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Mario Alberto Gomez PhD Oral Defense Department of Mining and Materials Engineering, McGill University, Montreal, QC, Canada January 6th, 2011
1
Outline
In our study three distinct phases were found : Scorodite, Scorodite, Ferric Arsenate sub-Hydrate (FAsH) and sub(FAsH) Basic Ferric Arsenate Sulphate (BFAS)
Scorodite : FeAsO4 2H2O Ferric Arsenate sub-Hydrate (FAsH) : FeAsO4 3/4H2O sub(FAsH)
NOT (Fe2(HAsO4)3 zH2O by Swash) confirmed via vibrational spectroscopy
P.M. Swash and A.J. Monhemius, Hydrometallurgy 94, Published by Chapman & Hall, 1994.
Fe
FeAsO4 2H2O
H As
Scorodite
Rlative Intensity
Orthorhombic Pbca
FeAsO4 3/4H2O
10
20
30
40
50
60
70
80
Ventruti and Gomez et al. (2011) unpublished
2U
Evidence of well grown monoclinic type of crystals. With the aid of FEG-SEM FEGand TEM-SAED, a snap TEMshot of the rounded particle re-crystallizing to reform the well defined monoclinic like crystal was captured.
W avenumber (/ cm -1 ) 1000
Trasmission Intensity
W avenumber (/ cm -1 )
10 0
Trasmission Intensity
Trasmission Intensity
9 0
8 0
7 0
6 0
0
Trasmission Intensity
3700
3300
2900
2 00
AsO43-
OH-/H2O
AsO43-
OH-/H2O
Raman Intensity )
Raman Intensity )
3600
3200
2800
1000
800
600
400
200
W avenumber (/cm -1 )
3700
3300
2900
2 00
W avenumber (/cm -1 )
Wavenumber(/cm-1)
Wavenumber(/cm-1 )
1000
800
600
400
200
Raman Intensity)
Raman Intensity)
900
800
700
600
3600
3200
2800
Wavenumber(/cm-1 )
Wavenumber(/cm-1)
Wavenumber (/cm-1)
600
Trasmission Intensity
1200
1000
800
3700
3300
2900
2500
Fe-O
SO42AsO43-
OH-/H2O
Raman Intensity )
600
200
Raman Intensity )
AsO43-
3700
3300
2900
2500
Wavenumber (/cm-1)
C2v
SO4
AsO4
C2v
~Td
In general, the AsO4 (SO4) group symmetry is reduced from a Td C2, 2v while that of the AsO4 (SO4) group remains ~ Td (equivalent).
This demonstrated that each sulfate and arsenate can occupy similar molecular sites in the crystal structure. This was later confirmed upon solution of the crystal 11 structure (unpublished -Ventruti and Gomez 2011).
1994
As-O As-Fe
XANES/EXAFS determines average local coordination up to 4 . For Scorodite and FAsH crystallographic information exist to fit the EXAFS. However, for BFAS no crystallographic information exist for now.
FAsH
Scorodite
13
Short term stability tests showed that all phases yielded < 1ppm As.
At lower pH (3 and 5), the FAsH phase was found to yield higher amounts of arsenic then the corresponding low and high sulphate BFAS phases. However at lower pH (3), the BFAS with lower sulphate content gave slightly higher arsenic release in comparison to the higher sulphate containing BFAS. Interestingly at higher pH (7.5) both FAsH and the lower sulphate containing BFAS yielded similar arsenic release, while the higher containing sulphate BFAS gave the 14 highest arsenic release.
Case1
Case 2
Case 3
Case 5
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XRD and IR of all trials at 0 hrs (i.e. 2.5hrs) and after 10hrs (i.e.12.5hrs) reaction time determined: sulphate-containing scorodite: (Fe(AsO4)1-x(SO4)x(OH)x 2H2O. Interestingly, the H-bonding environment in case 1 was not fully ordered.
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In case 1 (Fe/As 1.5) at 2.5 hrs and 150 C, the H-bonding environment was found not to be well ordered in comparison to other cases (Fe/As 1.5 ) under the same reaction times. Similar results were also observed for tests at 175 C. Extension of reaction time (3.5 hrs) in case 1, allows the structure to fully develop the H-bonding environment similar to longer times or lower Fe/As ratio ( 1.5 ) and independent of the presence of copper. Powder XRD indicated that in all cases the product was crystalline scorodite but was 18 not able to detect the disorder in the H-bonding environment. H-
A precipitate was seen to form before 150 C, this was unlike scorodite and unlike any of the other cases.
Solid samples were collected and analyzed by various techniques.
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The intermediate phase throughout the reaction was found to contain various amounts Fe, As, Cu, S and O (ICP-AES, EDS and XPS). The gel-like product was made up of smaller particles which exhibited ordered and unordered domains.
20
The unknown gel-like precipitate was further analyzed via XRD and cross polarized microscopy. XRD showed that indeed this gel-like precipitate was composed of an X-ray ( = 1.78897 ) amorphous phase but also some domains existed where longer range order exist. This is in agreement with cross polarized microscope results.
21
Both BFAS and this intermediate phase were found to have similar molecular groups, symmetry and bonding in both IR and Raman analysis. 22
The residue was produced under bench scale pressure oxidation CESL
processing conditions (150C and 60 min).
Element As Fe S Total S elemental Pb (ppm) Assay (%) 0.54 29.3 36.3 32.1 4290
From the literature, the general view is that under these conditions arsenic should precipitate as Scorodite in addition
to having hematite, and elemental sulfur in the residue.
23
Match to Hematite
Match to S S
Match to Arsenopyrite
Match to Scorodite
24
25
600
-1
700
800
900
1000
Wave numbers(cm )
600
700
800
900
1000
700
750
800
850
900
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During the synthesis work an unknown amorphous phase was first observed, followed by some scorodite impurities and finally the yukonite [Ca2Fe3-5(AsO4)3(OH)4-10xH2O where x = 2-11]. Single crystal and synchrotron analysis ( = 0.71 and 0.41 ) of the natural Tagish Lake sample was conducted to observe if any crystallographic information could be extracted 27 (space group and lattice parameters).
= 1.54
TL yukonite
Lab based PXRD indicated that the synthetic yukonite material was in excellent agreement with that of the natural Tagish Lake sample and unlike that of arseniosiderite. The Grotta della Monaca yukonite was found to have scorodite impurities (PXRD) and sulfate impurities in the form of K2SO4 28 (ATR-IR and SEM-EDS).
Romanech Arseniosiderite
TL yukonite
TEM and SAED of the Tagish Lake yukonite showed that at 100 nm it was essentially amorphous. However, at 5nm nano-crystalline domains ranging from 1-15 nm in size were observed and all exhibited lattice fringes of 0.32nm. This is in contrast to arseniosiderite which is composed of micro-size single crystal domains and exhibits lattice fringes of 0.54 nm. In addition an hexagonal symmetry 29 lattice was observed and no monoclinic domains were observed.
As K-edge XANES
To probe the local As and Fe structure (and oxidation states) of yukonite and arseniosiderite XAS analysis was conducted. The oxidation states for the Tagish Lake yukonite and Romanech arseniosiderite were found to be in the As5+ and Fe3+ states, in agreement with that of the synthetic samples where pure As5+ and Fe3+ sources were used. More importantly, the local structure and order of arsenate and ferric octahedral states in yukonite and arseniosiderite were found to be similar in both minerals. 30
Therefore, we decided to conduct Ca L-edge XANES analysis on yukonite and arseniosiderite to investigate if the local structure was the same in arseniosiderite and yukonite. As it can be seen from the Figure above, the Ca L-edge XANES of both minerals are exactly the same indicating that crystal field splitting, coordination and site symmetry around the Ca atoms should be the same. This is in contrast to the previous EXAFS findings.
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In the case of yukonite, the IR analysis showed that the arsenate molecules were found in an ~Td environment, and its hydroxyl (as well as its arsenate) environment was quite diffuse in nature typical of a semi-crystalline phase. Raman analysis further confirmed this behavior. For arseniosiderite the arsenate molecules were found to be in an ~Td environment but in addition HAsO42- molecules were observed in both the IR and Raman spectra. More importantly the hydroxyl environment is indicative of two distinct H-bonding environments and this was postulated to cause the higher degree of order. 32
Unequivocal and systematic identification of the type of phases produced under high temperature autoclave conditions in the Fe(III)-AsO4-SO4 Fe(III)system. Correction and determination of a new phase diagram, name and molecular formulae for the phases produced in the Fe(III)-AsO4-SO4 Fe(III)system. The first time the importance of reaction time (kinetics) was shown to affect the stability of these phases via metastable phases. Clarification of the discrepancies in previous works (Swash and Dutrizac) Dutrizac) and unification of the ideas (including our own studies) and theories for the Fe(III)-AsO4-SO4 system. Fe(III)New vibrational (IR and Raman) and group analysis data for the phases produced in the Fe(III)-AsO4-SO4 system as well as new XAS data (As KFe(III)Kedge and Fe L-edge) presented. LAnalysis of industrial residues indicated that scorodite was not the main arsenic form found but rather a BFAS like phase was observed. Long term arsenic release data for the non scorodite phases (FAsH and (FAsH BFAS).
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The first time the effect of copper on the Fe(III)-AsO4-SO4 system was Fe(III)investigated at 150 C (CESL temperatures). Copper (or Mg) was found not to interfere with scorodite formation at 150 C and 2.5 hrs. Excess ferric iron in starting solutions (Fe/As ~ 2 and 2.5 hrs) was found to affect the H-bonding (IR) in the produced scorodite without Haffecting its crystallinity (XRD). Existence of a never before observed metastable Cu-Fe-AsO4-SO4 phase Cu-Feat lower temperature (< 150 C), time (< 60 min) and equimolar Fe, Cu, As was discovered. This metastable phase was found to consist of ordered and disordered domains (XRD, TEM and Polarized Microscoscopy) but its molecular structure was found to be similar to BFAS and unlike scorodite. Analysis of an industrial residue produced under CESL conditions found the arsenic to be in a BFAS like form (or arsenate adsorbed onto hematite) and not scorodite.
34
First time Yukonite was successfully synthesized (Dr. L. Becze). Becze). Comparison with the natural specimens from distinct locations in the world (Italy and Canada) showed the synthetic product to be equivalent at the elemental, molecular and structural level. First time vibrational (IR and Raman) and XANES (Fe and Ca LLedge) data was presented for both yukonite (synthetic and natural) and arseniosiderite. arseniosiderite. First time a molecular (IR, Raman, XANES) and structural (XRD, TEMTEM-ED) link was given between these two otherwise similar minerals. Yukonite was found to consist of nano-crystalline ordered domains nanowhile arseniosiderite was found to consisit of micro size ordered domains and the link between the order of these structures was found to arise from the difference in their H-bonding. H-
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Future Work
Determine the crystal structure of BFAS and how it relates crystallographically with BFS. Does varying the [Fe3+] and fixing the [As5+] produce different phases. How does precipitation via in-situ oxidation (O2 or air) of inFe2+ and As5+ affect the arsenic phases produced. These phases must be thoroughly analyzed via elemental, electronic, molecular and structural analysis. No phase transformation to ferrihydrite of the ferric arsenate phases produced herein was observed at 25 C; is this idea a real experimental occurrence or just a computational thermodynamic calculation ?
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Acknowledgements
Dr. Demopoulos and Dr. Cutler Dr. Becze and Dr. Le Berre Dr. Assaaoudi Laboratoire de Caractrisation des Matriaux (Dr. Eluatik) Centre for Self Assembled Chemical Structures Canadian Light Source (Dr. Warner and HXMA, SGM team)
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