Accepted Manuscript

Physicochemical and Mineralogical Characterization of Musina Mine Copper and

New Union Gold Mine Tailings: Implications for Fabrication of Beneficial
Geopolymeric Construction Materials.

Gitari M. W, Akinyemi SA, Thobakgale R, Ngoejana PC, Ramugondo L, Matidza M, Mhlongo SE,
Dacosta FA, Nemapate N

PII: S1464-343X(17)30401-6

DOI: 10.1016/j.jafrearsci.2017.10.016

Reference: AES 3031

To appear in: Journal of African Earth Sciences

Received Date: 22 February 2017

Revised Date: 06 October 2017

Accepted Date: 16 October 2017

Please cite this article as: Gitari M. W, Akinyemi SA, Thobakgale R, Ngoejana PC, Ramugondo L,
Matidza M, Mhlongo SE, Dacosta FA, Nemapate N, Physicochemical and Mineralogical
Characterization of Musina Mine Copper and New Union Gold Mine Tailings: Implications for
Fabrication of Beneficial Geopolymeric Construction Materials., Journal of African Earth Sciences
(2017), doi: 10.1016/j.jafrearsci.2017.10.016

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 ACCEPTED MANUSCRIPT

Highlights
 Copper tailings leachates had alkaline pH (7.34-8.49) while the gold tailings had

acidic pH.

 Geochemical fractionation indicates that majority of the major and trace species

are present in residual fraction.

 A significant amounts of Ca, Cu and K was available in the mobile fraction and is

expected to be released on tailings contacting aqueous solutions.

 The SiO2/Al2O3 ratios indicates the tailings would require blending with Al2O3 rich

feedstock for them to develop maximum strength.

 Moreover, the tailings have particle size in the range of fine sand which indicates

potential application as aggregates in conventional brick manufacture.

 ACCEPTED MANUSCRIPT

1 Physicochemical and Mineralogical Characterization of Musina Mine Copper

2 and New Union Gold Mine Tailings: Implications for Fabrication of Beneficial
3 Geopolymeric Construction Materials.
4
5 a*Gitari M W, aAkinyemi SA, aThobakgale R, aNgoejana PC, aRamugondo L, aMatidza M,
6 bMhlongo SE bDacosta FA and bNemapate N.

7 aEnvironmental Remediation and Water Pollution Chemistry Group. Department of

8 Ecology and Resource Management, University of Venda. Private Bag x 5050
9 Thohoyandou 0950, mugera.gitari@univen.ac.za
10 bDepartment of Mining and Environmental Geology, University of Venda. Private Bag x
11 5050 Thohoyandou 0950, emmanuel.mhlongo@univen.ac.za
12
13 *Corresponding author email: mugera.gitari@univen.ac.za

14 Abstract
15 The mining industries in South Africa generates huge amounts of mine waste that
16 includes tailings; waste rocks and spoils. The tailings materials are dumped in surface
17 impoundments that turn to be sources of hazards to the environment and the
18 surrounding communities. The main environmental hazards posed by these tailings
19 facilities are associated with their chemical constituents. Exposure to chemical
20 constituents can occur through windblown dust, erosion to surface water bodies,
21 inhalation by human beings and animals and through bioaccumulation and bio
22 magnification by plants. Numerous un-rehabilitated tailings dumps exist in Limpopo
23 province of South Africa. The communities found around these mines are constantly
24 exposed to the environmental hazards posed by these tailing facilities. Development of
25 a cost-effective technology that can beneficially utilize these tailings can reduce the
26 environmental hazards and benefit the communities. This paper presents the initial
27 evaluation of the copper and gold mine tailings in Limpopo, South Africa with a view to
28 assessing the suitability of conversion into beneficial geopolymeric materials. Copper
29 tailings leachates had alkaline pH (7.34-8.49) while the gold tailings had acidic pH. XRD
30 confirmed presence of aluminosilicate minerals. Geochemical fractionation indicates that

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31 majority of the major and trace species are present in residual fraction. A significant
32 amount of Ca, Cu and K was available in the mobile fraction and is expected to be
33 released on tailings contacting aqueous solutions. Results from XRF indicates the tailings
34 are rich in SiO2, Al2O3 and CaO which are the main ingredients in geopolymerization
35 process. The SiO2/Al2O3 ratios indicates the tailings would require blending with Al2O3
36 rich feedstock for them to develop maximum strength. Moreover, the tailings have
37 particle size in the range of fine sand which indicates potential application as aggregates
38 in conventional brick manufacture.
39
40 Keywords: Copper tailings, Gold tailings, Sequential extraction, Geopolymer materials,
41 Leachates, Trace inorganic contaminants.
42 1. Introduction

43 South Africa mining industries generates huge amounts of mine tailings which are
44 disposed of in surface impoundments. These impoundments are a danger to the
45 environment and surrounding communities. Although the government has instituted
46 frameworks and environmental policies that guides disposal of mine tailings and
47 mitigation of environmental impacts, most of the current mine tailings facilities have a
48 mitigation plan in place and are required by law to rehabilitate the tailings dumps in a
49 such a way that they reduce the impact to the environment and surrounding community
50 at large (Hoadley et al., 2002; Limpitlaw et al., 2005). However, mine tailings facilities
51 that were in existence before enactment of this policy and regulations are still in
52 existence in most of the abandoned mines (Colvin et al., 2011). Several of these
53 abandoned mines and tailing facilities are found in rural Limpopo province of South Africa
54 and the surrounding communities are constantly exposed to the hazards posed by these
55 tailing facilities (Mhlongo et al., 2013; Auditor General-South Africa, 2009)
56 A technology that can utilize these tailings in a beneficial way would solve a huge
57 environmental challenge posed by these tailing dumps. Moreover, current mining houses
58 spend a lot of money managing these tailings facilities. One such technology would be
59 beneficiation into geopolymer construction materials suitable for utilization in road or for
60 construction of low cost houses. A visit to one of the abandoned copper mine tailings

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61 dumps in Musina Limpopo province informs us (personal communication: community

62 members, Oct. 2013) that the tailings materials are being used currently by the
63 community members for construction of foundation for their houses, indicating that this
64 material could be a suitable candidate for application in construction (Figure 1).
65
66 Several studies elsewhere in the world have observed that copper mine tailings can be
67 converted or utilized in environmental friendly construction materials through
68 geopolymerization (Ren et al., 2014; Oluwasola et al., 2014; Tarig and Yanful, 2013;
69 Yun Wang Choi et al., 2009; Ahmari and Lianyang, 2012). Geopolymerization is a
70 relatively new technology that utilizes high alkaline conditions at room temperature or
71 slightly elevated temperatures to transform aluminosilicate material into geopolymers.
72 This is a useful product that can be used in construction. The geopolymerization is also
73 credited with stabilizing toxic metal species in mine tailings in an environmental benign
74 way (Mendez et al., 2008; Van Jaarsveld et al., 2000). It is postulated that geopolymer
75 gels formed during the alkali activation of Al-Si rich materials bind the mine tailing
76 particles together.
77 The geopolymer consists of an amorphous binder with a polymeric network structure
78 consisting of repeating units of Al, Si, and O (- Si – Al - O -). Researchers (Skyaraa et
79 al., 2009; Yusheng et al., 2007) have pointed out that geopolymers offer superior
80 mechanical properties, rapid strength development compared to ordinary Portland
81 cement (OPC) based binders, resistance to attack by corrosive agents and efficient
82 immobilization of mine tailing contaminants. Moreover, the binding of contaminants
83 reduces the hazard of leaching of contaminants and subsequent negative impacts on the
84 environment and makes the utilization of the material environmentally safe. This paper
85 presents an initial evaluation on the suitability of selected gold and copper mine tailings
86 in Limpopo for utilization in fabrication of beneficial geopolymeric materials.
87
88
89
90

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91 2. Materials and methods

92
93 2.1 Samples description and sampling technique
94 Copper mine ore was processed in an erected concentrator, and copper concentrates
95 were recovered by flotation thickening, and the waste was discharged from the
96 concentrator and disposed at the tailings dump. The abandoned copper tailings dump in
97 Musina has been exposed to weathering for a period of 25 years (Matshusa and Makgae,
98 2014). The Musina mine tailings dump is situated between longitude 29⁰ 54’ E and
99 latitude 22⁰16’ S. Copper mine tailings were collected from Musina copper mine tailings
100 facility in Musina. The mine tailings were sampled from five randomly selected points in
101 the facility code-named S1, S2, S3, S4 and S5. The copper mine tailings were obtained
102 by hand augering to various depths and preserved in polyethylene plastic bags. The New
103 Union gold mine is located between Latitude 23º 1’ 2’’ S and Longitude 30º 43’ 44’’E
104 Limpopo, South Africa. Representative gold tailings samples obtained from the New Union
105 gold mine tailings facility in Malamulele.

106 Gold mine tailings samples were collected by scooping with a shovel to a depth of 1 m
107 followed by storage of the samples in tightly sealed and oxygen diffusion-free
108 polyethylene plastic bags.
109
110 2.2 X-ray Fluorescence Analysis
111 The samples were milled in a tungsten - carbide milling pot to achieve particle sizes of
112 <75 <mu>m. The samples were dried at 1000C and roasted to determine Loss On Ignition
113 (LOI) values. One gram of the samples was mixed with six grams of Lithium tetraborate
114 flux and fused at 1050C to make a stable fused glass bead. The Thermo Fisher ARL
115 Perform 'X Sequential XRF (Thermo Fisher Scientific, USA) with OXSAS software was used
116 for analyses. The analysis was triplicated on one samples from each tailing. The technique
117 reports the major elements concentration in % and trace elements in ppm.

118 2.3 Pore water chemistry

119 Paste pH and Eh were determined by weighing 20 g of air-dried and homogenized wash-
120 out samples and adding 20 ml of distilled water until a slurry was obtained. After mixing

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121 for 5s the slurry was left to stand for 10 min. The pH/EC electrodes were then inserted in
122 the slurry and after swirling slightly the pH and Eh were measured until a constant value
123 was obtained. For generation of leachates, a 10 g tailings wash-out sample was
124 suspended in a 100 ml MilliQ water in plastic bottles. Sample suspensions were agitated
125 in a shaker for 24 hrs at a temperature of 22 ± 3oC, at 200 rpm, until a stable reading of
126 pH and electrical conductivity (EC) was obtained. After shaking, and after pH/EC
127 stabilization, the batches were centrifuged at 2,500×g for 20 mins, and filtered through a
128 0.45 µm pore membrane filter. The clear aqueous extract was divided into two
129 subsamples and the procedure were duplicated. One was acidified to pH < 2 by HNO3 for
130 cation analysis using ICP-MS, and the other was left unacidfied for anion analysis using
131 850 professional IC (Metrohmn, Switzerland).

132 2.4 X-ray Diffraction and Optical Microscopy Analyses

133 A bulk mineralogical composition of both copper and gold tailings were determined using
134 Philips PANalytical instrument (PANalytical, The Netherlands) with a pw3830 X-ray
135 generator operated at 40 kV and 25 mA was used. The tailing samples were oven-dried
136 at 1000C for 12 hrs to remove the adsorbed water. The samples were pressed into
137 rectangular aluminium sample holders using an alcohol wiped spatula and then clipped
138 into the instrument sample holder. The samples were step-scanned from 5 to 85 degrees
139 2 theta scale at intervals of 0.02 and counted for 0.5 sec per step.
140 The procedure for the quantitative XRD according to Akinyemi et al. (2012) are as follows:
141 After addition of 20% elemental silicon (Aldrich 99.9%) for quantitative determination of
142 amorphous compounds, and micronizing in a McCrone micronizing mill. A 1 gram of less
143 than 20 µm sized tailing samples were used for XRD analysis using a back-loading
144 preparation method. They were analysed with a PANalytical X’Pert Pro powder
145 diffractometer (PANalytical, The Netherlands) in θ–θ configuration with X’Celerator
146 detector and variable divergence- and fixed receiving slits with Fe filtered Co-Kα radiation
147 (λ=1.789Å). The phases were identified using X’Pert Highscore plus software. The relative
148 phase amounts (weights %) were estimated using the Rietveld method (Autoquan
149 Program).

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150 Thin section was made from samples by preparing a thin slice of about a centimetre thick
151 with a diamond saw. The slice was glued to glass slide and further thinned with diamond
152 saw. The slide was progressively grinded with finer abrasives for further thinned. A thin
153 cover was glued to the top of the slice to complete the thin section when a thickness of
154 0.03 mm was achieved. Thin sections of each sample were examined using a conventional
155 optical polarizing microscope known as Eclipse LV100 Polarizing (Nikon Instruments Inc.,
156 Americas).

157 2.5 Geochemical Fractionation

158 A three-step sequential extraction method proposed by the European Community Bureau
159 Reference (BCR) (Rauret et al., 1999; Tokalioglu et al., 2003) was adopted for this study.
160 The summary of BCR protocol adopted in this study is shown in Table 1.
161 2.5.1 Water/acid soluble and Exchangeable fraction: The exchangeable fractions consist
162 of weakly adsorbed metals such as K, Ca, and Mg which show high mobility under acidic
163 conditions and readily bioavailable to the environment (Tessier et al., 1979). Tessier et
164 al. (1979) showed that high mobility of metals in this fraction is pH dependent, and metals
165 are bound to the solid surface by relatively weak electrostatic interaction. Besides, Okoro
166 et al. (2012) verified that metals in this fraction can be easily released by ion exchange
167 processes, and can also be co-precipitated with carbonates present in the solid waste.
168 Nonetheless, the most extensively used chemical reagents for extracting metals bound
169 to the exchangeable fraction are acetate and chlorite salts, ammonium salts and nitrate
170 salts (Filgueiras et al., 2002). Acetate (NH4OAc) and chlorite (MgCl2) salts at 1 M
171 concentration have been the most widely used reagents (Tessier et al., 1979).

172 2.5.2 Reducible or Fe oxides fraction: It is well documented that iron and manganese
173 oxides exists as nodules, concretions, cement, or coatings between particles (Tessier et
174 al., 1979). These oxides have been stated to be excellent scavengers for potentially toxic
175 elements species due to their greater adsorption capacity, and are thermodynamically
176 unstable under anoxic geochemical conditions i.e., they dissolve as the redox potential
177 decreases (at low Eh) and re-precipitate as the geochemical environment becomes
178 oxygenated (Hiller et al., 2013). Though, the scavenging of potentially toxic elements

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179 species by Fe and Mn oxides can occur as a combination of precipitation, adsorption,

180 surface complex formation, and ion exchange (Hall et al., 1999).

181 In principle, the reducible fraction could be split into three fractions; easily reducible
182 fraction (Mn oxides), moderately reducible fraction (amorphous Fe oxides), and poorly
183 reducible fraction (crystalline Fe oxides) (Hall et al., 1999). Nevertheless, this
184 classification is addressed in a few schemes, and in the present study this classification
185 was considered for a single extraction, as agreed by some authors (Tessier et al., 1979;
186 Lu et al., 2014). Several chemical reagents at 0.25 M concentration of hydroxylamine
187 hydrochloride (NH2OH.HCl) in 0.25 M HCl or in 25% (v/v) acetic acid (HOAc) have been
188 widely employed for the extraction of metals bound to Fe and Mn oxides (Tessier et al.,
189 1979; Chao and Zhou, 1983).

190 Chao and Zhou (1983) compared the efficiency of these chemical reagents to dissolve
191 the amorphous and poorly crystalline iron oxides. They reported that the extraction of
192 these oxides by hydroxylamine hydrochloride (NH2OH.HCl) in 0.25 M HCl depends on acid
193 concentration and the temperature of the reaction. At elevated temperatures,
194 hydroxylamine hydrochloride (NH2OH.HCl) in 0.25 M HCl can attack primary and
195 secondary silicate minerals although managed to dissolve 60% of the tested minerals,
196 temporarily at room temperature, this reagent seemed to be specific and dissolve 1 to
197 2% of the minerals tested. However, the extraction of these oxides by 0.25 M
198 concentration of hydroxylamine hydrochloride (NH2OH.HCl) in 25% (v/v) acetic acid
199 (HOAc) demonstrated that at 70ºC dissolved 1 to 4% of the crystalline Fe oxides,
200 depending on the reaction time. Chao and Zhou (1983) further indicated that a longer
201 reaction time can overestimate the amorphous Fe oxide fraction. Nevertheless, they
202 concluded that a better reaction time for the use of hydroxylamine hydrochloride
203 (NH2OH.HCl) in 25% (v/v) acetic acid (HOAc) as an extractant is 90 min with < 2% of
204 the crystalline Fe oxides dissolved.

205 2.5.3 Bound to sulphides and organic fraction: Trace metal may be bound to various
206 forms of organic matter such as living organisms, detritus, or coatings on mineral
207 particles, through bioaccumulation or process (Okoro et al., 2012). This fraction is
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208 considered as the immobile fraction and the extracts obtained from this fraction are
209 metals bound to sulphides under oxidizing conditions. However, according to Filgueiras
210 et al. (2002) the organic matter can be degraded under oxidizing conditions leading to
211 the release of soluble trace metals, although the organic fraction released is considered
212 not to be bioavailable since it is thought to be associated with stable humic substances
213 that release small amount of trace metals in a slow manner. Several chemical reagents
214 have widely been used for the dissolution of sulphide minerals or trace metals bound to
215 the organic fraction, and these include H2O2-asorbic acid, oxalic acid, mixture of
216 KClO3/HCl, mixture of KClO2/HCl followed by 4 M HNO3 (Tessier et al., 1979). However,
217 Chao and Sanzalone (1977) observed that a mixture of KClO2/HCl followed by 4 M HNO3
218 leach was most efficient in dissolving sulphides such as pyrite, galena, cinnabar, and
219 chalcopyrite, although there is a probability of causing partial destruction of silicates along
220 the edges and surfaces. As such to overcome this drawback Chao (1984) reported that
221 the H2O2-asorbic acid leach will not attack other mineral phases such as silicates. The
222 H2O2-asorbic acid leach is also prescribed by Tessier et al. (1979).
223
224 2.5.4 Bound to residual or silicate fraction: The residual fraction comprises mainly primary
225 and secondary minerals which may retain high quantity of trace metals within their crystal
226 structure. This fraction is also considered as the immobile fraction and the trace metals
227 retained are not expected to be released into solution in the long term, however care
228 must be taken since any change in the geochemistry (acidic conditions) may cause them
229 to be displaced to more mobile fractions, thereby increasing their mobility and availability
230 (Arenas-Lago et al., 2014). Nevertheless, this fraction is commonly dissolved with highly
231 concentrated acids such as HNO3, HF, HClO4, HCl and species digestion procedures
232 (Okoro et al., 2012).

233 2.6 Total acid digestion

234 To validate the results, a total acid digestion with aqua regia of the tailings was carried
235 out in a procedure like step D. 0.5 g of tailing samples were put in a volumetric flask and
236 36 ml of the aqua regia (HCl: HNO3: 3:1) added. The volumetric flask was covered with
237 watch glass to reduce the rate of evaporation and loss of metal species. The mixture was

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238 then put on a hotplate for 90 minutes at a temperature of 110°C. After boiling the
239 mixture to near dryness, it was then left to cool, then was diluted with 10 mL of 20% v/v
240 HNO3. The mixture was then filtered and put in 100 mL polyethylene bottles which were
241 then filled up to the mark with MilliQ water. The mixture was analysed for metal cation
242 by ICP-MS for trace elements and ICP-AES for major elements for accuracy.
243
244 3. Results and Discussions
245
246 3.1 Paste and leachates physical parameters
247 The copper tailings were dark grey in color, weakly altered with an alkaline to high alkaline
248 paste pH values (pH = 8.67- 9.11). This is mainly because of the abundance of alumino-
249 silicate minerals, such as chlorite, muscovite, biotite, and the relative scarcity of sulfide
250 minerals. The presence of neutralizing or pH buffering minerals such as alumino-silicates
251 in the tailings plays a significant role in mitigating the effects of acidic leachate effluent.
252 As expected the measured paste Eh values were lower in the tailings sample (Eh = -126.9
253 to -105.3 mV), mainly indicating a reducing environment. The copper tailings leachates
254 had pH (8.44-8.52) and EC (125.13 µS/cm). The gold tailings samples had leachate pH
255 (2.6-2.9), EC (125.7-203.3 µS/cm) and TDS (79.6-130.8 mg/L). The gold tailing leachates
256 were highly acidic, this could be due to presence of sulphidic minerals in the host rock
257 that was undergoing oxidation with release of sulphuric acid.
258 3.2 Chemical composition of tailing samples
259 Table 2 presents the chemical composition of the gold and copper mine tailings. Both
260 gold and copper tailings recorded high SiO2 content and significant levels of Al2O3. This
261 indicates the presence of aluminosilicate minerals in both tailings which are crucial for
262 geopolymerization. High concentrations of MgO, CaO, Na2O, and K2O were observed in
263 both materials which could indicate presence of soluble basic components. These soluble
264 basic oxides could contribute to the acid neutralization potential of the investigated
265 tailings dumps.
266
267 It is noted that the gold tailings had double the concentrations of Fe2O3 compared to
268 copper tailings and this, coupled with the high S content could be indicative of the
269 presence of pyrite and other Fe sulphide minerals. This could explain the low pH of the

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270 gold tailings leachates. A high CaO content in the copper tailings is observed that could
271 explain the alkaline pH of the leachates. The alkaline pH of the copper tailings leachates
272 could also be an indication that the Fe present is not inform of pyrite or other Fe sulphide
273 minerals. Of interest in geopolymerization of the gold tailings would be the behavior of
274 the pyrite/sulphide minerals, sulphate and the role they would play in the mineral phases
275 formation, during the geopolymerization process and the strength development of the
276 final geopolymer product.

277 3.3 Leachate and paste chemical parameters

278 Table 3 presents the chemical composition of leachates generated from the gold and
279 copper mine tailings. The results give an indication of the chemical constituents that are
280 likely to be present in the generated plume after a rainfall event and the rainwater
281 interaction with the tailings and the potential risk to surface and groundwater
282 contamination. The leachates from the gold tailings were highly acidic but the mobility
283 of metal species was rather low with concentrations being in the ppb range. This would
284 be an indication that most of the metal species are immobilised in the non-labile
285 geochemical fractions. Basic metal species Ca, Mg, and K were present in high
286 concentrations in addition to Fe and Mn. The concentration of As, Se, Sr, Pd, Si, Sn, Au
287 were all below 0.02 µg/L in the gold tailing leachates. The copper tailings leachates
288 recorded higher concentrations than the gold tailings with K, Mg, P, Si, Cl-, F-, NO32-, and
289 SO42- concentrations being in the ppm range (Table 3). The relatively high concentration
290 of heavy metals in the leachate from copper tailing than gold tailing is attributed to
291 alkaline pH of copper tailing leachates. This is validated by the presence of calcite and
292 aluminosilicate minerals which are potential acid neutralizer in the copper tailings.
293 The concentrations of all the chemical species in both the tailings leachates and paste
294 slurry were of the same order of magnitude for the copper tailings (paste data not shown).
295 Al and Fe were the metal species which recorded the highest water-soluble
296 concentrations (985.53 µg/L and 1756.34 µg/L, respectively). Water-soluble
297 concentrations of selected metal species decreased in the order: Cu > Mn > Cr > Zn >
298 Cd > Ni.
299

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300 3.4 Mineralogical composition

301 The mineralogical composition based on qualitative X-ray diffraction of bulk samples for
302 copper mine tailings is shown in Figure 2. The primary minerals are quartz (SiO2), epidote
303 (Ca2(Fe,Al)Al2(SiO4)(Si2O7)O(OH)), clinochlore ((Mg,Fe2+)5Al2Si3O10(OH)8), albite
304 (NaAlSi3O8), muscovite (KAl2(AlSi3O10) (F, OH)2), calcite (CaCO3), and occurrence of
305 secondary mineral such as hematite (Fe2O3) (Fig. 2). Quantitative X-ray diffraction
306 analysis confirmed the following mineral phases in copper tailings: calcite, chlorite (Mg,
307 Fe, Li)6 AlSi3O10(OH)8, epidote, hematite, hornblende((Ca,Na,K)2-
3(Mg,Fe
308 2+,Fe3+,Ti,Al) (Si,Al) O (OH,F), muscovite, plagioclase (Na,Ca)(Si,Al)4O8), and
5 8 22

309 quartz. Quartz and epidote occurred in the highest concentration for the copper tailings
310 at ≈49.53% and ≈22.60% respectively (Table 4).
311 X-ray diffraction analysis of bulk samples identified the following mineral phases in the
312 gold mine tailings: quartz, chlorite, magnetite, Jarosite (KFe3+3(OH)6(SO4)2), pyrophyllite,
313 albite, clinochlore ((Mg, Fe2+)5 Al2Si3O10(OH)8), and sepiolite (Mg4Si6O15(OH)2•6(H2O))
314 (Fig. 3). The quantitative X-ray diffraction analysis confirmed the presence of
315 anthophyllite (Mg3Si4O10(OH)2), chlorite, hornblende, Jarosite, magnetite (Fe3O4),
316 plagioclase, quartz, and sepiolite. Quartz was observed to occur in the highest
317 concentration (≈42.98%) followed by hornblende (≈14.10%) (Table 4). The presence of
318 Jarosite which is an iron-sulfate mineral, in soil or in mining waste indicate acidic or
319 sulphate rich conditions (Novhe et al., 2014). Aluminosilicate minerals such as muscovite,
320 chlorite and plagioclase are considered as potential acid neutralizers, but to a much lesser
321 extent and reaction rate compared to carbonate minerals such as calcite (Jambor, 2003).
322 Quartz on the contrary had no potential of acid neutralization, and this is mainly due to
323 its physical property (hardness) (Kwong, 1993 as referenced in Novhe et al., 2014).
324 Optical microscopy analysis confirmed the presence of Al, Fe, Ca, K and Mg containing
325 minerals such as chalcopyrite, bornite, biotite, and silicate gangue minerals and quartz
326 (Fig. 4). This confirms observations by X-ray diffraction analysis on the presence of
327 quartz and other Al-Si bearing mineral phases. Analysis carried out on several samples
328 confirmed the dominance of the aluminosilicate minerals and calcite which are were
329 thought to contribute to the high alkalinity of the copper tailing leachates (Tables 4 and

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330 2). Optical microscopy and XRD confirms both mine tailings consist of Al-Si bearing
331 mineral phases in significant quantities and could easily be used as feedstock for
332 geopolymer products.
333
334 3.5 Geochemical fractionation of tailings
335
336 Samples obtained by depth in the copper tailing dump and on the surface for the gold
337 tailing dump were subjected to sequential fractionation as described in the section 2.5.
338 This was done to give an indication of the mobility/bioavailability of metal species in the
339 tailings.
340 Figure 5 shows the results of sequential fraction of major metal species for the copper
341 mine tailings by depth for a selected site. In this work F1 (exchangeable fraction) + F2
342 (Iron and Manganese oxide fraction) + F3 (Organic matter and Reducible fraction)
343 represents the total metal fraction associated with the mobile phase and F4 (residual
344 fraction) with non-labile phase. For all the major species (Al, Ca, Fe, K, Mg) > 60% of
345 the concentrations was available in the residual fraction. However, a significant % of Ca,
346 Cu, K (8-90%) was available in the mobile fraction and is likely to be released on tailings
347 contacting aqueous solutions. Ca and K are most likely present as soluble salts. XRD
348 identified presence of calcite in the copper tailings.
349
350
351 High concentration of Cu could be attributed to the extraction process of Cu during the
352 ore processing that released Cu from the host rock. The processing would have led to
353 enrichment of copper in more labile phases especially during the high temperature
354 generated during grinding and during washing and concentration processes.
355 The partitioning pattern of Al, Ca, Fe, K, and Mg are obviously unaffected along depth.
356 This could indicate uniformity in the tailings generated in the ore processing. Moreover,
357 it could also indicate insignificant transformation or mobility of the tailings due to
358 influence of oxidation/weathering process. An explanation for this would be lack of
359 enough medium for reactions and mobilization due to low rainfall prevalent in Musina.
360 Cu recorded a higher % content in the mobile fraction at all depths (>80% content).
361

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362 Figure 5 shows the results of sequential fraction of minor and trace metal species for
363 the copper mine tailings by depth for a selected site. For minor and trace species, a
364 significant proportion was partitioned in the non-mobile fraction. However, the
365 proportion in the mobile fraction increased with depth especially for As, Se, Mo.
366 Molybdenum was the most mobile of the trace species with > 75% content in the mobile
367 fraction. This could be explained by the prevalent alkaline conditions where As, Se and
368 Mo exists as mobile oxyanionic species. Ti, Cr, Co, and Ni had the highest % content
369 (>90%) in the residual fraction indicating their non-availability in the easily leachable
370 fraction.
371
372 The general distribution among fractions is shown in Table 5. Only Cu was found mostly
373 concentrated in the exchangeable fraction followed by iron and manganese oxide.
374 Furthermore, metals such as K, Ni, Mg, Ca and Mn are mostly present in the residual
375 fraction followed by the exchangeable fractions of the tailings. This indicates that Cu and
376 K, Ni, Mg, Ca and Mn are weakly absorbed on the soil surface (such as clay minerals,
377 organic matter, and hydrous oxides) by relatively weak electrostatic interaction or by
378 precipitated or coprecipitated with the carbonates in the tailings (Filgueiras et al., 2014).
379

380 The mobility of the investigated metals copper tailings was calculated by using an
381 equation as described by Kabata-Pendias (2001). Mobility Factor (MF) =
382 [F1/(F1+F2+F3+F4) x 100]. The estimated mobility factor for all investigated analytes in
383 the copper tailings are shown in Table 6. The average mobility factor for investigated
384 metals such as Ti, Cr, Co, Ni, Zn, As, Se, Mo, Al, Fe, and Mg are less than 10%. This
385 suggests that these metals are least mobile and are stable in the copper tailings hence
386 less environmental risk. On the contrary, the average mobility factor for metals such as
387 Cd, Ca, Cu, Mn, and K are far greater than 10% which suggest highly mobile and are
388 unstable in the copper tailings thereby susceptible to leaching.

389 Metals such as As, Se, Fe and Al are mostly concentrated in the residual fraction followed
390 by iron and manganese oxide fraction. Therefore, these metals are expected to be found
391 as precipitates in reducible forms in the mining residues. Metals such as Cd, Zn, and Ti

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392 were abundant in the residual followed by organic matter and reducible fraction. There
393 are predominance of Cr and Mo in the residual fraction after that is organic matter and
394 reducible fraction of the tailings. In this study, cobalt shows abundant concentration in
395 the residual fraction and followed by iron and manganese fraction. Sequentially extraction
396 results show that As, Se, Cr, Co, Ni, Fe, Mn, Ca, Mg, K, Al, Cd, Zn and Ti have the lowest
397 environmental availability being mostly concentrated in the least mobile fraction (i.e.
398 residual). Elevated concentrations of arsenic in the residual fraction of of tailings is
399 consistent with previous studies using BCR extraction techniques (Luo et al., 2008; Li et
400 al., 2016).

401 On the other hand, Cu may be mobilised by a decrease in pH

402 leading to an ion exchange process. It is evident from the sequential extraction results
403 that a significant proportion of metals were immobilised in the non-labile phase (i.e.
404 residual fraction), indicating a low potential environmental risk. Therefore, the tailings
405 may potentially be used beneficially e.g. for geopolymerisation

406 3.6 Geopolymerization potential of mine tailings: Comparison of tailing

407 chemistry with feedstock applied in geopolymers.
408
409 3.6.1 Introduction to geopolymerization process
410 The concept of geopolymerization was first described by Davidovits (1976) as a family of
411 mineral binders closely related to artificial zeolites. They consist of Si-O-Al framework
412 similar to zeolites and are amorphous. Geopolymer binders are formed by the co-
413 polymerization of silica and alumina species dissolved from high Si and Al feedstock at
414 high pH. They depend on this copolymerization to attain structural strength. Several
415 authors (Khale and Chaudhary, 2007; Davidovits, 1994; Malone et al., 1986; Purdon,
416 1940; Glukhovsky et al., 1980) have investigated the chemistry, reaction mechanisms
417 and structural formation of geopolymers. They all agree that geopolymerization involves
418 dissolution of Al-Si from the source materials and formation of calcium aluminosilicate
419 hydrates to produce zeolite-like products of various compositions. Davidovits (1994)
420 further proposed that the hardening mechanism involves polycondensation of
421 geopolymeric precursors such as alumino-silicate oxides with alkali polysilicates to yield

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422 polymeric Si-O-Al bonds. The scheme of reactions below represents the process of
423 geopolymerization (Figure 6).

424 3.6.2 Chemistry of feedstock materials: A comparison of chemical composition

425 Materials rich in silica and alumina that dissolves in alkaline solutions have been used as
426 feedstock for geopolymerization. These include:
427  Waste materials such as coal fly ash (Ayaso et al., 2008; Hamid et al., 2015;
428 Boke et al., 2015), blast furnace slag and cement kiln dust (Ahmari and
429 Lianyang, 2013)
430  Natural materials such as kaolinite, feldspar, albite (Jaarveld et al., 2002)
431  Mine tailings (Ahmari and Lianyang, 2012)

432 Several authors have reported conversion of waste materials such as copper mine
433 tailings, blast furnace slag, cement kiln dust alone or in combination to eco-friendly bricks
434 or other geopoplymer products (Ahmari and Lianyang, 2012). Table 7 depicts the
435 chemistry of various materials applied in geopolymerization compared to mine tailings in
436 South Africa. Zhang et al. (2011) observed that Si/Al ratio is one of the most important
437 factors that affect geopolymerization. He further points out that a geopolymer of
438 maximum strength is obtained with Si/Al ratio in the range of 1-3. This is collaborated
439 by other researchers. Cheng and Chiu (2003) observed Si/Al ratio of 1.58-1.73
440 (SiO2/Al2O3) resulted in maximum strength for metakaolin and blast furnace mixtures.
441 An observation of the SiO2/Al2O3 ratios of the South African mine tailings indicates that
442 they can be successfully converted in geopolymeric materials but to attain maximum
443 strength they will require blending with material rich in Al2O3.
444 Geopolymers in comparison to ordinary portland cement (OPC) have advantages such
445 as rapid development of mechanical strength, high acid resistance, no/low alkali-silica
446 reaction expansion, excellent adherence to aggregates, immobilization of toxic and
447 hazardous materials and greenhouse gas emissions (Ahmari and Lianyang, 2012). Van
448 Jaarsveld et al. (1996) summarises the potential practical application of geopolymers
449 such as pre-casting for non-specific applications such as fences, paving materials, low
450 cost pipes and building components such as bricks, ceramic tiles, and cement. These

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451 studies have proven that waste materials such as silica and alumina rich tailings can
452 successively be converted into beneficial products and contribute to economic
453 development within communities hosting these tailings facilities and make available the
454 land occupied by the tailings for other developments.
455 4. Conclusions
456
457 A physicochemical and mineralogical appraisal of gold and copper mine tailings in
458 Limpopo has been carried out. The copper tailings leachates had pH in the range (8.44-
459 8.52) and EC (125.127.1 µS/cm) while gold tailings leachate pH ranged (2.6-2.9), EC
460 (125.7-203.3 µS/cm) and TDS (79.6-130.8 mg/L). The gold tailing leachates were highly
461 acidic due to presence of sulphidic minerals in the host rock that was undergoing oxidation
462 with release of sulphuric acid. The copper tailings were rich in alumino-silicate minerals
463 and low sulfide minerals hence the alkaline pH. Although the leachates from the gold
464 tailings were highly acidic and the mobility of metal species was rather low with
465 concentrations being in the ppb range. Basic metal species Ca, Mg, and K were present
466 in high concentrations in addition to Fe and Mn. The copper tailings leachates recorded
467 higher concentrations than the gold tailings with K, Mg, P, Si, SO42-, NO32-, Cl-, and F-
468 concentrations being in the ppm range. Al and Fe were the metal species which recorded
469 highest water-soluble concentrations (985.53 µg/L and 1756.34 µg/L, respectively).
470 Water-soluble concentrations of selected metal species decreased in the order: Cu > Mn
471 > Cr > Zn > Cd > Ni. Both gold and copper tailings recorded high SiO2 content and
472 significant levels of Al2O3. This indicates the presence of aluminosilicate minerals in both
473 tailings which are crucial for geopolymerization. Of interest in geopolymerization of the
474 gold tailings would be the behavior of the pyrite/sulphide minerals, sulphate and the role
475 they would play in the mineral phases formation, during the geopolymerization process
476 and the strength development of the final geopolymer product. Majority of the major
477 species were present in the residual fraction except Cu, Ca and K which are likely to be
478 released in leachates. Most of the Cu could have been transformed into the labile form
479 during the extraction and ore concentration process. For minor and trace species, a
480 significant fraction of As, Se, Mo was observed in the mobile fraction. This could be due
481 to existence of the species in oxyanionic form in the alkaline conditions prevalent in the

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482 tailings. The estimated mobile factor indicates that Ti, Cr, Co, Ni, Zn, As, Se, Mo, Al, Fe
483 and Mg are least mobile and are stable in copper tailings. On the other hand, chemical
484 species such as Cd, Ca, Cu, Mn and K are highly mobile and are unstable. Besides, the
485 concentration of the chemical species was observed to be mainly present in the residual
486 fraction and hence does not pose risk to their utilisation. A comparison of the chemical
487 composition of the mine tailings with other feedstock materials for geopolymers indicate
488 that they have potential for conversion into geopolymeric materials.
489
490 5. Acknowledgements
491
492 The authors would want to acknowledge the support from ESKOM Foundation, NRF and
493 THRIP for funding this study through student bursaries and consumables.
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1

Figure 1a: Excavation of copper mine tailings for construction by local community; b:
Erosion of the copper mine tailings; c: Eroded walls of the copper mine tailings storage
facility (Musina, Limpopo).

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2

Figure 2: X-ray powder diffractogram of copper tailings sample (Q=Quartz, E= Epidote,

C= Clinochlore, H=Haematite, A=Albite, M=Muscovite and C = Calcite).

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3

Figure 3: X-ray diffraction of bulk samples for gold mine Tailings.

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4

Figure 4: presents microphotographs of polished thin sections of the copper mine tailings
and mineral phases identified under transmitted polarized light.

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5

Figure 5: % major metal species content in various geochemical fractions for the copper
mine tailings (F1-exchangeable fraction, F2-Iron and Manganese oxide, F3-Organic
matter and Reducible, F4-Residual).

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6

Figure 5: % minor and trace metal species content in various geochemical fractions for
the copper mine tailings (F1-exchangeable fraction, F2-Iron and Manganese oxide, F3-
Organic matter and Reducible, F4-Residual)

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7

Figure 6: Formation and polycondensation of various geopolymer precursors (After Khale

and Chaudhary, 2007).

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Table 1: The summative BCR protocol adopted in this study

BCR Extraction conditions Target phases Analytical

Step techniques
STEP A 0.11 M Acetic acid, adjusted to Water/acid soluble and ICP-MS and
pH 7 exchangeable ICP-AES
STEP B 0.5 M Hydroxylamine Reducible i.e. bound to Fe "
hydrochloride, adjusted to pH2 oxides
with HNO3
STEP C 8.8 M Hydrogen peroxide + 1 Oxidisable i.e. bound to "
M Ammonium acetate sulphides and organic
phases
STEP D Aqua Regia (3HCl: 1HNO3) Residual i.e. bound to "
silicates

ICP-MS = Induced Coupled Plasma-Mass Spectrometry; ICP-AES = Induced Coupled

Plasma – Atomic Emission Spectroscopy

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Table 2. Chemical composition of the gold and copper mine tailings samples (n = 5)

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Table 3: Chemical composition of leachates generated from Copper and Gold mine
tailings (WHO = World Health Organisation) (n = 2)

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Table 4: Quantitative XRD analytical results showing average mineralogical

compositions of copper and gold mine tailings (n = 5)

Sample Copper tailings Gold tailings

Minerals Weight% 3σ Error Weight% 3σ Error
Anthophyllite - - 6.03 1.62
Calcite 1.63 0.30 - -
Chlorite 13.10 0.83 2.90 1.26
Epidote 22.60 0.85 - -
Haematite 1.13 0.31 - -
Hornblende 3.24 0.91 14.12 1.11
Jarosite - - 7.69 0.96
Magnetite - - 3.64 0.39
Muscovite 4.75 0.65 - -
Plagioclase 7.61 0.85 13.26 1.44
Quartz 49.53 1.01 42.98 1.86
Sepiolite - - 9.38 1.16
Total 100 100

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Table 5: Average distribution of elements in geochemical fractions of tailings. F1 =

Exchangeable, F2 = Iron and Manganese oxide, F3 = Organic matter and Reducible, and
F4 = Residual.

Elements Distribution in geochemical

fractions
As F4 > F2 > F3 > F1
Se F4 > F2 > F3 > F2
Mo F3 > F4 > F2 > F1
Cd F4 > F3 > F2 > F1
Cr F4 > F3 > F2 > F1
Cu F1 > F2 > F4 > F3
Fe F4 > F2 > F3 > F2
Mn F4 > F1 > F2 > F3
Ca F4 > F1 > F2 > F3
Mg F4 > F1 > F2 > F3
Al F4 > F2 > F3 > F2
Co F4 > F2 > F1 > F3
Ni F4 > F1 > F2 > F3
Zn F4 > F3 > F2 > F1
Ti F4 > F3 > F2 > F1
K F4 > F1 > F2 > F3

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Table 6: Calculated mobility factor (MF) of metals in copper tailings

Fractions Ti Cr Co Ni Zn As Se Mo
F1 11.50 53.86 8.45 40.95 123.88 0.48 2.63 2.25
S1
F1+F2+F3+F4 31096.36 1485.47 369.50 808.67 810.26 17.18 66.70 52.43
MF 0.04 3.63 2.29 5.06 15.29 2.79 3.94 4.29
F1 32.52 52.52 14.35 85.23 70.63 1.26 3.09 0.95
S2 F1+F2+F3+F4 14304.03 2576.23 413.39 1459.80 1228.83 16.12 89.57 31.24
MF 0.23 2.04 3.47 5.84 5.75 7.82 3.45 3.04
F1 13.20 36.50 10.67 60.26 50.40 0.84 1.90 0.72
S3 F1+F2+F3+F4 25007.55 2293.63 374.67 1186.98 919.39 16.61 63.73 35.37
MF 0.05 1.59 2.85 5.08 5.48 5.06 2.98 2.04
F1 16.69 94.80 20.76 27.58 73.33 0.98 8.24 1.89
S4 F1+F2+F3+F4 25233.30 1271.94 390.41 952.63 1042.99 14.09 60.00 32.98
MF 0.07 7.45 5.32 2.90 7.03 6.96 13.73 5.73
F1 41.22 20.70 6.44 22.00 59.76 1.38 0.95 1.06
S5 F1+F2+F3+F4 21107.27 1469.27 271.23 746.30 827.75 8.90 27.02 15.04
MF 0.20 1.41 2.37 2.95 7.22 15.51 3.52 7.05
Fractions Cd Al Ca Cu Fe K Mg Mn
F1 0.66 2.4 84.57 10.61 3.11 0.82 1.52 0.72
S1
F1+F2+F3+F4 1.92 413.35 369.96 14.35 726.11 14.5 171.73 3.13
MF 34.375 0.58062 22.8592 73.9373 0.42831 5.65517 0.88511 23.0032
F1 0.94 3.34 203.6 7.74 4.62 2.75 6.4 1.69
S2 F1+F2+F3+F4 2.07 427.07 446.57 15.05 826.47 14.4 313.87 7.29
MF 45.4106 0.78207 45.592 51.4286 0.559 19.0972 2.03906 23.1824
F1 0.62 2.49 92.2 8.44 3.11 1.18 3.03 0.59
S3 F1+F2+F3+F4 2.03 346.18 283.54 15.08 672.06 11.41 250.92 4.82
MF 30.5419 0.71928 32.5175 55.9682 0.46276 10.3418 1.20756 12.2407
F1 0.54 3.58 80.71 21.13 8.55 2.15 5.46 0.42
S4 F1+F2+F3+F4 1.67 294.79 205.93 29.35 658.56 12.38 210.83 3.92
MF 32.3353 1.21442 39.1929 71.9932 1.29829 17.3667 2.58976 10.7143
F1 0.36 2.77 57.01 3.93 3.96 0.57 2.01 0.46
S5 F1+F2+F3+F4 1.43 224.43 174.78 7.8968 442.45 4.59 148.77 2.78
MF 25.1748 1.23424 32.6181 49.767 0.89502 12.4183 1.35108 16.5468

F1 = Exchangeable, F2 = Iron and Manganese oxide, F3 = Organic matter and

Reducible, and F4 = Residual.

6
Table 7: Chemical composition of various materials applied in geopolymerization compared with proposed South African
mine tailings

Weight % Van Denise Ren et al., Thomas Ahmari Ahmari Zhang Ngoetjana, Present
/Element Jaarsveld and 2014. et al., and et al., et al., 2015. study
as oxide et al., Mauro, Aluminium 2013. Lianyang, 2012. 2011. Gold Mine
1999. 2014. Waste Copper 2013. Waste Copper Tailings
Sasol Fly Waste Tailings Cement Concrete Tailings (South
ash water (India) Kiln dust Powder (USA) Africa)
(South treatment (USA) (USA)
Africa) sludge
SiO2 50.1 30.2 1.50 75.0 11.0 40.1 64.8 63.8 65.5
Al2O3 28.3 39.1 31.7 12.16 3.90 9.6 7.08 5.5 12.06
CaO 8.2 0.2 0.20 0.16 42.0 20.6 7.52 3.1 5.91
Fe2O3 4.0 25.8 2.68 3.60 2.0 3.5 4.33 16.3 8.07
MgO 2.0 0.6 4.03 0.49 3.6 2.1 4.06 4.3 2.83
TiO2 1.5 1.4 0.01 0.013 -- -- -- 0.3 0.88
Na2O 0.5 -- 6.44 4.3 -- 1.7 0.90 1.1 1.22
K2O 0.9 1.4 0.08 1.85 0.6 2.3 3.26 0.6 0.56
SO3 0.4 0.6 13.3 -- -- -- 1.66 -- --
LOI 4.1 -- --- 2.10 -- -- -- 4.8 3.52
MnO -- 0.3 0.59 0.01 -- -- -- 0.1 0.07
P2O5 -- -- 0.21 -- -- -- -- 0.1 0.13
SiO2/Al2O3 1.77 0.77 0.047 6.16 2.82 4.18 9.15 11.6 5.43