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Acid rock drainage in the mine of Lavrion, Greece

N. Skarpelis and S. Triantafyllidis I. Baziotis
Section of Economic Geology & Geochemistry, Dept. of Geology, University of Athens, Greece Section of Geological Sciences, Dept. of Mining & Metalurgical.Engineering, National Technical University of Athens, Greece

ABSTRACT At Lavrion we are faced with a pollution problem with permanent and specific focus point, such as the acid drainage waters. Acid rock drainage is intense at the underground mines of Lavrion. Draining waters are characterized by strong metal enrichments. The measured concentrations of metals in the highly acidic waters are several orders of magnitude higher than the drinking water standards set by the E.U. Arsenic, cadmium, iron and copper are enriched in the highly acidic waters, whereas their concentrations drop sharply as pH increases. t seems that once the acid drainage waters form, they react with the carbonate host rocks, which can shift pH to less acidic values. The acid drainage in Lavrion is favored by the high pyrite content of the ore bodies and the occurrence of Fe-rich sphalerite. The geology of Lavrion and the occurrence of secondary Feand Zn ores indicate that the draining waters remained polluted since the uplift of the AtticoCycladic Belt, as a result of oxidation of sulfide ores and the release of metals into the natural environment. 1. INTRODUCTION Ancient miners in Lavrion were interested in exploitation of Ag-rich ore (hypogene and supergene). Thus they left great reserves of lowgrade Pb-Ag ore and mineral wastes, either on surface or underground, which were used and processed after the reactivation of the mine at the end of the 19th century AC. They also left

behind tailings coming out from processing and smelting of the ore. Mining and smelting activities which started at the same period have resulted in the production of millions of tones of mining wastes and tailings that are characterized as toxic and hazardous (Kontopoulos et al., 1998a). The flotation tailings and the slags constitute the major source of soil contamination in the Lavrion urban area. Improper waste management in the past contributed to soil and groundwater contamination. Thus local population is exposed to multiple hazardous pollution sources (Xenidis et al., 2003). Many scholars have evaluated the environmental impact of past mining and metallurgical activities at Lavrion. Soil pollution assessment studies and contaminated soil remediation research was carried out by Korre (1999) Korre & Durucan (1995), Demetriades et al. (1996), Kontopoulos et al. (1998b), Xenidis et al. (2003). Natural acid drainage is the result of both percolation and draining of groundwaters into sulfide ore bodies. Acid drainage phenomena are enhanced by the presence of increased concentrations of pyrite and Fe-bearing sphalerite. Their oxidation results in the production of sulfate iron, which is a highly oxidative agent. Acid rock drainage developed upon oxidation of the sulfide ore bodies resulted in dramatic changes of the water quality in Lavrion. The extended network of adits and shafts exposes substantial quantities of sulfides to air that, as a consequence, accelerate the oxidation process and create acid-rock drainage.

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Figure 1: Map indicating the location of the water samples collected in the underground mine of Kamariza, Lavrion.

Despite the generally accepted view that mining and metallurgical activities were responsible for the entire environmental problems of the Lavrion peninsula, we present data indicating that natural oxidation phenomena affecting the sulfide mineralization played and still play a key role in the dispersion of heavy metals in the ground waters. 2. GEOLOGY The SE part of Attica peninsula can be divided lithostratigraphically into two systems. A low angle thrust plane separates the two systems and juxtaposes deeply buried blueschist facies rocks (allochton) above low-grade upper Triassic lower Jurassic carbonates and schists (paraautocthon), which evolved in a different setting. The para-autocthon system is subdivided into three major horizons: the Lower marble, the Kaesariani schists and the Upper marble. A stock of an undeformed upper Miocene I-type granodiorite is exposed in Plaka area. Intrusion

of the Lavrion granodiorite resulted to contact metamorphism of the surrounding Kaesariani schists. A magnetitepyrrhotite skarn-type mineralization was explored in Plaka area. Undeformed subvertical dykes of fresh and mineralized porhyritic rock crosscut the autochthon system. Lavrion is a manto-type Pb-Ag-Zn massive sulfide ore deposit genetically related to the Late Miocene magmatism in the AtticoCycladic belt. The ore bodies are hosted within the Upper and Lower marbles, within marble layers intercalated within the Kaesariani schists (subordinate ores) and also within impure carbonate banks of the allocthon system, especially close to the low-angle thrust plane (Marinos & Petrascheck, 1956; Skarpelis, 2002). Massive sulfide mineralization comprises various proportions of sulfide minerals within a gangue of carbonates, fluorite, barite and quartz. Pyrite, galena, sphalerite (mainly the high-iron variety), arsenopyrite and chalcopyrite are the dominant sulfides. Numerous sulfosalts are

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identified (e.g. tetrahedrite, polybasite, proustite, boulangerite, enargite) (Skarpelis, 2004a). Arsenopyrite, loellingite, enargite and tetrahedrite are the main arsenic-bearing minerals. Sphalerite concentrates show substantial quantities of Cd (2500gr/tn on average). Sb is associated with galena, tetrahedrite and other sulfosalts. Thus the sulfides and sulfosalts give a polymetallic geochemical signature to the mineralization. Major and minor elements associated with the sulfides and sulfosalts are of significant environmental concern: Pb, Zn, As, Cu, Cd, Sb, Fe, Ni and Mn are the main toxic elements released upon weathering of the ores and mineralized rocks. The massive sulfide ores are deeply oxidized. The depth of the oxidation front should be greater than 270m. Gossans and secondary Feoxide and calamine ore bodies are found at all levels of the mines (Skarpelis, 2004b). Uplift of the Attico-Cycladic area, progressive erosion of the landscape and subsequent weathering of the protore, gave rise to supergene mineral assemblages. Two types of supergene mineralization are distinguished on the basis of the mode of occurrence and the origin: a. Gossans, resulted by direct, partial or complete, replacement of the protore by supergene minerals during weathering. b. Secondary marble - replacement ore bodies: They occur adjacent to remnants of sulfide ore bodies or their gossans and are podiform or pyramid-like in shape. They crosscut stratification of host marbles and were named griffons and croiseurs by the French miners. They comprise iron hydro/oxides, smithsonite (calamine) and numerous arsenate, carbonate and phosphate minerals of toxic metals. They formed as a result of the attack of the marble by acid draining waters, development of cavities and filling of open space by secondary minerals (Skarpelis, 2004b). It is clear that acid water generation at Lavrion is not only related to the mining activity in ancient and recent times, but at most to natural processes lasting probably since the Lower Pliocece. Karstification of the marbles and the extended network of adits and mining shafts greatly facilitate downward movement of water. Thus oxygen-laden waters can more easily

percolate to deeper horizons. Drainage within the schists is restricted to joints and fracture zones. The level of the local water table does fluctuate over the year. Temporal flooding of adits and old exploitation rooms - opened even within the marbles - has been observed during wet seasons. Efflorencences of secondary salts (e.g. halotrichite, brochantite, chalcanthite, alunogen, copiapite, melanterite) that form now at the expense of hypogene minerals, consist of typically soluble hydrous sulfates of a variety of elements (e.g. Fe, Cu, As, Zn). During flooding of the underground workings or rainstorm runoff, these salts are dissolved in draining waters resulting in lowering of the pH and increase of toxic metal load. 3. SAMPLING TECHNIQUES AND ANALYTICAL

Water samples from adits of the underground mines of Kamariza (levels +60 and +80) and Plaka were collected. Sample no 7 was collected from the mine drainage system of the adit no 80 at Adami (Plaka). Sampling took place during spring 2002 and spring 2003, applying standard sampling techniques. Temperature and pH were measured on site using a WTW pH 320/Set-2 electronic pH-meter. The water samples were commercially analyzed for cation analysis at OMAC Labs, Ireland. Concentrations of Pb, Cu, Zn, Fe, Cd, Ni, Co, Sb, As, and Mn were measured with an inductively coupled plasma atomic emission spectrometer (ICP-AES). Sulfate (SO4) concentrations were measured using a Hach DR 2000 spectrophotometer. 4. WATER CHEMISTRY Water samples collected from the adits of the underground mines at Kamariza and Plaka yielded pH values between 2 and 7.0 presenting diversity in quality from highly acidic with increased heavy metal and sulfate load to nearneutral with very low heavy metal concentrations (Table 1, Figure 2). The temperature of waters was around 14oC. Samples 1-02 and 2-02 are highly acidic and are collected from ground waters draining ore bodies. On the other hand, samples 3-02 to 7-03 are either buffered acid drainage or waters draining the carbonate rocks.

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Table 1: Concentrations of dissolved ions (mg/lt) and pH values in waters from the adits of the underground mines of Kamariza and Plaka. Sampling pH As points 1-02 2 2.99 2-02 3 0.04 3-02 6 b.d.l. 4-02 4 0.02 5-02 6.5 0.03 6-02 6 b.d.l. 7-02 7 b.d.l. 3-03 3.5 0.21 4-03 4.5 0.02 5-03 4 b.d.l. 6-03 4.5 0.36 7-03 6.5 b.d.l. E.U. standards 6.5-8.5 0.05 U.S.-E.P.A standards 6.5-8.5 0.05 b.d.l.: below detection limit Cd 15.17 5.7 0.03 2.06 3.34 0.01 0.01 9.42 0.04 0.95 0.01 0.01 0.005 0.005 Co 0.24 0.06 0.01 0.02 0.09 0.01 0.01 0.24 b.d.l. 0.02 b.d.l. b.d.l. Cu 48 9.9 0.01 1.4 0.03 0.01 0.01 11.4 0.02 0.72 0.01 0.01 0.1 Fe 1250 54.5 0.01 0.02 0.02 0.01 0.01 28.6 0.09 0.06 0.04 0.09 0.2 Ni 0.85 0.17 0.02 0.17 0.44 0.01 0.04 0.59 0.02 0.10 b.d.l. 0.03 0.05 Mn 55 10 0.01 2.4 13 0.01 0.04 33 0.01 1.3 0.01 0.06 0.05 0.05 Pb 0.07 0.08 0.01 0.01 0.06 0.01 0.01 0.47 0.02 0.02 b.d.l. 0.01 0.05 0.015 Zn 4446 1633 45 567 1165 0.16 0.6 1919 12.3 217 0.53 1.4 0.1 5 SO4 8600 3100 2200 1000 b.d.l. 60 780 185000 7500 10000 900 2900 250 250

0.13 0.3 Sb < 0.02 mg/lt

Highly acidic samples, collected in the proximity of the ore bodies, present pH values lower than 2 and increased load for the majority of the metals analyzed. Iron, As, Cd, Cu, Ni, Mn and Zn concentrations are several orders of magnitude higher than the drinking water standards set by E.U. and E.P.A. Distal from the ore bodies, the quality of the draining waters improves rapidly. This is a result of both the buffering capacity of the carbonate rocks and the mixing of acid drainage with near-neutral percolating waters draining the carbonate rocks. Less acidic water samples with pH values higher than 4 (e.g. 4-02, 5-02 and 4-03) present very low Fe, As and Cu concentrations. At the same time, the more soluble metals Ni, Mn and Zn remain at high concentrations. In the mildly acidic waters Mn is preserved dissolved, whereas adsorption of Ni and Zn on Fe hydroxides and oxides is not favored. The water samples draining carbonate rocks present very low concentrations for both insoluble and soluble metals. Secondary minerals precipitate as open space fillings along joints and fractures of the marbles, as coatings on the walls of adits and to a lesser extend on the drainage stream beds. Precipitation of soluble hydrous arsenates, sulfates and sulfo-arsenates is favored in the highly acidic environments in the proximity of

ore bodies. On the other hand, as the distance increases, the waters turn less acidic with increasing carbonate content, thus favoring the formation and precipitation of secondary carbonates, hydroxides and oxides. Moreover, besides procedures of formation and precipitation of secondary soluble salts, hydrous ferric oxides and hydroxides are another variable controlling the dissolved metal concentrations. In the highly acidic waters, Fe is present in very high concentrations as it is expected. As soon as pH reaches values around 3, Fe concentrations drop sharply. In these conditions Fe forms hydrous oxides and hydroxides that act as sink for most metals. Impressive stalactites of Fe-hydroxides can be seen on the roof of adits and mining rooms along open joints and fractures, which act as conduits for percolating acidic waters. Although As is soluble in acidic waters in the form of oxyanions (e.g. arsenates and arsenites), the presence of positively charged suspended particles (Fe hydroxides) results in the sharp decrease of the dissolved As concentrations through adsorption procedures (Sracek et al., 2004). Additionally, Cu adsorption on Fe hydroxides is effective in rather low pH values (between 4 and 4.5), while adsorption of Cd, Co, Ni and Zn is only effective in higher

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Figure 2: Plot of metal load vs pH as it is described by Ficklin et al. (1992).

10000 1000

Fe+Cu+As+Co+Ni

1-02 2-02

100 10 1 5-03 0,1 0,01 0 1 2 3 4 5 6 6-03 4-03 3-02 6-02 7 8 3-03 4-02 5-02 7-03 7-02

pH

10000 1000 1-02 2-02 3-03 4-02 5-03 100 3-02 10 1 0,1 0 1 2 3 4 6-03 5 6-02 6 7-02 7 8 4-03 7-03 5-02

Zn+Mn+Cd

pH

pH values (Smith, 1999), thus allowing these metals to preserve relatively increased concentrations in the mildly acidic water samples (e.g. 5-02). Though procedures of oxidation, dissolution and precipitation apply to most of the metals studied, this is not the case for Pb. Lead is a major constituent in the Lavrion manto-type mineralization (in the form of galena and Pbbearing sulfosalts), but its concentrations in the

drainage waters are very low, independent of pH fluctuations. Even in the highly acidic samples (e.g. 1-02 and 2-02) Pb concentrations are less than 0.1 mg/lt. Lead behavior is explained by procedures of direct (in situ) formation of secondary insoluble carbonates and sulfates, such as cerrusite and anglesite respectively. These minerals form directly in expense of Pb-bearing sulfides and sulfosalts, which are easily oxidized.

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5. CONCLUSIONS At Lavrion we are faced with a pollution problem with permanent and specific focus point, such as the acid drainage waters. Most of the massive sulfide ore bodies exposed on land have been transformed to gossans. Several outcrops of skarn-type mineralization at Plaka, comprising mainly pyrrhotite and pyrite, are exposed to weathering resulting in metal release, transportation by surface runoff and pollution of waters and soils. The alkaline nature of the host rocks through which the waters flow, favors the rapid deposition of secondary mineral precipitates as open space fillings along joints and fractures of the marbles, as coatings on the walls of adits and to a lesser extend on the drainage stream beds. The geology of Lavrion and the occurrence of secondary iron ore and calamine indicate that the surface and draining waters remained polluted since the uplift of the Attico-Cycladic Belt, as a result of oxidation of sulfide ore and the release of metals into the natural environment. The water samples collected from the underground mines of Kamariza and Plaka, yielded pH values between 2 to 7.0. Acid rock drainage is intense at locations where natural waters drain ore bodies. The draining acid waters are characterized by strong metal enrichments. The measured concentrations of metals in the highly acidic waters are several orders of magnitude higher than the drinking water standards set by the E.U. t seems that once the acid drainage waters form, they react with the carbonate host rocks, which can shift pH to less acidic values. REFERENCES
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Water-Rock Interaction no 7. Balkema, Rotterdam, 381-384. Kontopoulos, A., Komnitsas, K. & Xenidis, A. (1998a) Pollution, risk assessment and rehabilitation at the Lavrion Technological and Cultural Park, Greece. SWEMP 98 Conference Proceedings on Environmental Issues and Waste Management in Energy and Mineral Production (eds. A. G. Pasamehmetoglu, A. Ozgenoglu), Ankara, 18-20 May 1998, 105-110. Kontopoulos, A., Xenidis, A., Papassiopi, N., Ullu, F., Cambridge, M., Gomes, J., Pereira de Sousa, R. & Adam, K. (1998b) Innovative industrial technologies for the rehabilitation of land contaminated from polumetallic sulphide mining and processing operations (ROLCOSMOS). EUROTHEN 98, Athens, 12-14 Jan. 1998, 245-274. Korre, A. (1999) Statistical and spatial assessment of soil heavy metal contamination in areas of poorly recorded, complex sources of pollution. Part 2: Canonical correlation analysis and GIS for the assessment of contamination sources. Stochastic Environmental Research and Risk Assessment, 13, 288-316. Korre, A. & Durucan, S. (1995) The application of geographic information systems to the analysis and mapping of heavy metal contamination around Lavrio mine workings, Greece. Proc. APCOM XXV, Brisbane, 579-585. Marinos, G.P. & Petrascheck, W.E. (1956) Laurium. Institute for Geology and Subsurface Research, Geological & Geophysical Research, 4, 1, 1-247. Skarpelis, N. (2002) Geodynamics and evolution of the Miocene mineralisation in the Cycladic Pelagonian belt, Hellenides. Bull. Geol. Soc. Greece, 34, 6, 21912206. Skarpelis, N. (2004a) Mineralogy and minor element chemistry of the carbonate hosted replacement type sulfide mineralization of Lavrion. 10th Congress Geol. Society of Greece, Thessaloniki, Volume of Abstracts, April 2004. Skarpelis, N. (2004b) Geology and origin of supergene Iron and Zinc ores at Lavrion. 10th Congress Geol. Society of Greece, Thessaloniki, Volume of Abstracts, April 2004. Smith, K.S. (1999) Metal sorption on mineral surfaces: an overview with examples relating to mineral deposits. In: Plumlee, G.S. & Logsdon, M.J. (eds.) Reviews in Economic Geology, Society of Economic Geologists, 6A, 161-182. Sracek, O., Bhattacharya, P., Jacks, G., Gustafsson, J-P. & Von Bromssen, M. (2004) Behavior of arsenic and geochemical modeling of arsenic enrichment in aqueous environments. Applied Geochemistry, 19, 169-180. Xenidis, A., Papassiopi, N. & Komnitsas, K. (2003) Carbonate-rich mining tailings in Lavrion: risk assessment and proposed rehabilitation schemes. Advances in Environmental Research, 7, 479 494.