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Precipitation and characterization of Ca(II)-Cu(II)-Fe(III)Ca(II)-Cu(II)-Fe(III)-AsO4-SO4 phases

Mario Alberto Gomez PhD Oral Defense Department of Mining and Materials Engineering, McGill University, Montreal, QC, Canada January 6th, 2011
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Outline


This talk will be broken into three sections:


1. 2. 3.

Fe(III)Fe(III)-AsO4-SO4 system (150-225 C) (150Cu(II)-Fe(III)Cu(II)-Fe(III)-AsO4-SO4 system (150 C) Ca(II)-Fe(III)Ca(II)-Fe(III)-AsO4 system (95 C)

  

Contributions to Original Knowledge Future Work Acknowledgments


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The Fe (III) AsO4 SO4 System

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

Basic Ferric Arsenate-Sulphate (BFAS): ArsenateFe(AsO4)x (SO4)y (OH)z wH2O


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Phase Diagram for the High Temperature Fe(III)Fe(III)-AsO4-SO4 System (1994)

P.M. Swash and A.J. Monhemius, Hydrometallurgy 94, Published by Chapman & Hall, 1994.

Phase Diagram for the High Temperature Fe(III)Fe(III)-AsO4-SO4 System (2010)

The Fe (III) AsO4 SO4 System

Fe

FeAsO4 2H2O

H As

Scorodite

Rlative Intensity

Orthorhombic Pbca

FeAsO4 3/4H2O

Ferric Arsenate sub-Hydrate


Triclinic- P1

Fe(AsO4)x (SO4)y (OH)z wH2O

Jakeman et al., Inorg. Chem. 30, 2806 (1991)

Basic Ferric Arsenate Sulphate


Monoclinic(P21/c)-Orthorhombic(Pnma)?

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20

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60

70

80
Ventruti and Gomez et al. (2011) unpublished

2U

The Fe (III) AsO4 SO4 System


Scorodite : Orthorhombic FAsH : Triclinic BFAS : Monoclinic?

 Aggregates of crystallites.  On average, the size of individual crystallites is < 1 m.

 Aggregates of crystallites.  On average, the size of individual crystallites is 1 m.

 Aggregates of two distinct particles.  On average, the size of individual crystallites is 2 m.


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The Fe (III) AsO4 SO4 System




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.

The Fe (III) AsO4 SO4 System

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

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W avenumber (/cm -1 )

3700

3300

2900

2 00

W avenumber (/cm -1 )

Wavenumber(/cm-1)

Wavenumber(/cm-1 )

Scorodite contains arsenate in 1 distinct crystallographic site.

FAsH contains arsenate in 2 distinct crystallographic sites.


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1000

800

600

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200

Raman Intensity)

Raman Intensity)

900

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3600

3200

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Wavenumber(/cm-1 )

Wavenumber(/cm-1)

The Fe (III) AsO4 SO4 System


Wavenumber (/cm-1)
1400
Trasmission Intensity

Wavenumber (/cm-1)
600
Trasmission Intensity

1200

1000

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3700

3300

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Fe-O

SO42AsO43-

OH-/H2O

Raman Intensity )

1400 1200 1000 800

400 Wavenumber (/cm-1)

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Raman Intensity )

AsO43-

3700

3300

2900

2500

Wavenumber (/cm-1)

Basic Ferric Arsenate Sulphate


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The Fe (III) AsO4 SO4 System


Basic Ferric Arsenate Sulphate (molecular solid solution)
~Td
SO4 AsO4

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).

The Fe (III) AsO4 SO4 System


Comparison of our FAsH and BFAS to previously reported new and old phases (1994 & 2007)

McGill 2008 2007

McGill McGill 2008 2007 2007 1994 1994

1994

FAsH = Phase 4 = Type 1

BFAS = Phase 3 = Type 2


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The Fe (III) AsO4 SO4 System


FAsH BFAS
FAsH BFAS

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

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The Fe (III) AsO4 SO4 System

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.

The Cu (II) Fe (III) AsO4 SO4 System

Case1

Case 2

Case 3

Case 5

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The Cu (II) Fe (III) AsO4 SO4 System Results: Solid Composition


Test Case 1 Case 2 Fe % 24.1 23.9 21.1 23.9 21.2 24.2 As % 28.8 31.6 35.1 31.9 29.5 32.5 Cu % 0 0 0.4 0.30 0.80 Mg % 0 0 0 0 0.60 S% 1.6 0.2 0.6 0.1 1.2 Raman

*SD-SO4 SD*SD-SO4 SD*SD-SO4 SD*SD-SO4 SD*SD-SO4 SDSD

Case 3 Case 4 Case 5 Theoretical:

* SD-SO4 : sulphate containing scorodite SD16

The Cu (II) Fe (III) AsO4 SO4 System

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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The Cu (II) Fe (III) AsO4 SO4 System

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-

The Cu (II) Fe (III) AsO4 SO4 System


Evidence of metastable phase formation during the heat up period
(150C ~ 2.5 hrs) of Case 4 was observed.
101 C and 40 min

150 C and 750 min

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 Cu (II) Fe (III) AsO4 SO4 System

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.
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The Cu (II) Fe (III) AsO4 SO4 System


40 min (101 C)
Cross Polarized Microscope

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.
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The Cu (II) Fe (III) AsO4 SO4 System


The unknown intermediate phase was further analyzed via ATR-IR and Micro-Raman to determine its molecular structure Raman IR

Both BFAS and this intermediate phase were found to have similar molecular groups, symmetry and bonding in both IR and Raman analysis. 22

Characterization of Industrial Residues


(1) Teck Metals

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.
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(1) Teck Cominco Residue (XRD via Database Search Analysis)

Match to Hematite

Match to S S

Match to Arsenopyrite

Match to Scorodite
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(1) Teck Cominco (Vibrational: Raman Analysis)

Teck Residue Hematite (STD)

Teck Residue Elemental S (STD)

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(1) Teck Cominco (Vibrational: ATR-IR Analysis)

Scorodite (FeAsO4*2H2O) AsO4 region 600 700 800 900 1000

BIAS (FeAsO4SO4OH) AsO4 region

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-1

700

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1000

Wave numbers(cm )

IAsH FeAsO4*3/4H2O AsO4 region

Teck Cominco Industrial Residue AsO4 region

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The Ca (II) Fe (III) AsO4 SO4 System

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).

The Cu (II) Fe (III) AsO4 SO4 System

= 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).

The Ca (II) Fe (III) AsO4 SO4 System


Tagish Lake Yukonite

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.

The Ca (II) Fe (III) AsO4 SO4 System

As K-edge XANES

As K-edge EXAFS TL yukonite XANES Fe 2p-edge

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

The Ca (II) Fe (III) AsO4 SO4 System

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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Structural and molecular analysis of yukonite


HAsO42-

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

Expected Contributions To Original Knowledge


The Fe (III) AsO4 SO4 System


 

 

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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Expected Contributions To Original Knowledge


The Cu(II)-Fe (III) AsO4 SO4 System Cu(II)  

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.
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Expected Contributions To Original Knowledge


The Ca(II)-Fe (III) AsO4 System Ca(II) 

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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