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Procedia Earth and Planetary Science 17 (2017) 857 – 860

15th Water-Rock Interaction International Symposium, WRI-15

Formation of waste-rock drainage water on massive sulfide deposits


of the Urals (Russia)
P.A. Rybnikova,1, L.S.Rybnikovaa
a
The Institute of Mining, Ural Division of the Russian Academy of Science, Mamin-Sibirjak str. 58, 620075, Ekaterinburg, Russia

Abstract

The waste-rock stockpiles of copper pyrite mines are enriched by sulphide minerals; therefore their dissolution is the reason for
the acidic waters formation. Hydrochemical processes responsible for the water quality of the formed waste-rock stockpiles are
studied using several sites of the Urals as the examples. Sulphide mineralization causes the sulfate composition of water, iron,
aluminum and magnesium to prevail among the cations. The comparison of mine and waste-rock drainage composition shows
that waste-rock waters are more mineralized: TDC is 3-5 times higher and the aluminum, iron, copper and zinc concentrations are
4-8 times higher. The composition of rocks forming mine drainage and waste rock drainage is similar, thus it can be hypothesized
that the hydrogeochemical processes of mine drainage and of the waste-rock piles waters do not have significant differences.
However, the degree of rock disintegration and a temperature gradient in dumps is higher, while the rate of water interchange is
lower. The set of hydrodynamic, geomechanical and temperature factors promote the formation of more acidic mineralized
waters of the dump body. Computer simulation (Visual MINTEQ ver.3.0/3.1) has shown that with the rate of sulphides oxidation
of 3.6·103 mol/hour, the sulphides mass in the dumps would produce acidic leach-water in several hundred years.
©
© 2017 The Authors.
2017 Published Published
by Elsevier B.V. by Elsevier
This B.V.
is an open access article under the CC BY-NC-ND license
Peer-review under responsibility of the organizing committee of WRI-15.
(http://creativecommons.org/licenses/by-nc-nd/4.0/).
Peer-review under responsibility of the organizing committee of WRI-15
Keywords: waste-rock piles; acidic water; sulphide; simulation; heavy metals; the Urals.

1. Introduction

The development of the deposits of mineral resources frees the off-grade and enclosing rocks containing sulphide
mineralization. Mechanical processes that accompany mining lead to the rocks break-down and crushing, resulting
in the increase in interaction with weathering agents. Atmospheric precipitations enriched by oxygen come in
contact with the waste-rock stockpile over the large surface area. Due to the high permeability of rocks that make up

* Corresponding author. Tel.: +7-912-262-3280; fax: +7-343-350-21-11.


E-mail address: ribnikoff@yandex.ru

1878-5220 © 2017 Published by Elsevier B.V. This is an open access article under the CC BY-NC-ND license
(http://creativecommons.org/licenses/by-nc-nd/4.0/).
Peer-review under responsibility of the organizing committee of WRI-15
doi:10.1016/j.proeps.2017.01.038
858 P.A. Rybnikov and L.S. Rybnikova / Procedia Earth and Planetary Science 17 (2017) 857 – 860

the dump, almost complete absorption of atmospheric precipitations takes place. Therefore, the value of penetration
in these sections is several times higher than the regional infiltration of aquifers in undisturbed areas. The sealing of
the bottom of the dump promotes the formation of the aquifer near the bottom of the dump’s body. After redox
conditions change, several geochemical barriers and definite hydrogeochemical zones are formed in the dump. The
dump body is arranged above the earth surface; the temperature gradient between the dump surface and its center
changes depending on the season, leading to the variations in the solubility of minerals, at different times of the
year. The life cycle of the dump lasts decades and include cyclic processes of minerals oxidation, precipitation, and
dissolution. This leads to a particular hydrochemical water composition and to the uploading of water around the
dump perimeter. These waters are characterized by low pH values, have increased mineralization content and are
enriched in heavy metals1,2.
This work is aiming to understand the mechanism of forming acidic under-dump waters and to evaluate the
intensity and duration of AMD formation on copper pyrite deposits of the Urals.

2. Study area

The zone of pyrite mineralization of the Urals is located to the east of the Main Urals water shed and is within the
borders of evgeosyncline zone of the Urals3. The deposits are confined to a narrow band of volcanic and volcanic-
sedimentary rocks, 1600 km in length along the meridian. Chalcopyrite fields belong to copper and copper-zinc
type. There are many varieties of the ore minerals in this region, with the most common ore-forming minerals being
pyrite, chalcopyrite, and sphalerite. Thus iron, copper and zinc are the most abundant of the sulphide ores. Non-
metallic minerals that are present in the region include quartz, calcite, micas, chlorites, barites, gypsum and
anhydrite.
Materials that make up the dump are chemically and mineralogically heterogeneousand include shales,
albitophyres, porphyrites, and porphyres4. The predominant composition of the rocks is silicates, aluminum
compounds, and iron. The dump rocks contain considerable amounts of sulphides, approximately 3-10%. Its full
composition is: 95% pyrite, 2% chalcopyrite and 3% sphalerite. Copper content is 0.1 to 0.3%, zinc is 0.2-0.3%,
sulphur is quite variable between 2.8 and 10.9%. Pb, Co, Ni, Mo, As, Sb are in the amount of n·10-2÷n·10-3%. Rare-
earth elements are in the amount of n g/t, Ga makes an exception, reaching a concentration of up to 27 g/t. The
dump volume in one deposit is usually between 3.5 and 6.0 million tons4.

3. Results and discussion

Sulphide oxidation is the main process that determines the chemical composition of ground waters in the areas of
copper-pyrite mines5,6. As a result, groundwater is enriched by sulphates, iron, zinc and copper. The dissolution of
enclosing rocks is a source of aluminum, magnesium, calcium and other components. Groundwater saturation by
dissolution products leads to the formation of secondary minerals, changing the redox conditions. The conditions of
pyrite dissolution about 1 mol/kg content in the rock are considered in the current model. The saturation indexes of
ground waters are variable depending on pH: at pH <3 ferrous iron precipitates as melanterite (FeSO 4·7H2O), while
less acidity of the solution precipitated minerals containing trivalent iron, such as hematite (Fe2O3), goethite
(FeO(OH)) and ferrihydrite (Fe10O14 (OH)2). Melanterite solubility is variable: when the temperature is reduced
from 50 to 0oC, melanterite’s solubility decreases almost 6 times. The existence of redox, temperature, vaporizing
barriers causes cyclic nature of precipitation - dissolution of secondary minerals and formation of acidic waste-rock
waters.
The dependence of metals sum logarithm (Al3+, Fetot, Mn2+, Cu 2+, Zn 2+) from pH in samples from several mines
is displayed in fig. 1 (a). Two groups are compared: waste-rock waters that are more acidic and have increased
metals content and mine drainage waters.
The data showing the degree of main cations variability in mine drainage and waste-rock waters are presented in
fig. 1 (b). The components of under-dump and drainage waters of the Levikha and Degtyarsk mines are presented in
table 1. Waste-rock waters are acidic, and their anion composition is completely defined by sulphate-ion, which
reaches the concentration of 51 g/l. Iron, aluminum, and magnesium are the top common among cations. The
P.A. Rybnikov and L.S. Rybnikova / Procedia Earth and Planetary Science 17 (2017) 857 – 860 859

concentration of metals in waste-rock waters are very high: Fetot is 9.5 g/l, Al3+ is 2.7 g/l, Zn2+ is 581 mg/l, and Cu2+
is 479 mg/l.
Carbonate sediments are absent within the Levikha ore field; here the neutralization potential of acidic waters is
low, and thus, the mineral concentrations are higher than those within the confines of the Degtyarsk mine.

Table 1. The components composition of waste-rock and mine drainage waters of Levikha and Degtyarsk (mg/l).
Waste-rock water Mine water
Constituent of water
Levikha Degtyarsk Levikha Degtyarsk
Al3+ 2716 - 375 -
2+
Ca 335 252 260 258
Cu2+ 479 300 154 77
Fe2+ 9487 4710 730 551
Mg2+ 2724 420 340 267
Mn2+ 225 20 47 21
SO42- 51436 17940 5980 5570
Zn2- 581 750 317 4
TDS 61600 26600 11600 8540
pH 1.95 2. 0 2.75 2.68

Comparing to the waters draining mines, waste-rock waters are more mineralized (TDS is 3-5 times more). The
aluminum and iron concentrations are 7-8 times higher, and the copper and zinc concentrations are 3-4 times higher.
Considering that the composition of rocks forming waste-rock and mine drainage waters is similar, it can be
hypothesized that hydrogeochemical processes that lead to the waste-rock and drainage waters formation are
different.
The places that collect waste from the copper-pyrite mines are the source of acidic waters entering the
hydrosphere. Understanding the amount and the duration of waste release is essential for the prognosis and to
finding solutions for rehabilitation. To do such estimates, it is important to use the calculation of penetrating
contaminants in a time unit proceeding from the inverse simulation results 1. In this case, the results of underground
waters analysis are applied for calculation of the mass of dissoluted and precipitated minerals. Such calculations for
the Iron Mountain showed extremely high rates of sulphides weathering, 1.7·104 mol of pyrite per hour1.

Fig. 1. (a) the distribution of sum of metals concentration (Al3+, Fetot,, Mn2+, Cu2+, Zn2+) depending on pH; (b) basic cations content in waste-rock
and mine drainage waters.

The quantitative estimation of sulphides dissolution rate for the dumps of Levikha and Degtyarsk deposits was
performed using the program code Visual MINTEQ ver. 3.0/3.1. The results of solving inverse problems are shown
in table 2. In the process of forming acidic under-dump waters, sulphide dissolution in the amount of 214 and 106
mmol/kg takes place in these areas. Near the under-dump waters discharge that is 5 l/s, the rate of sulphides
dissolution is 1.9-3.6 ·103 mol/hour which is lower than in Iron Mountain, but still high for the waste water. The
overall volume of dumps accumulated in these mines is estimated approximately 3.5·106 m3, thus, complete sulphide
dissolution and environment pollution by acidic waters will continue for hundreds of years.
860 P.A. Rybnikov and L.S. Rybnikova / Procedia Earth and Planetary Science 17 (2017) 857 – 860

Table 2. Mass balance results for waste-rock stockpiles (precipitation – negative amount, dissolution – positive amount).

Mineral phase Levikha (mmol/kg) Degniarsk (mmol/kg)


Pyrite 200 90
Chalcopyrite 9 4
Sphalerite 5 12
Chrysotile 30 30
Kaolinite 5 25
Calcite 5 6
Quarz -150 -25
Goethite -62 -6

4. Conclusion

The waste-rock pile is a vertical structure that is a zone of oxidation with several subzones from top to down:
oxidation, leaching, and secondary enrichment3. In the zone of secondary enrichment, metals are taken out from
upper levels and are accumulating in the form of sulphides. The disintegration of rocks in the process of the
stockpile, filling and oxidation promote the growth of active surface of sulphides and infiltrated waters interaction.
The area occupied by piles is 1-2 km2, with the height of about 50 m4. The rate of water interchange is low, and the
precipitation, temperature gradient (the degree of surface exposition to frost) and evaporation are variable through
the year.
Mine drainage waters are formed within the depression cone that has a large area (tens of square kilometers) and
large depths (up to 600 meters). All hydrogeochemical and geomechanical processes initiated by dewatering are
reflected in the mine drainage water composition. These processes are the destruction of rocks when mine is in
operating; the infiltration of oxygen-rich water into dewatered mine rocks; the sulphides oxidation and the
composition of the rocks enclosing water. The features of forming mine waters chemical composition are: 1) vertical
temperature gradient, with temperature increase with depth; 2) the independence of the groundwater temperature
from seasonal changes; 3) high values of infiltration and flow gradient (due to a considerable depth of cone of
depression and constant pumping of groundwater). All these factors predetermine the high rate of mass exchange
within the limits of the mine field and, consequently, lower contents of components in mine water.

References

1. Nordstrom DK. Hydrogeochemical processes governing the origin, transport and fate of major and trace elements from mine wastes and
mineralized rock to surface waters. Applied Geochemistry. 2011. №26. P. 1777–1791.
2. Amos RT, Blowes DW, Bailey BL, Sego DC, Smith L, & Ritchie AIM. Waste-rock hydrogeology and geochemistry. Applied Geochemistry.
2015 №57. P. 140–156.
3. Emlin EF. Technogenesis of pyrite deposits of the Urals. Sverdlovsk: Publication of Ural State University. 1991 (in Russian).
4. Mormil SI, Salnikov VI, Amosov AL. Anthropogenic deposits of the Urals and their impact on the environment / ed. by Y. A. Borovkova.
Ekaterinburg: NIA – Priroda, DPR in the Ural region. AOOT VNIIZARUBEZHGEOLOGIA", geological enterprise "Devon". 2002 (in Russian).
5. Appelo CAJ, Postma D. Geochemistry, groundwater, and pollution. 2-nd edition. Rotterdam: Balkema, 2005.
6. Nordstrom DK, Blowes DW, Ptacek CJ. Hydrogeochemistry and microbiology of mine drainage: An update. Applied Geochemistry. 2015.
№57. P. 3–16

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