Geosciences in the 27't century.

ENVIRONMENTAL PROBLEMS ASSOCIATED WITH THE MtNtNG ACTTVTTIES tN THE APUSENT MOUNTATNS, ROMANTA

Elena-Luisa IATAN

lnstitute of Geodynamics ,,Sabba S. $tefdnescu" of Romanian Academy, D-21 Jeon-Louis Calderon St, o2oo32 Buchorest, e-mail: [email protected]

Mining is one of the oldest industries, and abandoned mines with the potential to release harmful substances into soil, water and air are found throughout Romanian territory. Due to the mining activity of ore deposits for more than 2000 years, in there are over 550 tailings dumps, covering an area of approximately 800 ha and storing over 200 million cubic meters of tailings and 54 tailings ponds, which covers an area of almost 1350 ha and stores over 350 million m3 of waste. Mining activities create a potential impact on the environment, both during exploitation and in the years after mine closure. Underground exploitation presents the risk of collapsing galleries and surface overflowing and involves the dislocation of a large amount of rocks. Quarrying is one of the most common forms of mineral extraction, being particularly harmful to the environment, as strategic minerals are often available in low concentrations, which increases the amount of ore extracted. Althou8h mininB activities are currently stopped in most areas, the potential risk of environmental contamination exists due to the huge quantities of tailings in the tailings ponds and the tailinBs dumps very close to the watercourses. These are permanent sources of pollution for surface and groundwater, soil and air in the area (Fig. 1). The oxidation of sulphide minerals led to the removal of soluble metal ions from the mineralization found in mining related wastes under the effect of water. As the water takes over the concentrations of minerals and heavy metals, it becomes a contaminant and a source of dispersion that can pollute the region around the mine and for considerable distances from the source. The South territory is crossed by a dense network of fluvial courses included in the fluvial system of the Muret and of the Crigul Alb, both of them discharging their waters into the Tisa and implicitly into the . The Mureg River ls the main collector of the waters in the studied region. The main tributaries of the Mureg, from the Southern Apuseni Mountains, are the Aries, the and the rivers. Downstream C6mpeni, the Ariet Rlver receives, from the Metaliferi Mountains, a series of right-bank small rills such as Stefanca, Musca, Sesei, which receive the waters from the Ro$ia Poieni and Baia de Ariet mining perimeter. The is the most important right-bank tributary of the Arie; (Fig 1. C). lt gathers the rills that flow radially around the igneous massif of Detunata and of lzbicioara, Abruzel and Bucumanilor triburaties reciving waters from Bucium Poieni, Bucium Sasa and Bucium lzbita old mining perimeters. The Corna Valley and the Ropia Valley (Fig 1. A) are among the most important tributaries of the Abrud, receiving the waters from the Rogia Montand and Ro;ia Poieni mining perimeter. The pollution sources of the Ariet basin proceed from the mining objectives of Rogia Montan6, Rosia Poieni, Bucium and Baia de Arieg. The main water collector within the Rogia Montani mining perimeter is the Ro$ia Valley stream, called Foiep (Fig 1.A), where the hydrographic network has been totally disorganized by mining activities. From the opencast pit, the pluvial waters infiltrate into underground through the old mining galleries, being collected at the level of the transport gallery "Sfanta Cruce din Orlea" from where they are discharged into the Foie5 stream (Fig 1. B). ExceedinB values are registered for almost all indicators of the mine waters, including very noxious elements and heavy metals such as lead, copper, zinc, arsenic, cadmium and manganese, with strong acidic conditions (table 1).

aJ Geosciences in the 27't centurY-

(Ro5ia Montane Valley), B.,,Sf6nta Cruce din orlea,,(Ro'ia MontanS) Fig. 1 Wnters affected by mining: A. Foie$ stream river, D. Barza gallery waters, E. g"ji*v ,r",orr, c. the confluence of Abrud river (ieddish-yellowish color) with Aries Barza Valley, F. Grimm gallery waters (Troila)'

which collects the waters from ln the Ro;ia Poieni mlning perimeter, the local hydrographic network' Steregoi, Sesei, Musca and the opencast pit and the mine waste dumps, is represented by the Stefancei, the Geamina and Cuibarului Valleys' Fintinilor Valleys, right-bank tributaries of the Aries River, as well as from the area present rigiruant tribuiaries of the Abrud River. The analysis of the collected samples exceedingvaluesforalltheWaterqualityindicators,withhighlyacidicpHandalarmingvaluesofcopper, zinc, cadmium and iron contents. lntheBaiadeArie'miningperlmeter,thelocalhydroSraprricnetworkhasbeendisorganizedasresu|t and with processing wastes (sart5s of stream blocking with ,nln" *rrt", (Hermlneasa and croara Valleys) Valley,BrazestiValley).MinewatersarecollectedBrav;tatronallyintotrvobasinsandtheaual'tvofthe watersdischargedintheAriegRiverisinfluencedbytheirmlneraii?ationdegree.Valuescxceedingthe admittedvaluesareregisteredforsuspensions,fixedresiduum,5ulphides.:ldmet;rllicions(cU.Pb,zn,Fe, Mn, Cd, As) (Duma, 2009). SeveralstudieshavebeencarriedoutinordertoevaluatetheWaterquaIityandthelevelofmetal mining operations. The physico-chemical contamination in the Arie$ river and its tributaries affected by the parametersindicatedthecontaminationoftheWaterbyminingactivities.lnthetributariesofAries,thepH valueswereintheacidrange(Senilaetal',2015).ThewateroftheAriegriverhasbeenfoundtobemostly (Fe, Zn, Cu and Mn) were poliuted with cu, Mn and Fe (Levei et al., 2014). The concentrations of metals Arieg river were hiShly contaminated with cd' higher in tributaries (senila et al., 2015). The sediments in the Ni and low with cr (Levei et al', 2014)' Their impact Cu-and ns, considerably with zn, moderate with Pb and onthewaterqualityoftheriverisstronglyfeltalongtheentirelengthoftheAriegriver,fromCSmpenito varies depending on the flow of the river the confluence with the Muret river, andlhe intensity of pollution (Corches,2011). units that have affected aquatic -s6c5ramb, , Troita-Bolcana and Vorla are the mlning environment in AmPoi Bosin- due to the ln l6e Zlotno mining perimeter, the hydrographic network has been disorganized constructionofthetailingpondsonSf6rciValleyandonValeaMiciandthroughtheminewastedumps blockingtheHanesandLargarills.TheWatersflowingfromthetailingssettlingpondsofzlatnaregister The mine water is affected by the values for copper, lead, zinc, iron, manganese and cyanides' "*.""OIngpresence of metallic ions (Cu, Pb, Zn, Fe) causing an acid pH (table 2)'

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- Geosciences in the 27't centuty.

3Duma, Table 1. Chemistry data of analyzed waters from Arieg basin (lWhitehead, 2OO9j '?Friedel et al, 2OO8; 2OOg; aCorcheg, slatan, 20L!.; 2019).

)ria \:allE.v losia \'liDc \\?tes ;llirl. Baia de patit-v oies)l l'rll.yl i'aIeyr '.'aller: Uvcl. la rpeuil laia de rql Ui,l {ar rIlD \Iin \rl!l hlax L,r \'1i,1 t5 t6 t.l 8 73S t84.1 )9 :2.1 165

3l lit 09 l?5 t1.3 L:] L.:9 :.1.: t.0.J 07.-1 1 ),J 336r.5 Dl70 l-6 ]61 4.6 II )8 0: i0r0 )6 .t90t 50 ),1 i7 6S ,9.01 t66 t.l t79 t.s 5.4 108 3S 100 \t:88 5i .{590 :50 l I:9 :-6-r.i I-S 7190 l0l r l4.l il l-l S :38?.8{ 4650 t96J t5 .36 i.5 :i8.ll tl )5-{ .-j-l lll (3 E 1.1 .rt00 1.0: i01000 16.5 ss l.o1 1tl t.l i .t6.r( )4 tr30 100 5t0 i4l0( 1l:4C 1i00 l:10 1S0 ,H] l.r r t6 t0 l.i t9 '0

ln the Certej - SdcEremb mining perimeter, waters are collected into the hydrographic basin of the Certej River, a right-bank tributary of the Mures River. The mine waters run freely into the emissary, the ones from the Bocga Mine into the Bocsa Rill, the ones from the Hondol-Bdiaga Mine into the Certej River, and the ones from the SScIr6mb Mine into the Nojag Rill. The mine and the opencast pit waters are characterized by high contents of solid suspensions, fixed residuum, metallic ions (cu, zn, Fe, Mn) and sulphate ions (So4). The waters flowing from the Mealu Valley tailings settling pond are characterized by exceeding values for suspensions, fixed residuum, metallic ions (pb, zn, Mn), so4, chlorine and cyanides. The waters of the certej Rill have polluted through infiltrations also the phreatic waters, which, in certain periods of the year become undrinkable (table 2). The waters from the Troita Mine have a discharge of 420 m3/day and run freely at the level of the Grimm gallery (Fig 1. F) into the Bolcana Rill, a left-bank tributary of the Caian Rill, downstream the locality of Soimus. These waters are characterized by low values for pH as well as exceeding sulphates and metallic ions (Cu, Pb, Zn, Fe). Mine waters have only little influence upon the water quality of the Caian Rill due to their low discharge value, as well as to the share of carbonates containing waters of the Crdciunesti lime opencast pit that regulate the pH.

Table 2. Chemistry data of analyzed waters from Ampoi basin (Duma, 2OO9).

HaD,-s lal!. B.iaga Hondot- PaFrl quality Miuc Baii Heiu! vatlGy gallay gall.,-1 urc I c\t t'.t 1.9 195 0.ll 56: 009 0 1.06 013 0li 0t PL' 06 0..15 0.1 001 0 t6.5 0t6 o tJ OI Zn :!.6 1.6.1 -.('.38 :46 0 073 o.l8 0 ts F. t 69t I5S -t o0 ,r.!9 30: 78 :0 I :.1 l4? 2.47 t.06 -10 ..! l'{n l-t0 lo.6 -16 -t9:9 r50.r0 5.60 Ca 1l {80 139.: t19 l 514 l0: r tf( l:l 40 6.1.9: pH 1.5 'Il .l 16 5 -r1 730 E09 t:8 s.tt ll-

The waters evacuated from the Vorta Mine through the two flank galleries from Heius Valley and Biii Creek (table 2) are discharged into the Vorta Valley, their quality being characterized by the presence of metallic ions (Cu, Zn, Pb, Fe), but their influence upon the waters of the Vorta Valley is insignificant due to ihe low dlscharges of the mine waters (Duma, 2OO9).

The Crisul Alb River is the main collector of the waters in the northern sector of the Meta liferi-Za ra nd Mountains. At Criscior it receives the left-bank waters from the Valea Arsului-Valea Morii, Barza and Rovina Mines and at Brad the ones ofthe Luncoi Valley (Ruda-Brad mine) (table 3).

84 Geosciences in the 21r century.

Table 3. Chemistry data of analyzed waters from Crisul Alb basin (Sima et al., 2008)

Water qualiry Barza B^126 tubira Ar'tllui Ro.;i11a Cris A1b River Clis.4'lb Rivct' Vallcy \Iine tailling Valley Ruda railliDg before mirg afta uunrg

Cu t0 190 r1000 0l l-l 50 Pt) .l 00J 0.: Zn 5700 1000 I II r06 .l FE 9.10 :8000 4r0 190 (d 006 100 <0 05 <0 0r 0.0i 0: ls l0 -l I4400 tr0 18000 t0 I I0 lrl DH 16 71 40 sl r_1 s0 :s

Heavy metal contaminations in the CriS Alb basin (table 3), combined with high sulfate concentrations and low pH values, are found in valleys, Arsului Valley and Barza Valley (Fig 1.E). The outflow of the open pit mined for copper situated in Valea Arsului, exhibits clearly high dissolved metal contents. The drain of underground galleries and waste dumps in Valea Barza, shows high manganese, iron, zinc and cadmium concentrations. Due to the high contents of dissolved iron and particulate Fe, these waters display an ochre-brownish color, the distinct and classical optlcal sign of mining pollution (Duma, 2009) (Fie 1. D). Results and conclusions: High values of the contents of metallic ions were recorded for the waters from Rogia MontanS, Hanes Mine, Larga Mine, SIcIr5mb Mine, Barza Mine and Troita Mine (tables 1, 2, 3). ln Rotia poieni, high contents of copper were registered in the waters flowing from the mine waste dumps. High contents of cyanides were recorded in the waters of the S6liste Valley tailings settling ponds - Rogia Montan5 (0.32 mg/l), in the Sart59 tailings settling pond - Baia de Arie' (0.75 mg/l) and in the Valea Mealu tailings settling pond of certej- SdcEramb (0.040 me/l) (Duma, 2009) The potential for acid generation is directly related to the potential oxidation of sulphide minerals to sulphate (sulphuric acid). The experiments made by Jennings et al. (2000) demonstrated that under strongly oxidizing conditions, pyrite, marcasite, pyrrhotite, arsenopyrite, chalcopyrite and sphalerite are acid-producing minerals but chalcocite and galena were found to be non-acid producing minerals. ln the studied area, the main sulphide-producing acid is pyrite. ln the Southern Apuseni Mountains, long-term mining activities have caused environmental problems, affecting waters, soils and sediments, which must be remediated. The rehabilitation of the environment in the Southern Apuseni Mountains has to be done, in order to reduce the impact of mine waters and of the ones flowing from the tailings settling ponds and waste dumps, by the construction of water treatment stations.

Acknowledgments. This work was supported by two Romanian Ministry of Research and lnnovation grants, project PN-lll-P1-1-2-PCCDI- CCCDT - UEF|SCDt, project number PN-lll-P4-lD-PCCF -20L6-4-O0f4 and number 2017-0346/29, within PNCDI lll.

References

::.ches, M.T., 2011. The Arieg river anthropic pollution due to mining activities, Journal of Agroalimentary Processes and Technologies 2077,77, 4. :' .cel, M.J. Tindall, J.A., Sardan, D., Fey, D., Poptua, G.1., 2008. Reconnaissance study of water quality in the mining- affected ArieS River basin, Romania: U.S. Geological Survey Open-File Report 2008-1176, 40 p. peroxide . . - - ngs, S, Dolhopf, D, lnskeep, W., 2OOO. Acid production from su lfide minerals using hydrogen weathering Appl Geochem 15, 247-255. N. M., Frenliu, T., 20L4. Assessment of contamination and origin of metals in ,:, = . E., Ponta, M., Senila, M., Mlclea, -ining affected river sediments: a case study of the Aries River catchment, Romania. Journal of the Serbian :'remical Society 79, 8, 1019-1036.

85 Geosciences in the 27't century.

Senila, M., Levei, E, Senila, L.R, Roman, M., 2015. Preliminary investlgation concerning metals bioavailability in waters of Ariet River catchment by using the diffusive gradients in thin films technicue Journal of Chemistry Volume 2015, Article lO 7 6272r, I pages http://dx.doi.ory/ 70.1-15s/20L5/7 62721. Sigismund, D., 2009. The impact of mining activity upon the aquatic environment in the Southern Apuseni Mountains. Romanian Review of Regional Studies V, L. Sima, M., Zobrist, J., Senila, M., Levei, E.A., Abraham, 8., Dold, 8., Btlteanu, D., 2008. Environmental pollution by mining activities - A case study in the CriS Alb Valley, Western Carpathians, Romania, Proceedings of the Swiss - Romanian Research Programme on Environmental Science & Technology (ESTROM), 14-2008. Whitehead, P. c., Butterfield, D., Wade, A. J., 2009.5imulating metals and mine discharges in river basins using a new integrated catchment model for metals: pollution impacts and restoration strategies in the Aries-Mures river system in , Romania. Hydrology Research 1 April 2009; 40, 2-3, 323-346. doi: https://doi.orgl10.2166/nh.2009.069.

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