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Hydrometallurgy, 34 (1993) 171-185

Elsevier Science Publishers B.V., Amsterdam

171

Carbon paste electrodes in mineral processing: an electrochemical study of galena

E. Ahlberg and J./~sbjSrnsson

Department oflnorganic Chemistry, Chalmers Universityof Technologyand Universityof GOteborg, S-41296 GOteborg,Sweden

ABSTRACT

(Received

January 10, 1993; revised version accepted March 1, 1993)

Electrochemical theories are often used to explain leaching of sulphide minerals and it is therefore desirable to study the individual processes with electrochemical methods. For good conducting min- erals this comprises no difficulties since the mineral itself can he used as an electrode. However, for poorly conducting minerals this is not possible and direct electrochemical measurements cannot be performed. The aim of the present study was to examine the applicability of the carbon paste electrode tech- nique to mineral processing. The mineral is embedded in graphite and the reaction at the heteroge- neous electrode/electrolyte interface is investigated. In order to quantify the use of carbon paste elec- trodes a conducting mineral was chosen:galena.This makes a critical comparison ofthe electrochemical properties of the carbon paste-galena electrode and pure galena electrode possible. Potentiodynamic sweeps in acidic perchlorate solutions and with both stationary and rotating disk electrodes were used for the qualitative examination. In order to investigate the nature of the overall anodic dissolution reaction of galena, chronocoulometry in conjunction with atomic absorbance spec- trometry was used. It was exclusively shown that the electrochemical behaviour of the carbon paste- galena system was the same as for pure galena. The overall anodic dissolution reaction involves two electrons and the stoichiometry of the galena sample was determined to be Pbl.,S.

INTRODUCTION

The electrochemical behaviour of sulphide minerals is an important factor in mineral processes such as leaching, flotation and electroreduction. It is, therefore, desirable to use electrochemical methods for the detailed studies of the different reactions taking place. Since many sulphide minerals are good conductors, they are suitable for use as massive electrodes in electrochemical experiments. Two main theories have been used to explain the electrochemi- cal reactions taking place; namely, the mixed potential model and the semi- conductor model. The mixed potential model is borrowed from the concept of corrosion and presumes an electrically conducting sample. However, not all sulphide minerals are good conductors [ 1 ] and in those cases traditional

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172

E. AHLBERG AND J. ASBJ(~RNSSON

electrochemical experiments cannot be performed. The use of carbon paste electrodes allows the study of poorly conducting minerals as well. The carbon paste electrode (CPE) was first introduced for organic polar- ography by Adams in 1958 [2 ]. Since then the CPE has mainly been used for analytical purposes for organic as well as inorganic compounds. The CPE consists of two components, a finely dispersed spectroscopically pure graph- ite and a binder. The binder can be either conducting or non-conducting. The electrochemical behaviour of a CPE with conducting binder is quite different f?om a CPE with non-conductingbinder. A CPE with a non-conductingbinder can be regarded as an inert electrode in the same sense as glassy carbon and Pt electrodes. Therefore the CPE has been used as an alternative to these for various electrochemical purposes. The sensitivity of the CPE is high, due to its low residual currents and high polarisation range. This constitutes an ad- vantage compared to other inert electrodes, such as platinum, which can be oxidised at anodic potentials and also has lower overpotentials for the oxygen and hydrogen evolution reactions. The low residual current is due to the small double layer capacitance at the electrode-electrolyte interface. The hydro- phobic binder used in the CPE lowers the double layer capacitance. The ca- pacitance of a CPE, and consequently the residual current, decreases with the increasing density of the binder used in the paste (i.e., the length of its molec- ular chains) [3 ]. However, this is accompanied by a decrease in the rate of the charge transfer processes taking place at the interface [4 ]. A CPE with electroactive material introduced into the carbon paste is termed a carbon paste electroactive electrode (CPEE). A CPEE with organic binder is highly hydrophobic, which lowers the rate of the reactions taking place at the electrode interface [4 ]. Penetration of the electrolyte into the electrode is unlikely, due to its hydrophobic nature. Thus, electrochemical reactions take place solely at the interface. As a consequence, the dissolution of the electroactive material more or less stops after depletion of the outer layers of the paste [5,6 ]. In a CPEE with conducting binder the electrochemical reactions may take place not only at the electrode surface but also inside the electrode bulk ma- terial. The electrochemical response of a CPEE with conducting binder is sim- ilar to that of a thin layer cell [7,8 ]. In this case, the electroactive material and the graphite particles can be regarded as electrochemically active, and hence galvanic couplings may occur. Species with more noble potentials than carbon introduced into the paste may thus undergo redox reactions with the graphite particles, for example Fe 3÷ [9 ]. Mathematical models have been constructed for both types of systems [5-7,10, I 1]. A review of the applica- tions and possibilities of CPEEs has been given by Branina et al. [ 12]. Thus, by mixing low conducting minerals, in pulverised form, with carbon paste it becomes possible to study the electrochemical reactions taking place. The fraction of reactive semiconducting particles is proportional to their vol-

CARBON PASTE ELECTRODES IN MINERAL PROCESSING

173

ume concentration in the carbon paste in the range 0-40%, while the perco- lation threshold is attained at 68%. The reason for this percolation phenom- ena is probably the diminishing contact between the active conducting area of the graphite particles in the paste as the amount of poorly conducting ma- terial is increased [ 13 ]. Percolation thresholds were first studied formally by Broadbent and Ham- mersley in 1957 [ 14,15 ], who introduced lattice models for the flow of a fluid through a static random medium and showed rigorously that no fluid will flow if the concentration of active medium is smaller than some non-zero threshold value. They also introduced the concept of a percolation probabil- ity, which is the likelihood that any given region of the medium is sufficiently well connected to the rest to be available for conduction. The percolation ef- fects have been suggested to play a role in the metal-semiconductor transi- tions seen in some disordered systems, or in the usually low mobilities asso- ciated with free carriers in amorphous materials [ 16 ]. However, when highly conducting substances are introduced into the paste, no percolation threshold exists and the amount of material introduced into the paste is only limited by the physical stability of the electrode. Galena (natural PbS) is, in most cases, a highly conducting mineral which makes it suitable to use as a conventional electrode. In the literature one can find a considerable number of papers examining the electrochemistry of gal- ena or PbS in connection with mineral processing [ 17-28]. Galena can dis- play both n-type and p-type semiconduction, but most naturally found galena is n-type; that is, sulphur deficient [29]. It has been shown in some previous electrochemical studies on galena that its semiconducting properties do not affect its general electrochemical characteristics [ 18-20,22 ]. However, illu- mination of galena increases the current at low anodic potentials without af- fecting the bulk dissolution of galena [ 18,24,27 ]. Recently, it has also been shown that the electrochemical behaviour of galena at low potentials can be ascribed to its semiconducting properties [27 ]. The aim of the present study was to investigate and compare the electro- chemical behaviour of massive galena with galena in carbon paste. Since the minerals used in flotation and leaching are in powder form the CPEE consti- tutes a closer connection with the industrial processes. It is, therefore, of ul- timate importance to investigate if the carbon paste influences the reactions. The choice of galena for this purpose was dictated by the need for a good conducting material that could also be used as a massive electrode. Natural galena was thus investigated, both as a solid electrode and pulver- ised in CPE, with the aid of potentiodynamic sweeps in the potential range from - 1 V to + 1 V. Chronocoulometry at anodic potentials, together with analysis of the amount of dissolved lead, detected with atomic absorption spectrometry (AAS), were conducted in order to determine the number of electrons consumed at various potentials. The experiments were performed

174

E. AHLBERGAND J. ,6.SBJ(3RNSSON

in acidic perchlorate media in order to avoid any complex formation of the generated species formed upon polarisation of the electrode. The results show that the carbon paste does not influence the electrochem- ical characteristics of galena. For potentials lower than 800 mV two electrons are consumed for the anodic dissolution reaction for both type of electrodes. The stoichiometry of the mineral was also determined, yielding the overall reaction:

PbH S~ 1.1Pb 2+ +S ° + 2.2e-

(1)

EXPERIMENTAL

A conventional three-electrode cell was used with a platinum gauze as the auxiliary electrode and a saturated sodium chloride calomel electrode (ssce), E°= 236 mV vs. nhe (normal hydrogen electrode), as the reference electrode. The electrochemical cell was a Metrohm titration vessel with a specially de- signed lid. The rotating electrode assembly was constructed in the laboratory of the Department of Inorganic Chemistry, University of G&eborg.

Chemicals

The electrolyte solution was made from stock solutions of pro analysi so- dium perchlorate and perchloric acid and was diluted with doubly distilled water.

Voltammetric studies

Prior to experiments, the electrolyte solution was de-aerated with purified nitrogen for 1 h or more. A nitrogen atmosphere was maintained in the cell during the experiments. A PAR (Princeton Applied Research) 173 poten- tiostat with a model 276 interface, and an HP (Hewlett Packard) computer, printer and plotter was used for generation and recording of the polarisation curves. A Solartron frequency response analyser 1174, connected to the po- tentiostat, was used to measure the ohmic resistance between the working and reference electrodes. The current data are given in milliamps because the geo- metrical area of the CPE-galena electrode is not comparable to its active elec- trochemical area. The recorded current/potential data were compensated for ohmic drop. All measurements were performed at room temperature. The potentials given in this work refer to the ssce scale.

CARBON PASTE ELECTRODES IN MINERAL PROCESSING

Chronocoulometricstudies

175

In the chronocoulometric experiments the total charge consumed during the electrolysis was calculated from the current/time data. The cell was dis- connected and the Pb 2÷ content in the solution was determined by AAS. The experiments were conducted in de-aerated solutions of 1 M NaC104, pH = 2. For the galena electrode experiments were performed at various potentials and for different electrolysis times. For the CPE-galena electrode, various compositions as well as various potentials were investigated at a constant electrolysis time.

Preparationof workingelectrodes

A natural galena sample from England was used in this study. Chemical analysis of the ground material revealed the composition: 83% Pb, 13.2% S, 1.76% Fe and about 0.02% of Ag, Cu, Ni and Ti. The solid galena electrode was made from cut specimens of natural galena crystals which were mounted and glued with a carbon conducting glue on a brass rod. The electrode was moulded in epoxy, with one side of the galena exposed to the electrolyte. Prior to the experiments the surface of the galena electrode was wet ground on sili- con carbide paper ( 1000 and 4000 mesh) and carefully washed with doubly distilled water. Immediately after this pretreatment the electrode was trans- ferred to the cell. The carbon paste electroactive electrode (CPEE) consisted of commercial carbon paste with a non-conducting binder (Metrohm) and a finely grained galena with mesh size 75-150 ktm. The carbon paste and galena were thor- oughly mixed together in a mortar in order to obtain a homogeneous paste. The electroactive paste was laid as an approximately 1.5 mm thick layer over a carbon paste mass, which had been previously filled and pressed into the cavity of an epoxy vessel. This was done in order to ensure good adhesion between the electroactive paste and the rest of the electrical connections in the electrode. The surface of the electrode was smoothed with a spatula and excess paste was removed with a sharp steel blade. Electrical connection to the graphite paste was made with a platinum wire at the bottom of the vessel. The platinum wire was plugged into a brass rod. The geometrical area of the electrode surface was 0.07 cm 2. The mixing ratio between the paste and gal- ena was in weight proportions: 4: 1, 3 : 1, 2: 1, 1: 1 and 1: 2. The ohmic resis- tance was always less than 30 ohms.

Reproducibility

The reproducibility of the currents depends highly on the homogeneity of the mixture of carbon paste and galena. Thus, great care must be taken when

176

E. AHLBERGAND J. ,~SBJORNSSON

mixing paste and galena in order to obtain reproducible results. For detailed studies one batch of mixed paste should be used in order to obtain consistent results. Pure galena electrodes show deviations with respect to the current response, even though these are small. These deviations can probably be at- tributed to local defects and impurities on the electrode surface and to imper- fections in the mechanical pretreatment of the electrode surface [ 18 ].

RESULTS AND DISCUSSION

Potentiodynamic studies

The carbon paste electrodes (without any electroactive material added) used in this study are stable over the entire potential range investigated (from

- 1 V to 1 V). At potentials more negative than - 1 V, hydrogen evolution

was found to occur. At high anodic potentials oxygen evolution takes place at

the electrode surface. It is well documented in the literature [4,30] that oxi-

dising treatment of various carbon species will cause the formation of various organic functional groups at the surface. These compounds are easily detected by means of voltammetric methods and can mediate electron transfer and thus influence the rate of the reaction studied. Thus, extreme anodic polaris- ation of a CPE has to be avoided.

Cathodic polarisation curves

In Fig. 1 the polarisation curves for a stationary galena and CPE-galena

electrode are shown. The CPE-galena electrode has a weight composition of 1: 1. The polarisation was initiated in the negative direction and at about - 700

mV the reduction of galena starts according to the reaction:

PbS+2H + + 2e---,Pb ° +HES

yielding metallic lead and hydrogen sulphide. With the CPE-galena electrode

a well defined reduction peak, C 1, is observed with a maximum at about - 775

mV. The peak height is limited by the available amount of galena present at

the electrode surface. Thus further reduction to more cathodic potentials gives only hydrogen evolution at the CPE-galena electrode, Fig. 2. In this case, the reduction of galena and the hydrogen evolution can be observed separately. This is due to the higher overpotential for the hydrogen evolution on carbon paste compared to galena.

For the massive galena electrode (Fig. 1) the reduction of galena is not

limited by the material present at the electrode surface. Further cathodic po- larisation leads only to an increase in this reaction and to hydrogen evolution. As the reaction proceeds, the electrode surface becomes covered with metallic

lead. The hydrogen evolution process developing on the metallic lead and the

(2)

CARBON PASTE ELECTRODES IN MINERAL PROCESSING

0.5

0.4

0.3

r

I

~

~

:

17 7

V,.::,.:: ~ :~

A2

I

0.2

C.I

'

o

IIITZ:::::

-0.1

-0.2

-0.3

-0,4

-0.5

J

,

 

-800

-700

-600

-500

-400

-300

-200

E/mV vs ssce

Fig. 1. Polarisation curves for electrodes in 1 M NaC104, pH = 2. Sweep rate 10 mV/s. Contin- uous line = stationary galena; dotted line = CPE-galena, weight composition 1 : 1.

0.4

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-900

-800

-700

-600

E/mV vs ssce

 

A2

-5~

-400

-300

-200

Fig. 2. Polarisation curve for a rotating CPE-galena electrode in 1 M NaC104, pH=2. Sweep

rate = 10 mY/s,

The weight composition of the CPE-galena electrode

rotation speed = 30 s-'.

IL78

E. AHLBERG AND J. ,~SBJORNSSON

reduction process of PbS occur in the same potential region and can, there-

tbre, not be observed separately.

When the polarisation sweep is reversed at -800 mV, a pre-peak, A 1, fol-

lowed by a larger peak, A2, are observed at about - 500 mV for both systems.

The pre-peak on the CPE-galena electrode develops at slightly more anodic

potentials. This is probably due to the binder in the paste, which decreases

the reaction rates at the electrode/electrolyte interface. Peaks A 1 and A2 ap- pear only if the preceding sweeps exceed about -700 mV. These peaks cor- respond to the oxidation of the products formed during the cathodic reduc-

tion of galena. Peak A 1 represents the reverse of reaction (2) while peak A2

corresponds to the oxidation of lead to soluble lead complexes:

Pb °-,Pb e+ +2e-

(3)

Peak A2 is much higher than peak A 1 because most of the hydrogen sulphide

formed during the reduction has diffused away from the electrode surface and

thus more of the Pb ° will be

Integration of the cathodic and anodic charges in Fig. 1 yields a charge ra-

tio, QA/Qc< 1, which indicates that hydrogen evolution takes place simulta-

neously with the reduction of galena on both electrodes. For the CPE-galena electrode the two processes are easily separated. The cathodic polarisation curves obtained under hydrodynamic condi- tions, that is, with a rotating galena or CPE-galena electrode, are shown in Fig. 3. The general appearance is the same as for stationary electrodes, with the exception that peak A1 is no longer observed. In this case, the hydrogen sulphide formed during the reduction of galena is swept out into the bulk solution and does not participate in the reverse reaction. The charge ratio,

QA/Qc, in this case, is also less than 1. From the results presented in Figs. 1 and 3, the general conclusion can be drawn that the CPE-galena electrode shows the same electrochemical behav-

iour as a massive galena electrode in the cathodic polarisation domain, apart

fi:om the evolution of hydrogen. The result also illustrates the advantages in

using the CPE-galena electrode for the study of the reduction of galena, be- cause unwanted hydrogen evolution can be avoided with CPE-galena. Figure 4 shows three subsequent polarisation sweeps of a rotating CPE-

galena electrode with the weight composition 1:2. The sweep started at - 180

oxidised to Pb 2÷ on the anodic scan.

mV

and proceeded in the cathodic direction. One can see from the polarisa-

tion

curves that the cathodic peak current and its corresponding anodic peak

current decrease after each subsequent polarisation sweep. This indicates that the current obtained is directly proportional to the available amount of PbS present at the surface. Moreover, this result also indicates and supports the assumption that the electrochemical reactions are restricted to the outer lay- ers of the electrode surface, due to the hydrophobic nature of the binder [5 ].

CARBON PASTE ELECTRODES IN MINERAL PROCESSING

0.5

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-200

Fig. 3. Polarisation curves for electrodes in 1 M NaC104, pH= 2. Sweep rate = 10 mV/s, rota- trode, tion speed weight = 30 composition s-L Continuous 1: 1. line = rotating galena electrode; dotted line--CPE-galena elec-

<

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-800

-700

-600

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-300

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Fig. 4. Three subsequent polarisation sweeps for a CPE-galena electrode in 1 M NaC104, pH = 2. Continuous line = first; dotted line = second; dashed line = third sweep. Sweep rate = 10 mV'/s, rotation speed = 30 s-1. The weight composition of the CPE-galena electrode was 1:2.

180

Anodic polarisation curves

E. AHLBERG

AND J. ASBJORNSSON

The results from the anodic polarisation of galena and CPE- galena are shown in Figs. 5 and 6, with three subsequent sweeps of the electrode. The sweeps were initiated at 0 mV and proceeded in the anodic direction. An ox- idation peak, A3, is observed at about 650 mV, followed by further oxidation of the galena bulk (Fig. 5 ). In subsequent sweeps the current is approximately restored. The height of the peak A3 on massive galena is dependent on the prehistory of the electrode and it has been attributed to the dissolution of

active sites [ 18 ].

of the CPE-galena system, the A3 peak appears at slightly more anodic poten- tials. No further oxidation takes place in the potential region investigated. In

subsequent sweeps the dissolution current is very low, since the galena at the surface has already been consumed in the first scan. A3 corresponds to the anodic dissolution of PbS according to the overall reaction:

In Fig. 6, which represents the anodic polarisation sweeps

PbS~Pb

2+ +S

° +2e-

(4)

This was confirmed by chronoamperometric experiments and the analysis of the Pb2+ content of the solution, which will be discussed in more detail below.

2.5

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<

A3.~

-.E-1.5

s

~'\

.

I

 

71

,"

0.5

 

_J

i

100

200

300

400

500

600

700

800

E/mV vs ssce

Fig 5. Three subsequent polarisation sweeps for a galena electrode in 1 M NaC104, pH = 2. Continuous line = first; dotted line = second; dashed line = third sweep. Sweep rate = 10 mV/s, rotation speed = 30 s- 1.

CARBON PASTE ELECTRODES IN MINERAL PROCESSING

181

 

2.52

*.

A3

!'

<

 

1.5

I

0.5

 

0

100

200

300

400

500

600

700

800

E/mV vs ssce

Fig. 6. Three subsequent polarisation sweeps for a CPE-galena electrode in IMNaC104, pH = 2.

and

Continuous line = first; dotted line = second; dashed line = third sweep. Sweep rate 10 mV/s

rotation speed 30

s- 1. The weight composition of the CPE-galena electrode was 1 : 1.

Chronocoulometry

Chronocoulometric measurements were conducted in order to investigate the number of electrons consumed during the overall reaction. The amount of charge was correlated to the concentration of lead ions in solution, as de- termined by AAS. Measurements were made with CPE-galena electrodes of different composition at constant potential (Fig. 7) and also at one compo- sition at different potentials (Fig. 8). In these experiments the time of elec- trolysis was constant. Similar measurements were made on the solid galena electrode. In this case the time of electrolysis as well as the potential was changed (Fig. 9). From Figs. 7-9 it can be seen that a linear relationship between the charge and the lead ion concentration is obtained, as predicted by theory. The fact that the lines do not cross exactly at the origin of coordi- nates indicates that some parallel processes occur, such as double layer effects and/or adsorption. From the slope of these straight lines the number of elec- trons can be calculated using Faraday's law:

Q=n.F.c.V

(5)

where: n = the number of electrons; F= Faraday's constant; c= the concentra- tion of lead ions in M; and V= the volume.

182

100

8o

E. AHLBERG AND J. ,~SBJORNSSON

 

6O

.+

 

,a~

40

 

2O

0

i

i

 

0

100

200

300

Q/mC

Fig. 7. Chronocoulometry at CPE-galena electrodes of weight composition 1 : 2, 1 : 1, 2: 1, 3 : 1 and 4: 1. E=600 mV, electrolysis time= 1000 s.

_-.IL

~

150

100

5o

0 0

'

100

200

300

Q/mC

400

500

Fig. 8. Chronocoulometry at CPE-galena electrodes of weight composition

range = 500-800

mV, electrolysis time = 1000 s.

1 : 1. The potential

For both CPE-galena and galena n was found to be 2.2 by this treatment. This may suggest that the overall reaction can not solely be explained by eq. (4), with the formation of elemental sulphur, but that a certain part proceeds to form soluble sulphur compounds of a higher valence. However, if the gal- ena sample used is slightly unstoichiometric, reaction (4) can still hold, but with the composition of galena as Pbl.~S. Galena can show both p-type and n- type conduction, but most natural galena samples are n-type, that is, sulphur deficient [29]. Thus, the stoichiometry of the sample can be determined,

CARBON PASTE ELECTRODES IN MINERAL PROCESSING

"~'

800

6O0

400

20O

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,

I

500

,

I

1000

,

I

1500

Q/mC

,

I

2000

,

2500

Fig. 9. Chronocoulometryat a galenaelectrode.The potential range= time rangedfrom200 to 1000s.

183

500-800 mV, electrolysis

which, in turn, may be important for the optimisation of the leaching process. Carbon paste electroactive electrodes have been used to study the stoichiom- etry of oxides [ 12,13 ]. These experiments exclusively show that no interaction between galena and carbon takes place that influences the electrochemical properties of the sys- tem. One reason for this may be the use of a non-conductive binder, which prevents reactions within the electrode. The present study was made as a fundamental investigation of the applica- bility of carbon paste electrodes in mineral processing. The results obtained can be extended to poorly conducting minerals that are otherwise excluded for electrochemical studies [ 31 ]. However, care must be taken with minerals that contain a redox couple, such as pyrite. Further studies on these type of minerals are in progress. The use of carbon paste electrode opens up the possibility of not only study- ing single minerals but also of investigating mixtures and flotation concen- trates. This makes it possible to optimise the leaching conditions for different samples.

CONCLUSION

From the above the following conclusions can be drawn:

( 1) It is exclusively shown that the electrochemical behaviour of galena mixed with carbon is the same as for pure galena. Thus galvanic effects can be excluded. (2) For the study of the reduction of galena, the CPE-galena electrode is

184

E. AHLBERG AND J. ,~SBJORNSSON

preferable, since the reduction reaction is clearly separated from the compet- ing hydrogen evolution. On pure galena these reactions overlap. (3) The electrochemical activity of CPE-galena is directly proportional to the amount of galena present at the electrode surface. (4) The reproducibility of the CPE-galena electrode is very good if care is taken in the mixing of the paste. (5) With the use of carbon paste electrodes, minerals in powder form and flotation concentrates can be used directly as electrode materials. This im- plies a unique possibility for individual optimisation of the leaching process.

ACKNOWLEDGEMENTS

This work was financially supported by the Swedish National Board for Technical Development (STU). The authors would like to thank Dr. Kazi- mira Purom~iki for the AAS analyses.

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