Study of Arsenic release of atmospheric

Scorodite in reductive environments

Csar Verdugo
1
, Gustavo Lagos
1

Levente Becze
2
,

Mario Gmez
2
& George Demopoulos
2

1
Departamento de Ingeniera de Minera, Pontificia Universidad Catlica de Chile (ceverdug@uc.cl)
2
Departament of Mining and Material Engineering, McGill University (george.demopoulos@mcgill.ca)
Outline
1. Introduction
Problems and challenges of arsenic in metallurgic process
2. Objectives
What are the goals of this research?
3. Methodology
Synthesis
Stability test
Characterization
4. Results
Characterization of initial solids
Stability test
Characterization final
5. Discussion and Conclusions

2
Introduction
Arsenic (As) is major contaminant present in wastes from metallurgical and mining
industries of non-ferrous.
Due to its high toxicity, environmental regulations are becoming increasingly more
stringent regardings its environmental disposal.
Many efforts have been made to confine As for disposing in relatively stable phases
and therefore, immobilize this toxic element.
Mainly two
methods
Co-precipitation of As(V) with Fe(III) by lime
neutralization in the form of poorly-
crystalline Fe(III)-AsO
4
solids (molar ratio > 3)
Crystalline scorodite:
1.- Autoclave : 150 C or higher
2.- Atmospheric: 95 C, involving
supersaturation control, avoiding nucleation.
Introduction - Methodology - Results - Conclusions
3
Previous work on scorodite has focused on the determination of its stability in oxidizing
conditions. In fact, can dissolve either congruently or incongruently, depending on pH.

Congruent dissolution: FeAsO
4
2H
2
O + H
+
=> H
2
AsO
4
-
+ Fe(OH)
2+
+ H
2
O (Dove and Rimstidt, 1985)

Incongruent dissolution: FeAsO
4
2H
2
O + H
2
O => H
2
AsO
4
-
+ Fe(OH)
3(s)
+ H
+
(Zhu and Merkel, 2001)

FeAsO
4
2H
2
O + H
2
O =>HAsO
4
2-
+ Fe(OH)
3(s)
+ 2H
+
(Zhu and Merkel, 2001)


However little is known under reducing conditions.
Why would be important to study this condition?

The dissolved oxygen concentration decreases as the depth increases in tailings ponds, contributing to
various reducing media, generating the potential release of As to the environment.

The reductive dissolution of scorodite could be catalyzed by Fe (III)-reducing bacteria, such as
Shewanella alga or Desulfuromonas palmitatis amongst others, which release dissolved arsenate as a
result of dissimilatory reduction of Fe(III) to Fe(II) (Cummings, et al., 1999; Papassiopi et al., 2003).
4
Introduction - Methodology - Results - Conclusions
Introduction
First motivation
Gypsum!
5
Introduction - Methodology - Results - Conclusions
Introduction
Second motivation
Lime is widely used for neutralization of sulphate-containing
acidic effluents (Langmuir et al., 1999; Jia & Demopoulos, 2008).
Due to this, the porewater of mining and
metallurgical tailings ponds are gypsum-saturated
(Bluteau et al. 2009).
This opens the possible interaction of scorodite
and gypsum or its constituents Ca
2+
or SO
4
2-

Some facts:
Objectives

This research considers 2 goals under concentrated aqueous solutions of As (40 g/L):

1. To determine the stability of atmospheric scorodite from oxic to anoxic conditions
at pH 7 until its equilibrium is reached.
2. To evaluate the behavior of scorodite particles under Redox conditions and pH 7 in
the presence of gypsum-saturated environments.
6
Introduction - Methodology - Results - Conclusions
Methodology
Introduction Methodology Results - Conclusions
7
Methodology
Introduction Methodology Results - Conclusions
8
Methodology
1.- Synthesis and characterization of
atmospheric scorodite.
2.- Stability test and full characterization of
scorodite particles.
Methodology
Introduction Methodology Results - Conclusions
9
XRD
Raman
ATR-IR
SEM
Chemical
analysis
Methodology
Introduction Methodology Results - Conclusions
10
Methodology
1.- Synthesis and characterization of
atmospheric scorodite.
2.- Stability test and full characterization of
scorodite particles.
Methodology
Introduction Methodology Results - Conclusions
11
No gypsum
Saturated- gypsum
1M NaOH
0,5M CaO
1. Chemical analysis
2. XRD
3. SEM
4. ATR-IR
5. RAMAN
Redox conditions:
DI water 400 mV 250mV -100mV
Introduction Methodology Results - Conclusions
12
Results
Introduction Methodology Results - Conclusions
13
Results
1.- Synthesis and characterization of atmospheric scorodite.
Atm. scorodite
I
n
t
e
n
s
i
t
y

(
r
e
l
a
t
i
v
e
)

Figure 1: XRD patterns.
R
a
m
a
n

i
n
t
e
n
s
i
t
y

(
r
e
l
a
t
i
v
e
)

Figure 2: Raman spectroscopy.
Introduction Methodology Results - Conclusions
14
Results
1.- Synthesis and characterization of atmospheric scorodite.
Figure 3: ATR-IR spectrum. Figure 4: SEM images.
Figure 5: 1M NaOH No Gypsum.
Introduction Methodology Results - Conclusions
15
Results
2.- Stability test and full characterization of scorodite particles.
Introduction Methodology Results - Conclusions
16
Results
2.- Stability test and full characterization of scorodite particles.
Figure 7: 0,5 CaO - Gypsum saturated.
Figure 6: 1M NaOH - Gypsum saturated.
Introduction Methodology Results - Conclusions
17
Results
2.- Stability test and full characterization of scorodite particles.
Wavenumber (cm
-1
)
Figure 8: XRD patterns after stability test. Figure 9: Raman spectroscopy after stability test.
Introduction Methodology Results - Conclusions
18
Results
2.- Stability test and full characterization of scorodite particles.
Wavenumber (cm
-1
)
Figure 10: ATR-IR spectra after stability test. Figure 11: SEM images after stability test.
Introduction Methodology Results - Conclusions
19
Conclusions

It was found that the use of NaOH as base during stability test, caused problems
resulting in high arsenic release, due to apparent strong local release of alkalinity.

The release of arsenic from scorodite particles was dramatically mitigated, due to
the presence of gypsum.

With the exception of the 100 mV severe anoxic environment, the release of
arsenic from atmospheric scorodite in the presence of calcium/gypsum did not
exceed 5 mg/L, even under mild reducing potential of about 250 mV.

This implies that from a disposal point of view scorodites arsenic release rate is
manageable when it is codeposited with gypsum near neutral pH and not less than
250 mV reducing environment.
Introduction Methodology Results - Conclusions
20
Conclusions

In fact, some publications support this phenomenon:

i. Harris and Monette, 1987 and Krause and Ettel 1989 found that Ca(OH)
2

yielded lower residual As concentration than NaOH.
ii. Similar results were found by Emett and Khoe 1994, where the presence
of calcium ions decreased significantly the dissolved As in neutral to
alkaline pH range conditions.
iii. Latter Jia and Demopoulos 2005, observed soluble calcium sulphate
enhanced the uptake of arsenate by ferrihydrite.
iv. Bluteau and colleagues 2009, postulated that the co-adsortion of Ca
2+
with
arsenate on ferrihydrite was one of the As retention enhancement
The real interaction of scorodite with Ca
2+
and/or SO
4
2-
is still unknown
Acknowledgment
21
This research was carried out at McGills
Hydrometallurgy Laboratory supported
via NSERC CRD grant.
Additional support was provided by:

Beca apoyo de realizacin de
tesis doctoral CONICYT N
24091003.
Vicerrectora de Investigacin
(VRI), Pontificia Universidad
Catlica de Chile.
Direccin de Postgrado de la
Escuela de Ingeniera UC (DIPEII),
from Pontificia Universidad
Catlica de Chile.
Study of Arsenic release of atmospheric
Scorodite in reductive environments
Csar Verdugo
1
, Gustavo Lagos
1

Levente Becze
2
,

Mario Gmez
2
& George Demopoulos
2

1
Departamento de Ingeniera de Minera, Pontificia Universidad Catlica de Chile (ceverdug@uc.cl)
2
Departament of Mining and Material Engineering, McGill University (george.demopoulos@mcgill.ca)