differences between the VIs results across the three geologies (VL – Ventersdorp Lavas, BR – Black Reef, D – Dolomite) and for the six Landscape Functional Types (LFTs) for the two tree species. Significant differences between geologies and between LFTs within geologies are differentially shaded. (Kruskal-Wallis non-parametric test)
NDVI Euclea sp S. lancea (n=209 D.f. (n=250, = 2) D.f. =2) Ventersdorp Lavas VLS VLR Red Edge NDVI Combined Euclea sp S. lancea (n=459, (n=209 (n=250, D.f. = 2) D.f. = 2) D.f. =2) NDWI PS RI Combined Euclea sp S. lancea (n=459, (n=209 (n=250, D.f. = 2) D.f. = 2) D.f. =2) Combined (n=459, D.f. = 2)

Combined Euclea sp S. lancea (n=459, (n=209 D.f. (n=250, D.f. =2) D.f. = 2) = 2)

a b b a c c c b bc b a

a abc a ab b bc b a a

a a a a b b b a a

a a b b c bc ab a

a ab a ab b c cd ab ab

a a ab bc c d a a a

a a a a a st

ab a a a b a a a a a a a

a a a a a a a a a

a a a a a nd

a abc b c a bc ab ab c b a ab

a a b b ab a

Black Reef Quartzite BR1 BR2

Dolomite D1 D2

Red-edge inflection point Red-Edge Wave-length 1 Derivative ratio (702/725) 2 derivative ratio (702/725) Euclea sp S. lancea Combined Euclea sp S. lancea Combined Euclea sp S. lancea Combined Euclea sp S. lancea Combined (n=459, (n=459, (n=209 D.f. (n=250, (n=459, (n=459, (n=209 D.f. (n=250, (n=209 (n=250, (n=209 (n=250, D.f. = 2) D.f. = 2) D.f. = 2) D.f. = 2) = 2) D.f. =2) D.f. = 2) D.f. =2) = 2) D.f. =2) D.f. = 2) D.f. =2) Ventersdorp Lavas VLS VLR

a a a a a a c a ab a bc

b bc a a b c b a ab

ab ab a ab b ab c bc ab

a a b bc b b a a

a a a a b a d bc ab

a a b bc c cd b a a

a a b b b ab a a

a a a a b b b a a

a a b b c b bc ab abc

a a b c b ab b a

a a b a c b c ab a

a ab b bc c c

Black Reef Quartzite BR1 BR2

Dolomite D1 D2

Data to address this question is being acquired from analyses of leaf pigments, oxidative indices, elemental concentrations and nutrient ratios, and fertility of the soils. Smith et al. (2004) found that the use of the 702/725 ratio of the 2nd derivative was successful in detecting where plants were growing in the vicinity of leaks from gas pipelines. However, this study found that the 702/725 ratio of the 1st derivative showed greater variation between the six LFTs, and supports the findings of Mutanga and Skidmore (2007), where the 1st derivative of the red edge was used to identify nitrogen deficiencies in pasture grasses. Table 2 presents the results of the Dunn’s multiple pairwise comparisons between geologies for each test, and between LFTs for each test. By comparing the results between geologies and LFTs one can determine how much of the variation in the dataset is due to topographic and landscape effects on the leaf spectral reflectance compared to effects as a result of parent geology. LFTs are defined on the basis of physical factors such as shape, slope steepness, aspect, surface roughness, landscape heterogeneity and litter flow pathways, whereas the factors associated with parent geology would include salinity and osmotic potential, and metal deficiencies or toxicities. Both LFTs and geology would incorporate the influence of water availability and soil fertility to varying extents. There were very few significant differences between LFTs within geologies, for all the VIs tested, which suggests that the topography (also a product of underlying geology) or physical landscape was playing a lesser role in tree spectral reflectance than the factors related to parent geology.
45

5 Conclusion
Vegetation indices are an established method of detecting changes in plant physiology as a consequence of growing conditions. This study demonstrated significant disjunctions in foliar spectral data for two native phreatophyte tree species, which link to the changes in parent geology across a savannah in a semiarid region. Whether the differences found in this study are directly related to substrate mineralogy and ARD, including changes in nutrient status or toxicities, among other factors, is under investigation.

Acknowledgements
This study is funded by THRIP award for 2011 to 2013 (National Research Foundation and Department of Trade & Industry of South Africa), and AngloGold Ashanti Ltd SA Region Environmental Management and Mine Services Departments. The authors are grateful to B. McLeroth (Red Earth cc, South Africa) for soil mapping and to H. Wilson for field assistance.

References
AngloGold Ashanti Ltd (2011) Chapter 3: Baseline, In, Environmental Management Programme (EMP) for the Vaal River mining operations. Report to the Department of Mineral Resources (DMR) of South Africa, 2011, pp. 1–70 Bonferroni CE (1936) Teoria statistica delle classi e calcolo delle probabilit `a. Pubblicazioni del R Istituto Superiore di Scienze Economiche e Commerciali di Firenze 8: 3–62 Brooks RR, Dunn CE, Hall GEM. (1995) Biological Systems in Mineral Exploration and Processing, Ellis Horwood Limited, Hertfordshire

IGCP/SIDA Project 594, Annual Workshop, Windhoek, Namibia, 2012, © Czech Geological Survey, ISBN 978-80-7075-781-9
DME (2002) The Minerals and Petroleum Resources Development Act (MPRDA) No. 28 of 2002, Department of Minerals and Energy of South Africa, Government printers, Pretoria Dunn OJ (1964) Multiple contrasts using rank sums. Technometrics, 5:241–252 Dunn CE (2007) Biogeochemistry in Mineral Exploration, Handbook of Exploration and Environmental Geochemistry, Vol. 9: Elsevier, Oxford, 462 pages Gao B (1996) NDWI – A normalized difference water index for remote sensing of vegetation liquid water from space. Remote Sensing of Environment 58: 257–266 Garrett N, Mitchell H, Lintzer M (2010) Promoting legal mineral trade in Africa’s Great Lakes region: A policy guide on professionalisation, formalisation and increased transparency, Department for International Development,79 pages Gitelson AA, Merzlyak MN (1994) Spectral reflectance changes associated with autumn senescence of Aesculus hippocastanum L. and Acer platanoides L. leaves. Spectral features and relation to chlorophyll estimation. Journal of Plant Physiology 143: 286 –292 Govender M, Dye PJ, Weiersbye IM, Witkowski EFT, Ahmed F (2009) Review of commonly used remote sensing and groundbased technologies to measure plant water stress, Water SA 35 (5): 741–752 Govender M (2011) Assessing groundwater access by trees growing above contaminated groundwater plumes originating from gold tailings storage facilities, PhD Thesis, University of the Witwatersrand, Johannesburg, 285 pages King TVV, Johnson, MR, Hubbard BE, Drenth BJ (2010) Identification of mineral resources in Afghanistan – Detecting and mapping resource anomalies in prioritized areas using geophysical and remote sensing (ASTER and Hymap) data. USGS Afghanistan Project Product No. 201, Open-File Report 2011–1229 Kooistra L, Salas EAL, Clevers JGPW, Wehrens R, Leuven RSEW, Neinhuis PH, Buydens LMC (2004) Exploring field vegetation reflectance as an indicator of soil contamination in river floodplains, Environmental Pollution 127:281–290 Kruskal and Wallis (1952) Use of ranks in one-criterion variance analysis, Journal of the American Statistical Association 47 (260): 583–621 Marschner H (1995) Mineral nutrition of higher plants (London, Academic Press) Merzlyak MN, Gitelson AA, Chivkunova OB, Rakitin VY (1999) Non-destructive optical detection of pigment changes during leaf senescence and fruit ripening. Physiologia Plantarum 106: 135– 141 Motulsky HJ (1998) InStat guide to choosing and interpreting statistical tests, GraphPad Software, Inc., San Diego California USA, www.graphpad.com Mucina L, Rutherford MC (2006) (Eds), The vegetation of South Africa, Lesotho and Swaziland, Strelitzia Vol. 19, South African National Biodiversity Institute, Pretoria, pp. 349–539 Muller MH, Weiersbye IM, Hardwick D (2012) Pattern and vegetation indices (VIs) of phreatophyte trees as indicators of sinkhole formation in dolomitic grassland. Manuscript based on M. Muller (2010) BSc Honours project, University of the Witwatersand, Johannesburg Mutanga O, Skidmore AK (2007) Red edge shift and biochemical content in grass canopies, ISPRS Journal of Photogrammetry & Remote Sensing 62: 34–42 Reid N, Hill SM, Lewis DM (2005) Tanami geobotany and biogeochemistry: towards its characterisation, role in regolith evolution and implications for mineral exploration, In: I.C. Roach (ed.), Regolith 2005 – Ten Years of CRC LEME. CRC LEME, pp. 256–259 Reid N (2008) Phyto-exploration in arid subtropical, arid Mediterranean and tropical savanna environments: Biogeochemical mechanisms and implications for mineral exploration, PhD thesis, School of Chemical Engineering, School of Earth and Environmental Sciences, University of Adelaide, Australia, 230 pages Reid N, Hill SM, Lewis DM (2009) Biogeochemical expression of buried gold mineralization in semi-arid northern Australia; penetration of transported cover at the Titania gold prospect, Tanami Desert, Australia. Geochemistry - Exploration, Environment, Analysis 9 (3): 267–273 Reid N, Hill SM (2010) Biogeochemical sampling for mineral exploration in arid terrains: Tanami Gold Province, Australia, Journal for Geochemical Exploration104: 105–117 Schellekens JH, Gibles F, Rivera GD, Ysa YC, Chardon S, Fong Y (2005) Reflectance spectra of tropical vegetation as a response to metal enrichment in the substrate of west-central Puerto Rico, Transcriptions of the 16th Caribbean Conference, Barbados, Caribbean Journal of Earth Science, Vol. 39, pp. 9–12 Sims DA, Gamon JA (2002) Relationship between leaf pigment content and spectral reflectance across a wide range of species, leaf structures and developmental stages, Remote Sensing of the Environment, Vol. 81, pp. 337–354 Smith KL, Steven MD, Cols JJ (2004) Use of hyperspectral derivatives ratio in the red-edge region to identify plant stress responses to gas leaks, Remote Sensing of the Environment, Vol. 92 (2): 207 Sutton MW, Weiersbye IM (2007) South African legislation pertinent to gold mine closure and residual risk, In (eds) A.B. Fourie, M. Tibbett and J. Wiertz. Mine Closure 2007, Proceedings of the 2nd International Seminar, Australian Centre for Geomechanics, University of Western Australia, Perth, ISBN 978-0-9804185-0-7, pp 89–102 Tucker CJ (1979) Red and Photographic Infrared Linear Combinations for monitoring Vegetation. Remote Sensing of the Environment 8: 127–150 Weiersbye IM, Witkowski ETF (2003) Acid rock drainage (ARD) from gold tailings dams on the Witwatersrand Basin impacts on tree seed fate, viability, inorganic content and seedling morphology, In: D. Armstrong, A.B. de Villiers, R.L.P. Klein Mann, T.S. McCarthy and P.J. Norton (Eds), Impacts of Acid Mine Drainage on the Environment, Proceedings of the 8th International Mine Water Association (IMWA), Johannesburg, pp. 311–330 Weiersbye IM, Margalit N, Feingersh T, Revivo G, Stark R, Zur Y, Heller D, Braun O, Cukrowska EM (2006) Use of airborne hyper-spectral remote sensing (HSRS) to focus remediation and monitor vegetation processes on gold mining landscapes in South Africa. In: A.B. Fourie and M. Tibbett (Eds), Mine Closure 2006, Proceedings of the 1st International Seminar, Australian Centre for Geomechanics, University of Western Australia, Perth, ISBN 0-9756756, pp. 601–611 Weiersbye IM, Witkowski ETF (2007) Impacts of acid mine drainage on the regeneration potential of Highveld phreatophytes. In JJ Bester, AHW Seydack, T Vorster, I.J Van der Merwe, S. Dzivhani (Eds), Multiple Use Management of Natural Forests and Woodlands: Policy Refinements and Scientific Progress IV. Department of Water Affairs and Forestry of South Africa. www.dwaf.gov.za/forestry, pp. 224– 237

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IGCP/SIDA Project 594, Annual Workshop, Windhoek, Namibia, 2012, © Czech Geological Survey, ISBN 978-80-7075-781-9

Mobilization processes of As, Cd and Pb in soils in the Tsumeb Area, Namibia
Jana Quinger and Helmut Mischo TU Bergakademie Freiberg, Faculty of Geosciences, Geoengineering and Mining, Freiberg, Germany, e-mail: jana_quinger@gmx.de

Abstract. In the frame of a thesis at the University of Freiberg the soils around the Namibia Custom Smelters (NCS) Namibia shall be examined in detail to describe the processes of mobilization and accumulation of arsenic, cadmium and lead. A soil map at a scale of 1:25,000 of the area is under development. The developed soil units and their distribution will support the design of a soil sample grid. The method of sequential extraction is used to determine the mobility of the different metal and metalloids fractions. Vertical transportation processes will be described in a 1D- linear model. It is then attempted to derive risk scenarios by transferring the point data into the spatial distribution of the described soil units in a numerical soil transport model. The results will deliver a clearer picture about the different sources of contamination and will especially indicate the potential role of increased natural background values. Keywords. Mobility of heavy metals, soil pollution, mapping, Tsumeb, Namibia

studies in the future. Samples will be taken from both pits and cores according to the soil horizons. The distribution of the heavy metal mobility fractions combined with geochemical and physical properties of the soils and other available data (geological map, morphology) will be processed in a conceptual soil model which will be used to numerically simulate heavy metal transport within and between the different soil classes under various environmental (changes in pH, T, redox potential, recharge) conditions.

1 Introduction
For more than 100 years a variety of metallic ores were processed in the area of the Tsumeb Custom Smelter. Various negative environmental impacts from different hazardous processes originated from this intensive mining- and processing activities. In numerous investigations within the area around the Smelter, raised concentrations of arsenic or heavy metals in soils, plants and humans were found. Different studies assign different severities to this contamination. However the environmental impact is mostly characterized by the bulk content of the respective heavy metals. This study concentrates only on the metal species which can be mobilized under given environmental conditions and reach the food chain by contaminating the groundwater or by accumulation in the crops.

Figure 1. Map of Namibia showing an area of Investigation in the year 2012.

2.2 Mobility of metals and metalloids: determination through sequential extraction The various degrees of mobility for metals and metalloids and their different appearances can be described through the terms “mobile“, “potentially mobile“ and “immobile“. While the total presence of an element often only provides information about a possible risk to the environment, knowledge of the form of speciation is a prerequisite both for forecasting presence on certain carrying paths and in certain media, and for assessing the actual risk potential. As the sequential extraction procedure a modified procedure proposed by Zeien and Bruemmer for analysing the speciation in soils will be applied to soil samples in respect of the element to be investigated. 1st step: treatment of the residue with NH4 acetate 47

2 Methods
2.1 Mapping The current knowledge concerning the predominant soiltypes of the Tsumeb area and their spatial occurrence to understand mobility pathways and distribution patterns of contaminants is not sufficient. To determine strategic soil sample sites, a soil map at a scale of 1:25,000 of the area will be developed. After the development of a conceptual map through GIS based surface analysis and the interpretation of aerial images, fieldwork consists of visual observations, description of soil profile pits and soil augering. A soil type classification for the region will be created to create a common basis for further

IGCP/SIDA Project 594, Annual Workshop, Windhoek, Namibia, 2012, © Czech Geological Survey, ISBN 978-80-7075-781-9

determination of the portion as exchangeable cations in clay minerals; 2nd step: treatment of the residue with Na acetate determination of the portion in carbonates; 3rd step: treatment of the residue with NH2OH/HCl and HNO3 - determination of the portion in easily reducible fractions; 4th step: treatment of the residue with organic acids determination of the portion in reducible fractions; 5th step: treatment of the residue with diluted NO3/H2O2/NH4-acetate - determination of the portion in organic matter and sulfidic minerals; 6th step: treatment of the residue with aqua regia determination of the strongly bonded portion The total concentrations of Cd, Pb and As and their concentrations in fractions after extraction will be determined by flame or electro thermal atomic absorption spectrometry (FAAS, ETAAS). 2.3 Spatial interpolation The mobility of heavy metals in Soil varies also due to different soil conditions and is influenced by a number of soil parameter, i.e. the chemical forms in which the metal is present in soil, pH value, CEC, content of organic matter and particle size distribution. Further factors are i.e. the aeration, water balance and the soil temperature. These parameters shall be examined in more detail at selected sites within the surroundings of the smelters. Vertical transportation processes will then be simulated in a 1D –linear model based on Hydrus-1D and the results will be interpolated over the whole study area. Hydrus-1D can be used to analyse water and solute movement in unsaturated, partially saturated, or fully saturated non uniform soils. The distribution of the heavy metal mobility fractions combined with other available data (geological map, morphology, geochemical and physical properties of soils) will then be processed in a conceptual and numerical soil – transport model. Risk scenarios for different environmental conditions will be derived and displayed on interactive maps.

3 Natural background vs. anthropogenic emission
A still open question is about the different sources of heavy metal contamination in the soils of Tsumeb. To distinguish between recent and historical emissions from the smelter, the influence from historical mining activities as well as the relevance of increased natural background values from the source rock, numerical modelling of heavy metal transport clears the picture of potential sources. The 1-D forward and backward modelling with Hydrus-1D through the different identified soil strata identifies potential mobilization scenarios under different time- and environmental conditions. A special focus will be put on the potential of elevated concentrations in the lowest soil layers and the related source rocks. The resulting maps will help to trace back the different sources of high heavy metal concentration.

References
Bruemmer GW, Welp G. (2001) Mobile und mobilisierbare Fraktionen anorganischer Schadstoffe in Böden: Konzeptionelle Grundlagen und Analysenbefunde. Mitteilungen Dtsch. Bodenkundl. Gesellsch. 96 (1):163–164 Kamona AF, Günzel A (2007) Stratigraphy and base metal mineralization in the Otavi Mountain Land, Northern Namibia—A review and regional interpretation: Gondwana Research11:396–413 Kribek B, Kamona AF (eds.) (2005) Assessment of the mining and processing of ores on the environment in mining districts of Namibia. Final Report. Czech Geological Survey, Prague. 102 p Pirajno F, Joubert BD (1993) An overview of carbonate-hosted mineral deposits in the Otavi Mountain Land, Namibia— Implications for ore genesis: Journal of African Earth Sciences 16 (3):265–272 Pruess, A. (1992): Vorsorgewerte und Prüwerte für mobile und mobilisierbare, potentiell ökotoxische Spurenelemente in Böden. Verlag Ulrich E. Grauer, Wendlingen, 145 S. Walmsley Environmental Consultants (2001) Environmental remediation of sites belonging to Ongopolo Mining and Processing LTD. MS., Walmsley Environmental Consultants, Rivonia, Rep. South Africa. Zeien H, Bruemmer GW (1989) Chemische Extraktion zur Bestimmung von Schwermetallbindungsformen in Böden. Mitteilungen Dtsch. Bodenkundl. Gesellsch. 59:505–515

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IGCP/SIDA Project 594, Annual Workshop, Windhoek, Namibia, 2012, © Czech Geological Survey, ISBN 978-80-7075-781-9

Mining & Exploration in Protected Areas in Namibia
Gabriele IC Schneider Geological Survey of Namibia, Private Bag 13297, Windhoek, Namibia, gschneider@mme.gov.na Abstract. Mining has been the backbone of the Namibian economy for more than a century, whille the tourism industry, currently Namibia´s fastest growing sector, is built on Namibia´s outstanding nature conservation efforts. The management of the coexistence of both of these important sectors requires sound scientic principles and sustainability issues have first priority. Namibia is currently drafting a policy for exploration and mining in protected areas. Keywords. Archaeology, Benguela Current Large Marine Ecosystem, conservancies, environmental impact assessment, exploration, fossils, geopark, marine protected areas, mining, national parks, protected areas, rock art, strategic environmental assessment

1 Introduction
Mining is the most important sector of the Namibian economy in terms of income generation, and its contribution to GDP, taxes and export earnings are higher than from any other sector. Diamonds and uranium are by far the most important commodities. At the same time, the maintainance of ecosystems and biodiversity is enshrined in the Namibian constitution, and Namibia proudly is the first country in the World to have the protection of the environment written into her supreme law. Consequently, national parks and communal, as well as private conservancies play an important role in Namibia, and at present some 42% of the country enjoy one or the other state of protection and conservation. The co-management of exploration and mining on the one hand side, and conservation and toursim development on the other is a clear challenge for Namibia.

also one of the first countries in the World to proclaim a marine protected area, the Namibian Islands Marine Protected area Fig. 1). From a historical and cultural point of view is is noteworthy that fossils, rock art and archaeological materials are without exception all protected by the Namibian National Heritage Act, and are found in vast areas of the country. All these protected areas and items are potential tourist destinations. Tourism is 3rd largest contributor to GDP, Tourism has a high job potential (18.6%), and Tourism is currently the fastest growing sector in Namibia. While some countries simply ban exploration and mining in protected areas, it is because of the high percentage of protected areas in Namibia, that this is not possible without sterilizing a huge part of Namibia´s mineral endowment. Diamonds are produced in the Skeleton Coast Park, the Sperrgebiet National Park and the Namibian Islands Marine Protected Area; uranium is recovered from the Dorob National Park and the NamibNaukluft Park; zinc is mined in the Sperrgebiet National Park; salt production occurs in the Dorob National Park; dimension stone is quarried in the Dorob National Park and the Namib Naukluft Park; both, gypsum and copper occur in the Namib Naukluft Park; certain phosphate licenses fall within the Namibian Islands Marine Protected Area; and last, not least, small scale mining of semi-precious stones occurs in the Brandberg National Monument Area and the Spitzkuppe Heritage Conservation Area.

2 Methodological approach
This study examines the spatial distribution of exploration licenses and mining areas in relation to Namibia´s protected areas. It also compares the economic benefits derived from these activities. The environmental research and rehabilitation efforts of mining companies operating in Namibia were investigated, and so were the potential negative impacts of exploration and mining, including the small scale mining activities. The various co-management efforts of Government are highlighted and potential synergies listed in an effort to place emphasis on sustainablilty, while at the same time enable the Namibian people to derive benefits from their mineral endowment.

Figure 1. Map of Namibia showing National Parks, other Protected areas and current EPL.

3 Results
Apart from the iconic Etosha National Park, Namibia boosts a Coastal Mega-Park with 10.8 million ha, the 6th largest national park in the World, and the largest in Africa, as well as 3 Transfrontier Parks, the KavangoZambesi, the Iona, and the Ai-Ais Parks. Namibia was
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The spatial distribution of Nambia´s current mining operations is such, that the majority occurs within protected areas. An analysis of only four of them, namely diamonds, uranium, zinc and salt, revealed that 9% out of the total 10% of mining´s contribution to GDP come from protected areas. The contribution to mining

IGCP/SIDA Project 594, Annual Workshop, Windhoek, Namibia, 2012, © Czech Geological Survey, ISBN 978-80-7075-781-9

royalties and taxes from mining operations in these areas amounted to some N$ 1170 million in 2010, and represents 75.19% of minings total contribution to royalties and taxes. Employment figures are of similar significance.
Table 1. Mineral production data, turn-over, tax, royalty and employment figures in mining sector of Namibia.

Production Diamonds Uranium Zinc Salt Total 1 471 000 cts 1 678 t 151 688 t 872 000 t

Turn-over 5 026 m 1 400 m 2524 m 352 m 9302 m

Tax 594 m ---14.8 m 7.7 m 616.5 m

Royalty 503 m 32.2 m 11.6 m 6.6 m 553.5 m

Staff 1651 268 682 131 2732

The majority of mining companies operating in protected areas in Namibia have accepted the challenge and carry out efficient enviornmental programmes to minimize the negative effects. The Namdeb Diamond Mines, including the offshore operations are ISO 14001 certified, and exemplary rehabilitation measures are carried out, even during the life time of the mines. The environmental impacts are carefully studied, documented and mitigation measures are devised and implemented. It must nevertheless be stated that large scale shoreline modification over decades has changed the ecosystem over vast areas, and, although the very dynamic south Atlantic Ocean undertakes a certain amount of natural rehabilitation in the surf zone, in some cases the return to pre-mining conditions is not possible. Likewise, the Langer Heinrich Uranium Mine in the Namib Naukluft Park is ISO 14001 certified, and runs a substantive environmental monitoring and mitigation programme. In addition, and in response to the uranium rush experienced from 2007 onwards, the Namibian Government through its Geological Survey of Namibia and with assistance from the German National Institute for Earth Sciences and Natural Resources and the Southern African Institute for Environmental Assessment, has carried out a Stategic Environmental Assessment of the uranium activities, which led to a Strategic Environmental Management Plan, under which the activities are now monitored. Skorpion Zinc Mine in the Sperrgebiet National Park has a comprehensive integrated risk management system in place, and the saltworks along the Namibian coast have actually enhanced the habitat for bird life in the area. However, there are also activities, which are, or potentially will be, more problematic. Because of the visual impact, dimension stone quarrying has been banned in National Parks for some 10 years now, however, existing rights had to be honoured, so that some activities still occur, and have a negative impact on landscapes and possibly biodiversity. The planned offshore phosphate extraction is currently carefully researched during the ongoing exploration phase, but because such an activity was not carried out before, and
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therefore the inherent lack of long-term data, the process of establishing long-term environmental impacts and mitigate them is rather difficult. The remoteness of a mineral deposit that occurs on the sea floor poses another challenge here. Exploration companies are often less environmentally sensitive, compared to established mining companies. Their business required large sums of money, while no profit through the sale of a mined product has been made yet. This results in many – albeit not all – cases in a reluctance to adhere to environmental standards, as this requires additional funds. In the same line the established small scale mining community often does not have the knowledge nor the funds to operate in an environmentally responsible manner. This has resulted in a situation where no mineral claims are registered in a National Park, but many small scale miners are also operating in communal and private conservancies. While justified for environmental reasons, the fact that no mining claims are registered in National Parks deprives Namibia´s small scale miners from benefiting from the country´s mineral endowment which occurs in the parks.

4 Discussion and conclusions
In order to raise to the challenges described, a good cooperation between the Namibian Ministries of Mines and Energy and of Environment and Tourism is essential. This is partly in place but can be improved. At present, the two Ministries are drafting a policy on exploration and mining in protected areas, which will, once in place, greatly enhance the co-management of explorarion, mining, and conservation. The potential and existing conflicts between the various sectors of industry utilizing the Benguela Current Large Marine Ecosystem (BCLME), which is also the carrier for Namibia´s wealth of fish and marine diamond resources, have been researched by rhe Worldbank-financed BCLME project over the last 14 years. This multi-lateral project includes Angola, Namibia and South Africa, and culminated in the establishment of an Interim Benguela Current Commission, to be replaced by a permanent commission once a treaty will been signed soon. All three countries have vested interest in marine fisheries as well as marine mining and petroleum production, and trans-boundary issues, such as potential oil spills, are receiving due attention. A solution for the negative environmental impacts posed by small scale mining activities lies in training, and the provision of equipment. Assistance with value addition and marketing can further enhance this important sub-sector of the Namibia mining sector, create employment, and make it more economically and socially sustainable. Efforts of mining companies have tremendously contributed to knowledge creation in the fields of zoology, botany, archaeology, history, and general understanding of ecosystems. It is noteworthy that some of the scientific data available in Namibia today would have never been created, had it not been for exploration and mining companies carrying out their environmental impact assessments or simply doing research in order to be good corporate citizens. This is an enormous bonus

IGCP/SIDA Project 594, Annual Workshop, Windhoek, Namibia, 2012, © Czech Geological Survey, ISBN 978-80-7075-781-9

for the Namibian scientific community, and further work should be enccouraged, in particular in protected areas. All aspects of items affected by exploration and mining in protected areas, be it landscapes, flora, fauna, biodiversity, or palaeontological, archaeological and historical materials are a the same time potential tourist attractions. Even disused mines become tourist attractions, if they are old enough and have a story to tell. The old Elizabeth Bay Mine and Kolmanskuppe are a point in case. Some operating mines are at present investing in preserving these tourist attractions in order to give the resident communities sustainable opportunities. While Namdeb is actively involved in

upgrading and maintaining the historic diamond mining structures in the Sperrgebiet National Park, as well as supporting biological studies in this park, the uranium mining companies intend to develop historical sites from World War I in the Namib Naukluft Park into sites which interestes people can visit. In recognition of the potential of geo-tourism, the Geological Survey of Namibia is proposing the establishment of a Geopark in conformity with UNESCO regulations, and this proposed park covers areas of the Dorob and Skeleton Coast National Parks, with past and present mining operations as potential places of interest for local and overseas tourists alike.

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IGCP/SIDA Project 594, Annual Workshop, Windhoek, Namibia, 2012, © Czech Geological Survey, ISBN 978-80-7075-781-9

The impact of mining activities on the environment and surface drainage in the Copperbelt, Zambia
Ondra Sracek Dep. of Geology, Faculty of Science, Palacký University, Olomouc, Czech Republic, e-mail: srondra@yahoo.com Bohdan Kříbek and Vladimír Majer Czech Geological Survey, Praha, Czech Republic Martin Mihaljevič Dep. of Geochemistry, Mineralogy and Mineral Resources, Faculty of Science, Charles University, Praha, Czech Republic

Abstract. The impact of mining in the Copperbelt, Zambia, has been studied using a combination of mineralogical and hydrogeochemical methods. There is formation of hardpan composed of gypsum and hematite in old tailings at Chambishi, but not in recent tailings at Mindolo. Values of pH in tailings remain neutral even after a long period of sulfides oxidation. Ochres composed of amorphous ferric hydroxide enriched in Cu and Co were found at seepage face at Chambishi. Regional Kafue River investigation revealed conservative behavior of sulfate and transport of metals in suspension close to the sources of contamination. The environmental impact of mining is relatively limited due to neutral character of mine drainage, but metals in sediments can be mobilized in the case of acid spills or re-suspended during rainy period. Keywords. Zambia, Copperbelt, neutralization, surface drainage mine tailings,

face and from the Kafue River and tributaries were filtered through 0.45 µm filter and acidified in the field. Fraction retained on filter was also collected and analyzed. Samples of water were analyzed by FAAS (Varian AA 280 FS) for cations and metals and by HPLC (Dionex ICS 2000) for anions.

3 Results
3.1 Mine tailings In both studied mine tailings paste pH values were higher than 6.5, i.e. neutralization capacity of solid phase has not been depleted. At old mine tailings at Chambishi a hard pan at a depth from 0.6 to 1.0 has been formed (Fig. 1). Principal minerals in hardpan were gypsum and secondary hematite (Sracek et al. 2010). At recent mine tailings at Mindolo no such hardpan has been found and there still was a large amount of dolomite in solid phase. At both sites concentrations of Cu and Co in water were low due to adsorption of both metals on ferric oxides and hydroxides.

1 Introduction
The Copperbelt in Zambia is one of the largest metalogenic provinces of the world. There are many tailings and waste rock piles in the catchment of the Kafue River, which is draining the Copperbelt. Exploited Cu and Co minerals such as chalcopyrite (CuFeS2), bornite (Cu5FeS4), linnaeite (Co3S4), and carrolite (Cu(Co,Ni)2S4) are mostly embedded in carbonate-rich shale, limestone and dolomite of Upper Roan, Mwashia, Kakontwe and Kundelungu formations of Neoproterozoic age and mine drainage has a neutral character. The aim of the project was to evaluate the environmental impact of mining wastes including the identification of principal attenuation processes.

2 Material and Methods
Samples of mine tailings material were collected to the depth of about 3.0 m by hand auger. Samples were analyzed by X-ray diffraction, electron microprobe (EMP), and sequential extraction based on the BCR procedure and total extraction in Aqua Regia. Additional samples collected at seepage face of mine tailings were also characterized by Mössbauer spectroscopy. Samples of stream sediments collected in the Kafue River catchment were analyzed by X-ray diffraction and optical microscopy. Water samples at Chambishi seepage
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Figure 1. Total iron in solid phase at old tailings at Chambishi (CT) and at recent tailings at Mindolo (MT, MT2).

3.2 Seepage face Fresh ferric hydroxide precipitates were found at seepage face close to the tailings dam at Chambishi site. These precipitates incorporate large quantities of Cu and Co. Based on sequential extraction results, amorphous ferric hydroxides are transformed into more crystalline

IGCP/SIDA Project 594, Annual Workshop, Windhoek, Namibia, 2012, © Czech Geological Survey, ISBN 978-80-7075-781-9

phase such as hematite deeper in sediments. Remaining dissolved metals are attenuated downstream in local wetland called dambo, probably by adsorption on organic matter (Sracek et al. 2011). 3.3 Regional drainage Samples of stream sediments and water were collected along the Kafue River course and at principal tributaries. River water was neutral everywhere and behavior of

and a Cu-Fe-S intermediate solid solution (ISS) from smelter in Kitwe (downstream from Mindolo tributary, Fig. 3) was confirmed in stream sediments (Sracek et al. 2012).

4 Discussion and Conclusions
Acidity produced by the oxidation of sulfidic minerals is already consumed in mine tailings by dissolution of carbonates and gypsum and secondary ferric minerals precipitate. Precipitated ferric hydroxides are coating sulfide grains and limit their on-going oxidation. There is formation of hardpan composed of gypsum and hematite in old tailings at Chambishi, but not in recent tailings at Mindolo. Ochres composed of amorphous ferric hydroxide enriched in Cu and Co were found at seepage face at Chambishi and remaining metals were removed in downstream wetland (dambo). Regional Kafue River investigation revealed conservative behavior of sulfate and transport of metals in suspension downstream from the sources of contamination. Metals in suspension are incorporated into sediments further downstream. In spite of its large scale, the environmental impact of mining in the Copperbelt is relatively limited due to neutral character of mine drainage, but metals in sediments can be mobilized in the case of acid spills or re-suspended at high flow rate during rainy period.

Figure 2. Concentrations of sulfate in the Kafue River and its tributaries. Empty circles-dry period 2009, black circles-after rainy period 2010.

Acknowledgements
The funding for this study was provided by the Czech Science Foundation (GACR 205/08/0321/1) and Ministry of Education, Youth and Sports (MSM 0021620855). This study was carried out within the framework of the IGCP Project no. 594, Assessment of impact of mining and mineral processing on the environment and human health in Africa.

References
Sracek O, Mihaljevič M, Kříbek B, Majer V, Veselovský F (2010) Geochemistry and mineralogy of Cu and Co in mine tailings at the Copperbelt, Zambia, J. African Earth Sci. 57:14–30 Sracek O, Filip J, Mihaljevič M, Kříbek B, Majer V, Veselovský F (2011) Attenuation of dissolved metals in neutral mine drainage in the Zambian Copperbelt, Environ. Monitor. Assess. 17: 287–299 Sracek O, Kříbek B, Mihaljevič M, Majer V, Veselovský F, Vencelides Z, Nyambe I (2012) Mining-related contamination of surface water and sediments of the Kafue River drainage system in the Copperbelt district, Zambia: An example of a high neutralization capacity system, J. Geochem. Explor. 112: 174–188

Figure 3. Concentrations of copper in the Kafue River and its tributaries, empty circles-dry period 2009, black circles-filtered samples after rainy period 2010, black inverted trianglesunfiltered samples after rainy period 2010.

sulfate was conservative (Fig. 2), i.e. there was no precipitation of sulfate minerals. Concentrations of Cu and Co in suspension was high close to the sources of contamination like Mushishima and Changa (Fig. 3), but decreased downstream as a consequence of suspension sedimentation. A big portion of iron in stream sediments was bound to residual (Aqua Regia) fraction of sequential extraction and came from flushing of tropical lateritic soils during rainy period. Presence of slag glass
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IGCP/SIDA Project 594, Annual Workshop, Windhoek, Namibia, 2012, © Czech Geological Survey, ISBN 978-80-7075-781-9

Acid rock drainage and pyrite oxidation rate in waste rock pile at the Mine Doyon site, Québec, Canada
Ondra Sracek Dep. of Geology, Faculty of Science, Palacký University, Olomouc, Czech Republic,e-mail: srondra@yahoo.com René Lefébvre INRS-Eau, Terre et Environnement, Québec, Canada Abstract. There is acid rock drainage at the Mine Doyon site north of Montreal, Québec, Canada. Waste rock pile about 32 m high is composed of sericite schist with 7 wt.% of pyrite and 2 wt.% of calcite. Calcite has been almost depleted and pH of acid rock drainage is about 2.0. Concentration of sulphate in pore water reaches 270 g/l and concentration of aluminium is about 33 g/l. There is convective oxygen supply close to pile slope and diffusion oxygen supply in the core of pile. Different oxygen transport mechanisms can be determined on the basis of oxygen and temperature profiles. Pyrite oxidation rate values determined on the basis on oxygen and temperature profiles, pyrite mass balance and oxygen consumption method are similar when oxidized material from the pile is used for testing. Keywords. Waste rock, acid rock drainage, oxygen transport, pyrite oxidation rate

3 Results
3.1 Water chemistry Concentrations in pore water reached extreme values close to the slope of pile (Sracek et al. 2004). At the end of dry period (September) they were extremely high at site close to the pile slope. Values of pH were about 2.0, sulphate reached 270 g/l and aluminium 33 g/l. Maximum concentrations were located at a depth about 10 m. Concentrations in the central zone of pile were lower, sulphate reached 150 g/l and aluminium 12 g/l. Maximum was located deeper, at about 22 m. 3.2 Oxygen and temperature profiles Oxygen and temperature profiles are in Fig. 1.
Temperature ( C)
0 0 5 10 20 30 40 50 60 70 0 5 10 0
o

1 Introduction
Acid rock drainage is a serious environmental problem linked to the oxidation of sulphidic minerals like pyrite. The oxidation produces low pH water with high concentrations of sulphate, iron and other metals. Compared to relatively homogeneous mine tailings, size of material in waste rock piles is very variable and unsaturated zone is very thick. In such case, high temperature and, as a consequence, high pyrite oxidation rate zone develops close to the pile slope because oxygen is transported into the pile by convection. Diffusion of oxygen is still a dominant oxygen transport process in the central zone of the pile (Silva et al. 2009). Mine Doyon pile north of Montreal is composed of sericite schist and initial contents of pyrite and calcite were 7.0 wt.% and 2.0 wt.%, respectively. Several methods were used for pyrite oxidation rate (POR) determination.

Oxygen (% vol.)
5 10 15 20 25

10

Depth (m)

Depth (m)

15

15 20 25 30
Site 6 Site 7

20

25 30

Figure 1. Oxygen and temperature profiles close to slope (Site 6) and in the middle of pile (Site 7).

2 Material and methods
Collection of data and sampling devices are described in Sracek et al. (2004, 2006). Pore water in unsaturated zone of the pile was sampled from suction lysimeters and water in saturated zone was sampled from piezometers. All boreholes in the pile were drilled by reverse circulation air drilling to avoid contamination by drilling fluid. Analyses for cations and metals were performed by AAS, analyses for anions were performed by ion chromatography. Chains of thermistors and oxygen sampling ports were attached to piezometer’s pipes made from PVC. Two contrasting sites were investigated: site close to the pile slope (Site 6) and site in the core of pile (Site 7).
54

At Site 6 close to the slope temperature reached 60 °C at 10 m depth and then slightly increased downward. At Site 7 in the core zone of pile temperature was only about 30 °C at 10 m depth, indicating much lower POR compared to Site 6. Both profiles converged in saturated zone at the base of the pile. Profile of oxygen concentration close to slope was irregular, with a minimum at 3 m depth, but there was increasing concentration at 12 m depth and diffusive profile below 15 m depth. This behaviour indicates convective oxygen supply from the slope. The same profile in the central zone of the pile at Site 7 was exponential, indicating diffusive transport of oxygen coupled with its consumption by the oxidation of pyrite.

IGCP/SIDA Project 594, Annual Workshop, Windhoek, Namibia, 2012, © Czech Geological Survey, ISBN 978-80-7075-781-9

3.3 Pyrite oxidation rate Temperature and oxygen concentration profiles (TOP) were used to determine pyrite oxidation rate (POR) by fitting 1-D analytical solution to the data (Sracek et al. 2006). Resulting values for slope site and pile core site were 1.1x10-9 mol(O2) kg-1 s-1 and 1.0x10-10 mol(O2) kg-1 s-1, respectively. Pyrite mass balance (PMB) was also used to estimate POR. Initial amount of pyrite in the pile was estimated and compared to the amount of pyrite in the pile in the time of sampling. This method is very rough because the estimate of initial amount of pyrite is not precise. However, resulting values for slope site and core site were consistent, reaching 2.21x10-9 mol(O2) kg-1 s-1 and 2.03x10-9 mol(O2) kg-1 s-1, respectively. Finally, oxygen consumption method (OCM) in laboratory was used to determine POR. In this case, crushed waste rock fragments were located in closed chamber, sprinkled with water and oxygen concentration in headspace of chamber was measured with a sensor. Rate of oxygen depletion was converted to POR values. Scale of this experiment was much smaller compared to field scale of the previous experiments. When partly oxidized material from the pile slope was used, POR values were in the range from 3.4x10-9 mol(O2) kg-1 s-1 to 1.0x10-10 mol(O2) kg-1 s-1. However, when fresh waste rock collected in the mine was used, POR values were about an order of magnitude higher.

supply. At site close to the pile slope, where convection predominates, temperature is already high at shallow depth, profile of oxygen concentration is irregular and concentrations of dissolved species reach extreme values e.g. concentration of sulphate is 270 g/l. At site in the core zone of pile temperature is lower, exponential oxygen concentration profile indicates diffusive transport and concentrations of dissolved species in pore water are lower. Results of pyrite oxidation rate determination (POR) gave consistent results and differences between large scale field methods and small scale laboratory method were relatively small. Small scale oxygen consumption method (OCM) may provide relatively representative values of POR in the zones without transport of oxygen limitations, i.e. where convective transport of oxygen is dominant.

References
Sracek O, Choquette M, Gelinas P, Lefebvre R, Nicholson RV, (2004) Geochemical characterization of aci mine drainage from a waste rock pile, Mine Doyon, Québec, Canada, J. Contam. Hydrol. 69:45–71 Sracek O, Gelinas P, Lefébvre R, Nicholson RV (2006) Comparison of methods for the estimation of pyrite oxidation rate in a waste rock pile at Mine Doyon site, Quebec, Canada, J. Geochem. Explor. 9:99–109 Silva da JC, Vargas Jr. EA, Sracek O (2009) Modeling multiphase reactive transport in a waste rock pile with convective oxygen supply. Vadose Zone Journal 8:1038–1050

4 Discussion and conclusions
Results of the study confirmed different pyrite oxidation rates and, thus, temperature, oxygen concentration, and pore water chemistry at a pile with convective oxygen

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IGCP/SIDA Project 594, Annual Workshop, Windhoek, Namibia, 2012, © Czech Geological Survey, ISBN 978-80-7075-781-9

Thallium geochemistry in soils affected by Zn smelting
Aleš Vaněk, Vít Penížek and Vladislav Chrastný Czech University of Life Sciences Prague, Kamýcká 129, 165 21 Prague 6, Czech Republic, vaneka@af.czu.cz Leslaw Teper and Jerzy Cabala University of Silesia, Bedzinska 60, 41-200 Sosnowiec, Poland Abstract. The study focused on Tl contamination of soils in the area historically affected by Zn smelting near Olkusz (southern Poland). Significant differences in Tl concentrations and chemical fractionation were observed between forest and grassland soil profiles, indicating the effect of land use on Tl behaviour. Our findings proved the ability of forest soils to concentrate high amounts of Tl (if present in smelter emissions), particularly within the organic layers. A comparison of Tl concentrations in the upper (O or A) and the bottom horizons (C) of forest and grassland soils clearly demonstrated both strong contamination and vertical mobility of Tl. The results of the sequential extraction procedure indicated the important role of soil organic matter in Tl mobilization, probably as a result of long-term alteration/dissolution of smelter-derived particles followed with Tl release; up to ~20% of total Tl amount was associated with the exchangeable/acid-extractable fraction in forest soils. The Tl concentrations detected in grassland soils were up to an order of magnitude lower than for forest soils. Taking into account the dominant bonding of Tl to the residual fraction, Tl associated with grassland soils poses lower environmental hazard with respect to the potential mobilization or uptake by plants. Nevertheless, further research on Tl dynamics with emphasis to the environmental stability of Tl-bearing phases (oxides, sulfides, silicates) is essential for precise understanding Tl behaviour in such polluted (agro)systems. Keywords. Thallium, Forest soil, Grassland soil, Fraction

To our best knowledge, there is a lack of data concerning the fate of anthropogenic Tl in soils with contrasting land use, i.e., forest and grassland soils. From this point of view, detailed knowledge of Tl geochemistry in such soil systems is essential. This research provides information about the effect of land use, soil chemistry and rate of contamination on the distribution, geochemical position and mobility of Tl in soils.

2 Methods
The Olkusz district, situated in the Silesia-Krakow region (southern Poland), can be characterized by largescale mining and processing of Zn-Pb ores (mainly sphalerite and galena) since the early 1950s. Due to these activities, the area belongs to the most polluted regions in Europe. Average concentrations observed in the forest floor humus or the upper soil layers at Olkusz commonly exceed X000 mg kg-1 for Zn and Pb and X0 mg kg-1 for Tl and Cd, respectively.

1 Introduction
Because of its acute and chronic toxicity for most living organisms, Tl belongs to one of the most dangerous elements in terrestrial environments (Nriagu, 1998). The main anthropogenic sources of Tl include emissions and solid wastes from coal combustion, ferrous/non-ferrous mining and smelting or cement production. Nevertheless, metallurgical processing of Tl-bearing ores (ZnS, FeS2 etc.) is probably the dominant activity leading to significant Tl contamination. Since Tl compounds are volatile at high temperatures, they are not efficiently retained in electrostatic precipitators or other emissioncontrol facilities during smelting. Consequently, a large portion of Tl may be released into the atmosphere and enter the surrounding ecosystems. Average Tl levels in topsoils from such impacted areas commonly exceed 10 mg.kg-1; in contrast, substantially lower Tl levels (0.01–1 mg.kg-1) were observed in non-contaminated soils (Kazantis, 2000). When Tl is present in soils it may be easily taken up by plants primarily as a result of its tendency to substitute K in biogeochemical reactions/cycling. Moreover, previous investigations proved that sulfur-rich species of Brassicaceae have a potential to (hyper)accumulate Tl (e.g., Al-Najar et al. 2005).
56

Figure 1. Location of the study area and soil sampling sites.

Particulate (and eventually gaseous) emissions from the primary/secondary Zn smelter at Bukowno (Boleslaw zinc works) are considered the predominant source of Tl contamination in the study area (Fig. 1); Tl-bearing particles derived from mining- and processing-related activities (e.g., crushing, milling or dressing operations) or remobilized from the open tailing ponds in the past can only locally contribute to total Tl contamination. The smelter has been operational for 60 years (opened 1952) and emissions of pollutants (mainly Zn, Pb and Cd) have resulted into severe contamination of the surrounding area. Recently, Zn ore concentrates and waste materials are processed. Four soil profiles were sampled at two sites as a

IGCP/SIDA Project 594, Annual Workshop, Windhoek, Namibia, 2012, © Czech Geological Survey, ISBN 978-80-7075-781-9

function of land use, distance from the smelter and prevailing wind direction in the area (pair design). At each sampling site, forest (F) and grassland (G) soil profiles were sampled. The sampling sites were situated along the SW-NE transect approx. 1 km and 6.5 km from the smelter. The location of the profiles is given in Fig. 1. Forest stands are dominated by middle-aged (40–50 years old) Scots pines (Pinus sylvestris L.), covering the intensive metal deposition in the area (between the 1960s–1970s). Soil samples were collected from 1×1 m wide pits according to the natural development of soil horizons, down to the bottom horizon C. The top surface composed of fresh litter or grass cover was removed. Approximately 1 kg of soil from each horizon was collected to get a representative sample. Prior to analysis, all samples were air-dried to constant weight, sieved to <2 mm using a stainless steel sieve and homogenized. The soils were classified as Dystric Arenosol, Rendzic Leptosol and Haplic Podzol. Soil pH was measured using a 1:5 (v/v) ratio of soil and water or 1 M KCl solution (ISO 10390:1994) using a pH-meter Handylab pH 11 (Schott, Germany). The contents of total organic carbon (TOC) and total sulfur (Stot) were determined by catalytic oxidation (1350 ºC) using a combination of Metalyt CS 500 and Metalyt CS 530 elemental analyzers (Eltra, Germany). Cation exchange capacity (CEC) was computed after saturation of soil samples with 0.1 M BaCl2 and Ba2+ release using MgSO4 (ISO 11260:1994). Excess of Mg present in the solution was determined using Varian SpectrAA 200HT flame atomic absorption spectrophotometer (FAAS). Acid oxalate extraction using 0.2 M ammonium oxalate/oxalic acid at pH 3 for the determination of amorphous and crystalline Fe-, Mn- and Al-(hydr)oxide content was performed. Oxalate-extractable amounts of Fe, Mn and Al were determined by FAAS. Particle size distribution was determined by the hydrometer method. In order to determine bulk Tl concentrations in the studied soils, 0.5 g of powdered sample was digested in a mixture of concentrated acids HF/HClO4/HNO3 using a microwave digestion unit (Mars 5, CEM, USA). Potentially mobilizable amount of Tl was predicted on basis of 0.05 M EDTA extraction according to Quevauviller (1998). The chemical fractionation of Tl in the soils was determined using the optimized BCR sequential extraction procedure (SEP) (Rauret et al., 2000). The residue from the third extraction step was digested in HF/HClO4/HNO3 and represents the residual Tl fraction. A detailed experimental scheme of the SEP is given elsewhere (Rauret et al., 2000). Three replicates of each soil sample were performed for all Tl analyses; the sum of individual SEP steps was in a good agreement with total Tl concentration (recovery differences were less than 10%). During all chemical procedures, deionized water (MILLI-Q Element, Millipore, France) and chemicals of analytical grade (Fluka, Germany; Lach-Ner, Czech Republic) were used. The concentrations of Tl in all digests were determined using ICP-MS (PQExCell, ThermoElemental, UK).

3 Soil properties
Surface horizons of forest soils were rich in organic C (up to 34 wt.%), while grassland soils showed significantly lower TOC amounts (2.6 wt.%, in maximum). In the carbonate-rich Leptosol (profile 1G), the portion of inorganic C (TIC) was determined and reached 4.3 wt.% in the bottom horizon Cr. Similarly to TOC, forest soils were abundant in total S (up to 3.1 mg kg-1). Circum-neutral pH values (7.0–7.9 in water suspension) were found for soil profiles 1F and 1G, i.e., for both forest and grassland soils located close to the smelter (~1 km). In contrast, profiles 2F and 2G located ~6.5 km away the smelter were more acidic (4.1–6.1). As expected the lowest pHs was observed in surface/subsurface horizons of forest soil (profile 2F). The CEC values varied from 10.3 to 43.2 cmol kg-1 and were generally higher in organic horizons compared to mineral ones (up to 3-times), corresponding to the increased soil organic matter (SOM) content. The clay content in mineral horizons was relatively uniform in all profiles and accounted for 1.3–15.9% of particle size distribution. Oxalate-extractable Fe was more abundant in organic horizons of forest soils with a maximum detected in the profile 1F, reflecting the formation of secondary Fe oxides (see Soil mineralogy). The enrichment of oxalate-extractable Mn was observed in soil profiles 1F and 1G.

4 Concentration and mobility of Tl in soils
Concentrations of Tl in soils were strictly dependent on the localization of soil profiles, i.e., substantially higher levels of Tl were found at the site located close to the smelter (Table 1, Fig. 1). The maximum Tl concentration (30.1 mg kg-1) was determined in the organic horizon O of forest soil profile 1F, indicating both an effective interception of smelter emissions by pine canopies followed with their enter the underlying soils as well as a positive role of forest floor humus on Tl retention, primarily in the solid state. On the other hand, the extent of Tl contamination in the bottom horizon C (up to 3.5 mg kg-1) suggests important metal migration through the profile. A comparable trend in Tl concentrations, i.e., rapid depth-dependent decrease of Tl, was observed for the less contaminated forest profile 2F (Table 1). Surprisingly, significant Tl accumulation was found in the Cr horizon of the grassland soil (profile 1G), reaching 4.1 mg Tl kg-1. These findings are consistent with elevated amounts of potentially mobilizable Tl (EDTA-extractable) in the organic/surface horizons O and A from which Tl can be potentially released and enter the underlying mineral layers; the portions of EDTA-extractable Tl detected in topsoils corresponded to 11–20% of total Tl contents (Table 1). A long-term interaction between metal-bearing phases derived from smelting (oxides, sulfides, sulfates etc.) and SOM with subsequent Tl mobilization is suggested for the forest soils. The vertical shift of Tl through its colloidal (or microparticle) transport, as can be expected by illite clays and possibly Mn oxides (identified by XRD), cannot also be excluded. A strong affinity of Tl to these
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IGCP/SIDA Project 594, Annual Workshop, Windhoek, Namibia, 2012, © Czech Geological Survey, ISBN 978-80-7075-781-9

phases has been reported and results from specific Tl adsorption and/or Tl–K replacement within the mineral structures, as the geochemical analogy of Tl+ and K+ is known (Nriagu 1998). It remains unclear to what extent smelter-derived particles (containing Tl) entered the mineral horizons. Nevertheless, based on mineralogical data, their role in a complex process of Tl movement in soils seems to be limited.
Table 1. Total and EDTA-extractable Tl concentrations in the soils.

smithsonite and cerussite). Despite the fact that the identified sulfides represent a minor component in dust/fly ash from ore roasting, they are relatively “insoluble” if altered, and thus can be also found in the studied soils. No Zn and Pb minerals were detected in the profiles 2F and 2G from more distant area, probably due to their concentrations below the detection limit of XRD.

6 Chemical fractionation of Tl
Figure 2 shows the chemical fractionation of Tl in individual horizons of the studied soils. The organic horizons of forest soils contained relatively large portions (up to 23%) of labile Tl (associated with the exchangeable/acid-extractable fraction), i.e., comparable to those obtained by the EDTA extraction. Regarding elevated CEC values, indicating a high sorption efficiency of the SOM, the presence of adsorbed Tl+ species is proposed. Retention of labile Tl in the mineral horizons of both forest and grassland soils is most probably controlled by non-specific sorption of Tl onto the soil exchange complex which consists of clay phases, oxides, or eventually carbonates. Taking into account the pH values determined in the mineral horizons of all profiles (lower for 2F and 2G), its direct role in the distribution of non-residual Tl fractions seems to be limited. In the case of the soil profile 1G (Leptosol) and eventually 1F, Tl coprecipitation with the newly formed carbonates, following partial CaCO3 dissolution, could be the important mechanism influencing Tl release from such an operationally-defined fraction, as the preferential association of Tl with carbonates in alkaline soils is known. All soils can be generally characterized with a majority of Tl bound to the residual fraction (95%, in maximum), followed with the reducible fraction (16– 47%), which corresponds approximately to soil oxides (Fig. 2). It is believed that reducible Tl is predominantly associated with Mn oxides, if present. This statement favors a statistically significant correlation (r = 0.603, p<0.05) found between the amounts of reducible Tl and oxalate-extractable Mn. According to Jacobson et al. (2005), efficient Tl retention by Mn oxides (especially δMnO2) arises from their low pHZPC values and the oxidation of Tl+ to Tl3+, which is then tightly adsorbed or precipitated as Tl2O3 on the oxide surface (Bidoglio et al., 1993). Moreover, a rapid incorporation of Tl into the Mn oxide structure has been proposed, i.e., in nonexchangeable K-exchanged layers. These Tl-bonding mechanisms can be expected in the profiles 1F and 1G with the identified Mn(III,IV) oxides. The sorption efficiency of Fe(III) oxides for Tl is generally low (Jacobson et al., 2005). Thallium associated with the oxidizable fraction, attributed to sulfides or theoretically strong binding sites on the SOM, was accumulated in the organic/surface horizons O and A and reached up to 22% of total Tl speciation. Since locally-processed sulfides are strongly enriched in Tl (mainly sphalerite), these can be thought as a major component of the oxidizable Tl fraction for topsoils. This is in accordance with the XRD results, proving the presence of Pb/Zn sulfides in upper soil horizons of the profiles 1F and 1G. Considering that
58

Profile

Horizon

Tltot (mg kg-1) 30.1 ± 0.7 18.8 ± 0.5 5.27 ± 0.17 3.50 ± 0.02 5.85 ± 0.47 4.08 ± 0.21 2.83 ± 0.14 0.90 ± 0.04 0.62 ± 0.07 0.16 ± 0.02 0.28 ± 0.02 0.21 ± 0.08

TlEDTA (mg kg-1) 5.65 ± 0.26 3.06 ± 0.01 0.48 ± 0.02 1.24 ± 0.03 0.89 ± 0.09 0.16 ± 0.03 0.56 ± 0.06 0.09 ± 0.01 0.02 ± 0.02 b.d.l. 0.03 ± 0 b.d.l.

1F

O Ai C1 C2

1G

Ah Cr

2F

O Ae Ep C

2G

Ap C

5 Soil mineralogy
The XRD results showed that the bulk mineralogy of forest and grassland soils is dominated by quartz (SiO2), K/Na feldspars (KAlSi3O8, NaAlSi3O8) and illite ((K,H3O)Al2(Si,Al)4O10(OH)2) with minorities of montmorillonite kaolinite (Al2Si2O5(OH)4), ((Na,Ca)0.3(Al,Mg)2Si4O10(OH)2·nH2O) and goethite (αFeOOH). The presence of crystalline/poorly crystalline Mn(III,IV) oxides in the profiles 1F and 1G was revealed. Furthermore, carbonates such as calcite (CaCO3), dolomite (CaMg(CO3)2) and ankerite (Ca(Fe,Mg,Mn)(CO3)2) were enriched in these soils, as expected. The detection of sphalerite (ZnS), galena (PbS), smithsonite (ZnCO3) and cerussite (PbCO3) in the upper soil horizons O and A of heavily polluted soils (profiles 1F, 1G) clearly indicates the predominance of airborne contamination originating from the nearby smelter area. Interestingly, Zn and Pb oxides (e.g., zincite, ZnO, litharge, PbO) were not revealed in these soils, despite their common abundance in dusts from smelting operations, primarily from ore roasting. This could be a complex result of expected intensive dissolution (low stability) of Zn/Pb oxides within soil environment (log Ksp = 11.2 for ZnO, log Ksp = 12.9 for PbO; MINTEQA2 database) and relatively high pH values (~7) of the soils followed by preferential formation of secondary metal carbonates (i.e.,

IGCP/SIDA Project 594, Annual Workshop, Windhoek, Namibia, 2012, © Czech Geological Survey, ISBN 978-80-7075-781-9

Tl complexation with most organic ligands (log K = 0.5– 2.0), and fulvic acids (log K = 3.3–4.8) is weak (Nriagu 1998), the formation of organic complexes is unlikely, even in the organic horizons of forest soils. As mentioned above, the residual fraction of Tl was dominant for the soils. Nevertheless, this fraction may be overestimated due to the drawbacks of the SEP, e.g., non-selective nature of the extracting solutions, redistribution of fractions during the procedure etc. Despite the fact that Tl readily enters the interlayers of illite and/or tends to accumulate in primary silicates (e.g., feldspars, micas) (e.g., Jacobson et al., 2005), we recorded an insufficient oxidation of Tl-bearing sulfide linked with the lower recovery of oxidizable Tl during the SEP. In other words, a part of the residual Tl amount detected in topsoils corresponds probably to late sulfide dissolution.

7 Conclusions
Our findings proved the ability of forest soils to concentrate high amounts of Tl (if present in smelter emissions), particularly within the organic layers. The results of SEP indicated the important role of SOM in Tl mobilization, probably as a result of long-term alteration/dissolution of smelter-derived particles followed with Tl release; up to ~20% of total Tl amount was associated with the exchangeable/acid-extractable fraction in forest soils. A comparison of Tl concentrations in the upper (O or A) and the bottom horizons (C) of forest and grassland soils clearly demonstrated both strong anthropogenic contamination and vertical mobility of Tl. The Tl concentrations detected in grassland soils were up to an order of magnitude lower than for forest soils. Taking into account the dominant bonding of Tl to the residual fraction, including surface horizons, Tl associated with grassland soils poses lower environmental hazard with respect to the potential mobilization or uptake by plants. On the other hand, previous investigations found that even such “stable” Tl may be to a great extent taken up by specific plant species, especially Brassicaceae. Therefore, further research on Tl dynamics with emphasis to the environmental stability of Tl-bearing phases (oxides, sulfides, silicates) is essential for complex understanding Tl behavior in such polluted (agro)systems.

Acknowledgements
This research was funded by the grants of the Czech Science Foundation (GAČR P210/11/1597 and GAČR P210/12/1413)

References
Al-Najar H, Kaschl A, Schulz R, Römheld V (2005) Effect of thallium fractions in the soil and pollution origins on Tl uptake by hyperaccumulator plants: a key factor for the assessment of phytoextraction. International Journal of Phytoremediation 7:55– 67 Bidoglio G. Bibson PN, O´Gorman M, Roberts KJ (1993) X-ray absorption spectroscopy investigation of surface redox transformations of thallium and chromium on colloidal mineral oxides. Geochimica et Cosmochimica Acta 57: 2389–2394 Jacobson AR, McBride MB, Baveye P, Steenhuis TS (2005) Environmental factors determining the trace-level sorption of silver and thallium to soils. Science of the Total Environment 345: 191–205 Kazantis G (2000) Thallium in the environment and health effects. Environmental Geochemistry and Health 22:275–280 Nriagu JO (1998) Thallium in the Environment. John Wiley & Sons, Inc., New York, NY, USA Quevauviller Ph (1998) Operationally defined extraction procedures for soil and sediment analysis. I. Standardization. Trends in Analytical Chemistry 17:289–298 Rauret G, López-Sánchez JF, Sahuquillo A, Barahona E, Lachica M, Ure AM, Davidson CM, Gomez A, Lück D, Bacon M, Yli-Halla M, Muntau H, Quevauviller Ph (2000) Application of a modified BCR sequential extraction (three-step) procedure for the determination of extractable trace metal contents in a sewage sludge amended soil reference material (CRM 483), complemented by a three-year stability study of acetic acid and EDTA extractable metal content. Journal of Environmental Monitoring 2:228–233

Figure 2. Chemical fractionation of Tl in forest and grassland soils; profiles 1F, 1G – heavily contaminated (~1 km away the smelter), profiles 2F, 2G – less contaminated (~6.5 km away the smelter). Data shown are means ± SD (n = 3). Same letters represent statistically identical values according to the Duncan test (P < 0.05); each soil profile was tested separately.

59

ENVIRONMENTAL AND HEALTH IMPACTS OF MINING IN AFRICA
Edited by Benjamin Mapani and Bohdan Kribek

Published by the Czech Geological Survey, Prague, 2011 Printed in the Czech Geological Survey, Klárov 3, Prague 1, Czech Republic First edition, 59 pages, 70 copies 03/9 446-408-12

© CZECH GEOLOGICAL SURVEY, PRAGUE 2012

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