• Aucun résultat trouvé

I. 2 Plan du travail

I. 3.1 Echantillonnage et méthodes de terrain

5.4 METHOLOGY

5.5.1 Piuquenes tailings impoundment, La Andina

5.5.1.6 Hematite-rich sediment of the pond area ........................................................... 1 00

The maximum extent of the pond is associated with the presence of a clay-sized (K

=

8.47x10-9 mis), intense red-brown laminated sediment with a maximum thickness in the center of the pond of 15 cm and paste pH 8 overlying the low pH (2.1 - 3.5) oxidation zone, separated by a weil defined contact (Fig. 2A and Fig. 6). The transition zone of this sediment to the underlying low pH oxidation zone was sampled in detail in a second field campaign 1997 (Fig. 1, AS 1 -AS4).

The thickness of this sediment decreases continuously towards the margins. Polished thin sections, as well as XRD and DXRD show that the red sediment is enriched in oriented tabular

Chapt er 5: Element cycling and secondary minera/ogy in p01phyry copper tailings

hematite and a higher ordered ferrihydrite. The high crystallinity (results of Mossbauer spectroscopy) of the hematite in relation to pedogene hematite (Friedl, 1997, persona!

Fig. 5: Microbial iron ( Fe2+) oxidation activity of representative sanzples from the three studied tailings. The drill core AS is from Piuquenes (Andina), T4 from Cauquenes (Teniente), and El from El Salvador No.] impoundnzents.

Filled dots are sanzples from the prùnary zone and unfilled dots are from the oxidation or neutralization zone. As expected, samples from the oxidation zone from Piuquenes and Cauquenes start to oxidized. ln contras!, none of the samples from the oxidation zone of El Salvador show important oxidation. This is interpreted as an effect of the higher molybdenite content in the Salvador tailings, which is lethal to oxidizing bacteria as Thiobacillus ferrooxidans leading to low microbial oxidation activity.

communication) and the fact that this type of tabular hematite is also found in the primary zone of the tailings, suggest a hypogene origin. The pond pH during sampling was 7.6 and the pas te pH of the sediment was between 7.6 and 8.4. The fine layering, the location at the lowest elevation of the impoundment, and the sharp contact with the low pH oxidation zone indicate that this sediment is a product of alluvial enrichment taking place on the tailings surface. The results of sequential extraction confirm this interpretation, showing strong enrichment of bivalent cations mainly in the exchangeable and Fe(III) oxyhydroxides fractions in the hematite-rich sediment, while the underlying oxidation zone is leached out with respect to these elements (Fig.

6 and Table 6). Mo is not enriched in this sediment, due to the low mobility of molybdate under a cid conditions prevailing in the oxidation zone, which surrounds this sediment. Below, in the oxidation zone, Mo shows its association to the Fe(III) oyxhydroxide leach and is enriched in the organic fraction in a coarser horizon. This may indicate that in coarser material the microbial activity is higher due to better 02 transport, resulting in higher molybdenite oxidation and increased poisoning of oxidizing bacteria as Thiobacillus ferrooxidans. However, coarser tailings material has generally higher sulfide contents, due to gravimetrically separation, so that higher concentration in the H202-leach could also indicate the leach of by oxidation destabilized molybdenite. This possibility is regarded as less probable as higher Mo concentrations in the El Salvador tailings are interpreted as the reason for minimal microbial oxidation activity.

At the geochemical interface between the hematite-rich sediment and the oxidation zone the different geochemical behavior of oxyanions and bivalent cations is clearly documented. The following genetic model for this hematite-sediment is proposed: Rainfall (pH 5.5) causes dilution of the acid in the oxidation zone, increases the pH, and hydroxide complexes of Fe, Al, or Mn

Chapter 5: Element cycling and seconda1y minera/ogy in porph_Vl)' copper tailings

hydrolyze and form polymers. The latter, together with fine-grained material as clay minerais and fine tabular hematite are transported following the hydraulic surface gradient to the pond and enriched in its depression, where the partiel es settle. In win ter, the low permeability (K =8.5x IQ-9

m/s) of the hematite-rich sediment forms a closed geochemical system, independent of the underlying low pH oxidation zone and the phreatic level. Bivalent cations are still mobile during the transport on the top of the low pH oxidation zone. But when they reach the pond with pH 7.6 they are adsorbed and ferrihydrite forms. In summer, cracking of the fine sediments permits oxygen and water flux into the underlying oxidation zone, reflected by increased concentrations of bivalent cations in the first centimeters under the hematite-sediment. The fact that the pond and the sediment have neutra! pH can not only be explained by dilution with rainwater (pH 5.5).

Ligand exchange of adsorbed elements with functional groups OH-can lead to an additional increase of the pH, due to strong adsorption processes in the hematite-rich sediment. In the pond water bicarbonate is also slightly enriched to 44 mg/1 possibly due to eolic input, as the surrounding oxidation zone can not be the source.

~ hrn "co~o~x~ 8.5 x10'~ffi!s:"-,;;~~~pH iij5

sh pH3.57

Ê fin~ ~a~dy: ··<':· ';;:·_ i~ /~~;of _Ptt 3_44

u '· K =·1.9 ~10·. mls· ' ·."pH 3.22

~10~sh~---~~---~

g.

1 l ' . ~ . -PI;i29(

-o silty-clayey •• · sh nm; ~do 5~

' O H,V6

16 •"- K=14x10"mls

sh pH3.28

tine~andy:'_;c.-,,.· ,. ~-/0 \: ·:-

>'

Fe(%) Cu (ppm) Mo (ppm)

0 1 2 3 4 5 0 200 400 600 0 20 40 60

Sequential Extractions

0 H2Ü (water-soluble)

0 NH .. Ac (exchangeable)

A NH .. OxD (Fe(lll)hydroxides)

+

NH .. OxH (Fe(lll)oxides)

a

H202 (organ ic +cv)

0

KCI03, HCI, HN03 ( sulfides)

HC104, HF. HN03 (residual)

Fig. 6: Zoom of the first 20 cm of the surface of the pond a rea of Piuquenes with the hematite-rich sediment and the uf!derlying schwertmannite rich oxidation zone (sampling campaign 1997, AS3). Geochemical results from sequential extractions of Fe, Cu, and Mo from the three upper horizons are presented. The Cu distribution is representative for the behavior of bivalent cations and Mo is representative of oxyanions in the oxidation zone. K values (hydraulic conductivity) were calculated from laser grain size analyses. For detailed discussions see text.

For data see Table 6.

Chapter 5: Element cyc/ing and secondary minera/ogy in porphyry copper tailings

Table 6: Resu/ts from sequential extraction (/CP-ES from sequence B) from the su1jace sampling AS3 from the Piuquenes tailings impoundment at La Andina.

~~=~~tL-idePih ~-~o-+NH.:OA~NH·;=o;oiN-H~~OxH / oo;-~-Suïiide+~~u-~t h~at~b-~ïk ----~~;J;.d;oth-f~oiNH~~OA~+NH;-o~-~00""

~~~t--.o~-A53~o~o2l '~ 2 1 BOL 1 0 ! 0 7 0.56 4.83 l_0.07J 0.93 1 0.99=m·45 8.07 .:.::· ~_5_3.!_o_<l?__E±2~-~- 513 385 __ _:3_2~-~ 52.8 8 1356 124Q __

-M.9~i::L___L~-""'' _ c:r_jp.";p""m"t-'-c-c;-l~-o-f=----::c--l--:-cc-c:-=+:ccc-:---cc+-c~-+-~-c-!~,--,--+---c-!~~1

sample 1 depth 1 I-bO NH··OAc NH.-OxD NH.-OxH , H._>()., sulfide residual. total bulk samole deoth H20 NH.-OAc NH.·OxD NH•·OxH H2Ü2 sulfide , residual total bulk determined chalcanthite occurs as secondary surface precipitates (Fig. 2C). The five drill cores (Tl - T5) show a very similar stratigraphy of the tailings (Fig. 1). The stratigraphy, pH distribution and geochemical data from the representative drill core Tl are presented in Fig. 7 and Table 7. The oxidation zone at the top reaches 1.05 to 1.65 rn depth (Tl= 1.05 rn; T2 = 1.65 rn; T3 = 1.50 rn; T4 = 1.53 rn; T5 = 1.40 rn), with paste-pH values of 1.72 to 4.12. The coloris yellow with orange-brown horizons, streaks, and dots (Fig. 2C). The grain-size is generally smaller than in the primary zone, due to increased breakdown to clay minerais. Fine sandy and silty-clayey horizons alternate. The oxidation zone is sharply separated from the dark gray to brown-gray colored primary zone. No neutralization zone as observed at Piuquenes is developed, possibly due to the lack of carbonate neutralization potential (see acid-base accounting). Sorne brown horizons in the primary zone indicate the precipitation of secondary Fe(III)

Chapter 5: Element cycling and secondary minera/ogy in p01phy1y copper tailings

oxyhydroxides. The pH increase in the primary zones generally up to maximum concentrations of 5, only in the drill core T3 neutral values are reached.

Quartz, albite, and micas (mainly biotite) dominate the gangue mineralogy, as shown by XRD. Illite, chlorite and kaolinite are the typical clay minerais. In the oxidation zone the secondary mineral ogy is dominated by disseminated jarosite and a vermiculite-type mixed layer mineral (11.7- 11.9Â) as well by schwertmannite. The latter is associated with dots or rims as well as horizon interfaces of different grain-size (Fig. 2C). The presence of schwertmannite was proven by DXRD. Gypsum is mainly associated with samples from the phreatic level and is interpreted as a tertiary mineral. The gypsum found in the oxidation zone may be secondary.

The study of polished sections show that the oxidation of the sulfides is nearly complete in the oxidation zone. Only sorne small residual grains of pyrite or chalcopyrite could be observed.

One pyrite grain was found to be coated by ferric hydroxides and thus protected from further oxidation; in general pyrite does not show this coating. Magnetite is also present with martite replacement. Following the stratigraphy downwards to the primary zone, the original sulfide paragenesis of the ore can be observed. It is dominated by pyrite, which shows strong fracturing.

In general it does not show alteration or Fe(III) hydroxide rims. Chalcopyrite is present as traces and sometimes intergrown with bornite. Both hypogene sulfides frequently show replacement to chalcocite, digenite, and covellite. As in the Piuquenes impoundment, two different generations of replacement can be differentiated. Camus (1975) reported that the most important supergene sulfide mineral present in the orebody is chalcocite, with minor proportions of covellite. Hence, the stronger digenite and chalcocite with traces of covellite replacement in the tailings is interpreted to be primary supergene enrichment, consistent with observations of fracturing and incomplete thick rims (Fig. 20). The secondary replacement is characterized by thin, complete rims of mainly covellite and digenite also associated exclusively with chalcopyrite (Fig. 2H).

The latter replacement, mainly associated with a 2-4 rn thick zone below the water-level, is interpreted as secondary. Magnetite is largely found as massive grains, partly altered to martite.

Traces of sphalerite, molybdenite, rutile, goethite, hematite, and galena were found.

5.5.2.2 Acid-Base Accounting

ABA results show that the Ctot is below the detection limit and the Ssulfide content in the primary zone has an average of 0.59 wt % (Fig. 7). With the assomption that ali Ssulfide is associated with pyrite, this tailings yield to an average of only 1.09 wt % pyrite in the primary zone. Correcting for Cu concentrations in the sulfide fractions of sequential extractions leads to an average pyrite content of 0.99 wt %. The variation between the total sulfide pyrite content and the correction for the Cu-sulfides ranges between 4.6 and 29.3% with an average variation of

10.8 %.

The acid flotation circuit has a pH of 4.5, which explains the absence of a carbonate NP.

The acid circuit is possibly also the reason for the low pyrite content, as under acid conditions a high percentage of pyrite will float and end up in the concentrate. In contrast, pyrite flotation is generally suppressed by an alkaline pH (lime addition). Low carbonate NP (0.12 & 0.16 wt.%

Ctot) was only found in two samples of the T3 drill core. This possibly is the reason that the pH

Chapter 5: Element cycling and secondary minera/ogy in porphyry copper tailings

increases up to neutra! values in this drill core. It might be that in this area, material was deposited before the change from the alkaline to the acid circuit.

5.5.2.3 Sequential extractions

In the Cauquenes drill core T4 (data not shown) the element distribution is very similar to that of Piuquenes tailings. T4 is situated at the edge of the tailings impoundment (Fig. 1), where the permeability is one order of magnitude higher than in the tailings center (e.g., T2). Bivalent cations e.g. Cu, and Zn are nearly completely leached out of the oxidation zone, whereas oxyanions such as Mo and As show low mobility as reported in the Piuquenes tailings through adsorption to Fe(III) oxyhydroxide sulfates. Data from a representative drill core in the center of the impoundment (Tl; Fig. 7) show that cations (Ca, K, Mg, Cu, Zn, Mn) and sulfate increase their concentrations in the water soluble-fraction to the top of the tailings. In contrast to the results of the exchangeable fraction of the Piuquenes tailings, the samples of this fraction from the Cauquenes tailings (Tl, T2, T3) have elevated Cu and Zn concentration in the oxidation zone (Fig. 4). Electron microprobe analysis on biotite from the oxidation zone show that Mg and K decrease to the grain edges and Cu and Zn increase. The position of the peak of the vermiculite-type mixed-layer mineral is at lower d-values (11.7- 11.9Â) than in the Piuquenes (Fig. 8, 12.25 - 12.67 Â). DXRD control of the dissolved phases have shown that in the exchangeable fraction (NH4-acetate) the vermiculite-type mixed-layer mineral disappears and a new peak at lower

ct-values at the flank of the 001 illite peak appears. Do to higher activity of Cu and Zn in the oxidation zone of the Cauquens tailings, Cu and Zn promotes the release of K of biotite as shown by Farquhar et al. (1997) and are fixed in the interlayer of the resulting vermiculite-type mixed-layer mineral, leading to the lower d-values. This mineral is broken down in the NH4-acetate leach possibly due to detachment of the interlayer cations and the peak shift to the lower d-values, indicating that the mineral is not completely dissolved.

Fe and Al are below the detection limit in the water-soluble fraction but show increasing concentrations in the oxidation zone in the exchangeable, Fe(III) oxyhydroxide and Fe(III) oxide leaches. In the oxidation zone Mo is associated with the Fe(III) oxyhydroxide and also to Fe(III) oxide fraction possibly adsorbed to jarosite as the sh/jt ratio is below 0.5 in the Cauquenes tailings, while in Piuquenes this ratio reaches concentrations > 1. The sulfide fraction is depleted in the oxidation zone but increase to a double enrichment near the water table compared to the primary zone. This may indicate that Mo is enriched by similar processes as Cu.

The total As content is distributed in the exchangeable and reducible fraction, no As is detectable in the sulfide fractions, possibly also a result of low pH conditions in the Cauquenes tailings. V does not display significant mobilization.

W a ter content and geochemical data from drill cores from the center of the impoundment (Tl; Fig. 7) indicate that in the upper 100 cm a significant upwards mobilization of S04, Ca, K, Mg, Cu, Zn, and Mn takes place during the dry season. Finer grain-size increases the water retention capacity and the capillary force, resulting in an increase of the water content at the surface and an enrichment of bivalent cations in the form of water-soluble phases, mainly sulfates (e.g., gypsum, chalcanthite), due to high evaporation rates in summer (Fig. 7).

Chapter 5: Element cycling and secondary minera/ogy in porphyry copper tailings

Table 7: Drill core Tl from Cauquenes/ Teniente /CP-ES results from sequence B

~:;,~~~--~i--d~Pih-1-H:i> l NH4~0A~NH4-0xë} NH4-o~-H 1-1-i202-!-s~ïtidë"j ~;;~id~~~J.t~i;J-\ b~lk- _ ~~~~:l~ -d~h

-\---H20-tNH4~A~~NH4~0ill~~H202+-;~;id~-+~;siduâlt--to~T1~--lt~~ j * ff~ct :{l l *':t n: 1 : ~1 : :H~u: t '<' j }" t .•• ;:~ 1 :: ~ :l j m - 1 m - ~f lil::J :Hf:~: ' ::il

~~~-;'Yd;;thl---.::i20-fNH4-0~4~-NH4-0xH H202 sultide residual total bulk -~!~th~-H20 NH4-0Ac NH4-0xD. NH4-0xH H202 sulfide 1 residual tol~b;:;ik

Tll010 10 BOL' 1 7 37 1 39 263 348 503 Tll010 10 BOL 6 37 25 BOL BOL BOL 68 72

Chapter 5: Element cycling and seconda1y minera/ogy in porphy1y copper tailings

This upwards migration superimposes the general trend of downwards mobilization during the raining season and is conserved in the leached oxidation zone in T4 and the secondary replacement of chalcocite by covellite below the ground water table.

Stoichiometric calculation of the jarosite content leads to an overestimation of the sulfate content. An increased AP+ content on the B site of the general formula of the alunite-jarosite group AB3(S04)2(0H)6 or the presence of alunite could be the source for the too high calculated S04 contents. This is supported by increasing concentrations of Al in the Fe(III) oxyhydroxide and Fe(III) oxide leach in the oxidation zone. Detailed XRD studies of the jarosites from the Piuquenes tailings and the jarosites from the T4 core (Cauquenes), which do not show increased concentrations of Al in this leach, show peak position near synthetic jarosite (Fig. 9). In contrast, jarosites from Tl show a peak shift to lower d-values, suggesting the substitution of Fe3+ (ion radius 0.65Â) by the smaller AP+ (0.53Â). This is supported by an increase of Al content in the Fe(III) oxide leach in samples from the oxidation zone. Correction with the Al content increases the accuracy of the stoichiometric calculation and suggests that up to 20 % of the B site of the jarosite is substituted by AP+. These findings show that the evaporation controlled upwards

mobilization of elements has direct influence on the composition of the secondary minerais.

As mentioned, Cu shows in these tailings a similar enrichment below the water table by replacement of chalcopyrite by covellite as in the Piuquenes tailings. Due to the lack of carbonate NP the neutralization sequence is not as weil developed as in the Piuquenes tailings and the secondary Cu enrichment is not as weil defined in the stratigraphy. Ti concentrations are below the detection limit in the Fe(III) oxides leach indicating, that no ilmenite is present in the Cauquenes tailings.

5.5.2.4 Microbiology

Four representative samples from the oxidation zone and primary zone of the Cauquenes tailings were submitted to bacterial count and iron oxidation activity tests. In ali samples high bacteria numbers by direct counting were observed (3.0x108 - 5.0xl08 bact/ml). Thiobacillus ferrooxidans could only be cultivated (1.4x105 bact/ml) in the sample from the oxidation front (T4/150). Oxidizing activity tests show that the sample from the oxidation front started first to oxidize Fe2+ to Fe3+ after an initial or lag phase of 144 h. This oxidation activity has to be related with the increased population of Thiobacillus ferrooxidans at the oxidation front. This is consistent with the findings of Davis ( 1997) where the highest population of Thiobacillus ferrooxidans was found at the oxidation front and the population of Acidiphilium spp. increased to the top of the oxidation zone. The sample from the upper part of the oxidation zone started the oxidation activity after 336 h growth time, indicating the lower population of active iron-oxidizing bacteria, possibly due to Mo poisoning. Once oxidation started, the oxidation velocity (growth rate) was similar. The sample from the primary zone did not start significant oxidation in the time range (432h) of the experiment (Fig. 5).

Chapter 5: Element cycling and seconda1y minera/ogy in po1phyry copper tailings Fig. 8: Peak position (XRD results) of the vermiculite-type mixed-layer mineral in samples from the oxidation zones of Piuquenes tailings impoundment (A2!020, A2!050, AJ/020, AJ/050) and the Cauquenes tailings ùnpoundment(T/1040, T/1/05, TJ/150). F01·discussion see text

"0 tailings impoundments, indicating Al-substitution in sample T 11040 and T/1105. For discussion see text.

Chapter 5: Element cycling and seconda1y mineralogy in porphyry copper tailings

5.5.3 El Salvador No.l tailings impoundment, Chile 5.5.3.1 Minera/ogy

The four drill cores in the El Salvador No.l tailings show that the stratigraphy is characterized by a 0.3 to 1.5m (El = 0.3m; E2 = 0.35m; E3 = 1.5m; E4 = 0.35m) thick evaporite zone at the top (Fig. 2D) with extensive blue, yellow, white and brown efflorescent salts formation (paste pH 2.00 - 3.53). Below, an oxidation zone with orange-brown horizons and paste pH values from 1.88 - 2.80 is observed. The "prùnary zone", which was defined visually by its dark gray color but that, as discussed below, is significantly affected by oxidation, was intersected by two drill cores at depths of 1.7 rn (El) and 4.7 rn (E2). It displays sorne dots and streaks of orange-brown Fe(III) hydroxides, possibly schwertmannite. In Fig. 10 and Table 8, geochemical data for the representative drill core E2 are presented. The moisture content in the evaporation zone was 0-8 wt.% and increased downwards to a constant 20 wt.%. This relative high moisture content is surprising in view of the extremely low precipitation rates (20 mm/a), the high evaporation and the age of the tailings (36 years). It should be noted, however, that similarly old tailings in hyper-arid climate (P. Cerda; chapter 6) also show moisture contents within this range.

XRD studies show that quartz, alkali-feldspar (mainly albite ± anorthoclase), biotite ± seri cite, jarosite and natrojarosite dominate the primary gangue mineral ogy. Kaolinite and illite

XRD studies show that quartz, alkali-feldspar (mainly albite ± anorthoclase), biotite ± seri cite, jarosite and natrojarosite dominate the primary gangue mineral ogy. Kaolinite and illite