Department of Metallurgical and Materials Engng.

Universidade Federal de Minas Gerais - UFMG

Arsenic in Mining Effluents: Removal and Stability

Virginia S.T. Ciminelli
Chem. Eng.; M.Sc; Ph.D. Professor Chair, Millennium Institute: Water- a mineral approach

ICM3 Iquique, August, 18 -20

Contents
n

Introduction: the problem of Arsenic in mining effluents Industrial Practice Scorodite; Type I e II Calcium Arsenates Arsenical Ferrihydrite Stability of precipitates Mobility of Arsenic Final Remarks

n n n

The Arsenic Problem

n

Found in Organic and Inorganic Forms

The most common hydrosoluble species are: As(III) Arsenite - H3AsO3 As(V) Arsenate - H3AsO4

High Toxicity carcinogenic/mutagenic

As(III) is more toxic and mobile than As(V)
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The Arsenic Problem

n

Sources of contamination anthropogenic natural (Bangladesh, India, and others) Recommended level of 10 ug As/L to WHO - World Health Organization Remediation in view of the lack of applications, Immobilization/ Inertization

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Treatment of Mining Effluents

Gas emissions Aqueous Effluents
Concentrated solutions: precipitation is usual Major challenge: Trace elements/large volumes
production of aqueous effluents

End Product - Solid Residues

Waste minimization, dense residues Recovery/recycling value added Stable residues V. Ciminelli, 04

Treatment of Mining Effluents containing As: industrial practice Precipitation of

n Scorodite and Type II (autoclaves) n Calcium arsenates n Arsenical Ferrihydrite
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Industrial Practice: Scorodite; Type I/II

Scorodite: FeAsO4.2H2O; Type I : Fe 2(HAsO4) 32H2O; Type II: Fe(AsO 4)x(SO4)y(OH) z
where x=0,8; y= 0,04-0,06 e z= 0,3-1,3

Crystalline product; High As content related to other processes Produced at T > 150 oC Autoclave needed Stoichiometric consumption of Fe Easy filtration; Less water retention; less area for disposal Requires polishing for As<0.1 mg/L Stability(?) Feasible at ambient pressure?
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Production of Scorodite at 95oC

Fe/As
(mol/L)

[As]I 1.02 0.52 0.23

[As]f 0.22 0.09 0.10

%As
removal

1.00 1.42 1.21

78 83 55

Seeds 200g/L; pH =1.6-2.4; T=95oC

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Production of Scorodite at 95oC

Investigated at McGill University
[As], ppm

Key point - control of supersaturation (pH vs. [As]) to avoid homogeneous nucleation Tested for high [As] :10 0.1 g/L Various stages needed Main operational difficulty is

C*
100

Cc = ScC*

Homogeneous nucleation

10

1 Heterogeneous nucleation

pH

the pH control at high temperatures. Large amounts of seeds, Peroxide and Iron sources needed. Real advantages related to the hydrothermal processing?
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Industrial Practice: Precipitation of Ca Arsenite/Arsenate

Ca3(AsO4).Ca(OH) 2 Costly attractive ($) compared with Fe. Higher residual As pH>12, As < 0.5 mg/L Major problem: instability by carbonation

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Industrial Practice: Solubility of

Fe Ca Ca

Arsenates and Arsenites

Fe

Fe

Exptal. conditions should be adjusted for maximum removal Robins, 1981 Better removal as Fe compounds and for As(III) V. Ciminelli, 04

Industrial Practice: Precipitation of Arsenical Ferrihydrite (FH)

H2O2 and Ferrous sulfate needed for As oxidation and precipitation. Polishing Fe/As~15 e pH 7,5-8,5 Composition (% w/w)
Fe As S Ca CaSO4.2H2O Ca3(AsO4)2 FeAsO4.2H 2O(amorf.) 14.72 6.40 9.15 10.52 46.53 1.78 17.65 20.30 9.90 5.23 7.11 24.10 1.57 28.67

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Industrial Practice: Precipitation of Arsenical Ferrihydrite (FH)

FexOy(H2O)z disordered solid (2L ou 6L DRX= f(T))
Elevated specific surface area, obtained through fast hydrolysis; pH 3-7; high adsorptive capacity
Broadening of FH main diffraction line w/ As adsorption/co-pptation

XRD of the arsenical FH after Gypsum leaching

Vasconcelos et al., 2003

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Industrial Practice: Precipitation of Arsenical Ferrihydrite (FH)

Most popular process and Best available practice according to the US EPA [As] may be reduced to < 0.1 mg/L Consumption of Fe source and oxidation agent High retention of water (~20% sol.) $ disposal Stable residue (30 years) for Fe/As> 4 Cations/anions (Si, P, org) increase stability, by slowing down the rate of conversion FHGoethite/Hematite
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Stability of Arsenic compounds

Short term - leaching std procedures such as the TCLP - toxicity characteristic leaching procedure Long-term prediction - ?
Thermodinamics and kinetics Phases and solubility
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Relative TCLP solubility of Iron and Calcium Arsenates

Precipitated Phase Scorodite, 95oC*
Type-1 Type-2 FH Fe:As 9:1 FH Fe:As 1.5:1 Guerinite** Hadingerite;Pharmacolite**
* *Ca arsenate compounds

TCLP Solubility (mgAs/L)

<0.8 <1.0 1-85 <0.34 0.4 50 1000 3000 Non-toxic Waste if [As]<1mg/L

Scorodite, 150oC

Adapted from Swash and Monhemius, 1995; except for *- our study

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Long-Term Stability - Thermodynamics

Stability of arsenates and sulfides are restricted to specific conditions of Eh-pH. Fe hydroxides/oxides are the most stable species under circumneutral pH and aerobic conditions !
Zhu e Merkel (2002)

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Long-Term Stability Effect of CO2

Robins, 1983

Fe(II) and Ca arsenates decompose in the presence of CO2

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Long-Term Stability: Fe(III) and Al hydroxides

are most common end products

Robins, 1983

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Usual Conditions of Precipitation

pH 3- 7 Fe/As >4 favor adsorption of Arsenic by oxihydroxides of Iron Adsorption on iron, aluminum and manganese oxyhydroxides play an important role on As mobility in the environment
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Factors controlling As mobility

n Soil characteristics Mineralogy/ Specific Surface Area/ Loading Capacity/Complex Stability n Eh-pH; drainage water composition n As Speciation Reactions involved: Precipitation/dissolution Adsorption/desorption
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Studied Materials at UFMG

n Natural soil samples
n Natural mineral samples: Al-, Fe- and Fe-Mn oxihydroxides n Modified samples of Me-oxides n Synthetic Fe-Mn materials n Biosorbents To understand and control As mobility in tailings ponds To select cheap materials for As remediation Approach: Selection, Molecular modeling, Design.
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Application: Adsorption on Fe and Al oxides - Irreversible immobilization of As

Arsenic Solution

Tailings
Sorbent

Sorbent Water Tailings Dam

Filters

Solution without arsenic

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A.C.Q. Ladeira (Ph.D. Thesis)

Factors controlling As mobility: Type of Soil

Sample red 1 sampl Sample yellow 2 Sample brown 3 Sample blue 4
Qmax.=3.6 Qmax .=3.6mg/g mg/g

3 As adsorbed (mg/g )

Qmax.=1.0 Qmax .=1.0mg/g mg/g Qmax.=0.7 Qmax .=0.7mg/g mg/g Qmax.=0.1 Qmax .=0.1mg/g mg/g

0 0 200 400 600 800 1000 V. Ciminelli, 04

As(III) eq. (mg/L)

Factors controlling As mobility: Soil Composition and SSA

Vermelho % Marrom % 18,91 4,90 0,002 8,17 5,00 61,06 57,70 16,2 Amarelo % 17,93 7,70 0,36 5,52 4,41 63,17 48,20 18,9 Rejeito % 19,35 0,92 0,002 4,90 2,33 63,74 41,00 5,2 V. Ciminelli, 04

Al 2 O 3 Al 2 O 3 As Fe 2 O3 Fe 2 O 3 SiO 2

( tot) ( sol )

23,25 17,28 0,002

(tot) (sol.)

11,90 10,56 50,48 44,00 35,7

SiO 2 (tot )
(silica)

Specific Surface Area (SSA)

Factors controlling As mobility: Soil Mineralogy

14 12

As(V) Qmax. (mg/g)

10 8 6 4 2 0

As(III)

Qmax. (mg/g)

10 8 6 4 2 0 goethite gibbsite trop. Soil kaolinite

goethite

gibbsite

trop. Soil

kaolinite

Relatively higher As(V) uptake

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Factors controlling As mobility:

Speciation
Eh (Volts) 2.0
1.5

As - H2O - System at 25.00 C

H3AsO4(a)
1.0 0.5 0.0 -0.5 -1.0

H2AsO4(-a) HAsO4(-2a)

H3AsO3(a)
-1.5 -2.0 0 2 4 6 8

H2AsO3(-a)

10

12

C:\HSC4\As25.iep
ELEMENTS As Molality 1.000E+00 Pressure 1.000E+00

pH

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In addition to a lower uptake, loaded As(III) on (Fe, Al) oxides is more easily remobilized.
As(V)/As(III) (mg.g-1) Gibbsite 2.5/1.1 Goethite 8/5.6 Oxisol 2/0.8 Leaching solutions TCLP TCLP TCLP TCLP TCLP TCLP K2SO4 0.5M H2O MgCl2 1M Leached As(III) (mg.L-1) 2.42 11.7 <0.1 62.6 2.46 6.6 19.5 12.0 9.9 V. Ciminelli, 04

Adsorption/Desorption of As on Fe and Al oxides

What is the reason for the different behaviour of As(III) and As(V)?
(Immobilization Mechanism)
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Adsorption on S/L Interfaces

Non-specific adsorption Electrostatic attraction; reversible
Outer sphere coordination

Specific adsorption Stronger bonds; may occur regardless the solid charge . Inner sphere coordination

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Electrophoretic Mobility and Electrostatic Interaction

Electrophoretic mobility (/sec)/(volt/cm)
-1

0.6 0.3

Goethite

IEP=8.1

0.0
IEP=6.3 IEP=7.9

-0.3 -0.6 0.6 0.3

IEP=7.7

Gibbsite

0.0
IEP=7.0

-0.3 -0.6 3

EM= f(Potential at the shear plane)

unloaded loaded with As(III) loaded with As(V) 4 5 6 7

IEP=7.6

10

11

pH

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Adsorption Structures evaluated by DFT calculations

H H

o O o O
As

As

O
O

O O
O

Al

Al

Al O

Al O O

bidentate_binuclear (bb)

monodentate_mononuclea (mm)
H H

O O

O O

As
O
O

As
O
O

Al O

Al O

Al

O Al

monodentate_binuclear (mb)

bidentate_mononuclear (bm)

Prof. H. A. Duarte, Chemistry Dept.

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Adsorption Structure by EXAFS and DFT: As(V)

O O O
1.92 3.19

As
1.68

o 109.3 3.19

O
1.92

O O Al

2.95 O

Al

O O

The distance of 3.19 (EXAFS) was consistent with a Bidentate-Binuclear Model. Release of two hydroxyls .
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Adsorption Structure by EXAFS/ DFT: As(III)

The distance of 3 (EXAFS) was consistent with a Bidentate-Mononuclear Model And no pH variation.

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Final Considerations

Low temperature As-FH, and High temperature Scorodite+ Type II (autoclave) are the best established processes for As removal from mining effluents.

As-FH most popular; product contains typically 3-9%

As (co-pptated/adsorbed); considered stable if molar Fe/As> 4; slow kinetics for phase transformation.

Short-term Stability can be evaluated by std. leaching

procedures - not always consistent with the conditions found in the actual disposal site. The results will dictate disposal constraints, e.g. as toxic or non-toxic waste.
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Final Considerations

Long term stability Thermodynamics indicates that usual As compounds are stable under restricted conditions of pH and Eh. Transformation to more stable phases will depend on the site conditions.

Arsenic Mobility is mostly controlled by adsorption on

Fe, Al and other metal oxihydroxides.

The relatively high remobilization of As(III) is explained

by a model where the arsenic molecule binds to the oxide surface without deprotonation; the hydroxyl group, OH, remains as the bridging unit.
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Acknowledgements
My co-authors Ana Cludia Q. Ladeira Hlio A. Duarte Claudia Lima Caldeira

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