Escolar Documentos
Profissional Documentos
Cultura Documentos
Carlos Ayora
Instituto de Diagnóstico Ambiental y Estudios del Agua, CSIC
caigeo@idaea.csic.es
Antes que nada
1.0
fraction
0.8
0.6 CO2(aq)
HCO3-
0.4 CO3-2
0.2
0.0
2 3 4 5 6 7 8 9 10 11 12
pH
oxidación de pirita
Acidithiobacilus ferrooxidans
Fe2+ + 0.25O2 + H+ Fe3+ + 0.5H2O
FeSO4·7H
Quien no2Oproduce
+ 0.25O2 =acidez?
FeOOH + 5.5H2O + SO42- + 2H+
CaSO ·2H O = 2H O + SO 2-
+ Ca2+
Consumo de acidez
CaCO3 + 2H+ = Ca2+ + CO2 + H2O
La clave es la mineralogía !!
Dold, 2017
+total S
Sobek +total S Sobek + CrR S
FeSO4
Tests cinéticos ácido-base
CELDAS HÚMEDAS, COLUMNAS, CAMPO
100.00
Sc
pH > 7 /
μg)
L
Y
10.00 Gd
La
pH<4
1.00
x
ee
pim
r n
ea
tl(
pH>5.5
0.10
0.10 1.00 10.00 100.00
pH >6.5pH > 5.5 100.00 conservative mixing (μg/L)
Al
10.00 Cu
Fe pH<4
1.00
m /
g)
L
pH <4
al(
0.10
x
ee
pi
rmn
et
0.01
pH>5.5
G
A B C 0.01 0.10 1.00 10.00 100.00
conservative mixing (mg/L)
Oxidación de pirita en galerías y residuos
100.00
1.00
pH<4
Fe2+ + 2SO42- + 2H+
x
ee
pi
rmn
ea
tl(
pH>5.5
0.10
0.10 1.00 10.00 100.00
pH >6.5pH > 5.5 100.00 conservative mixing (μg/L)
Al
10.00 Cu
Fe pH<4
1.00
m /
g)
L
pH <4
al(
0.10
x
ee
pi
rmn
et
0.01
pH>5.5
G
A B C 0.01 0.10 1.00 10.00 100.00
conservative mixing (mg/L)
El Fe(II) se oxida y precipita schwertmannita
100.00
Sc
pH > 7 Y
/
μg)
L
10.00 Gd
La
pH<4
1.00
x
ee
pi
rmn
ea
tl(
pH>5.5
0.10
0.10 1.00 10.00 100.00
pH >6.5pH > 5.5 100.00 conservative mixing (μg/L)
Al
10.00 Cu
Fe pH<4
1.00
m /
g)
L
pH <4
al(
0.01
pH>5.5
G
A B C 0.01 0.10 1.00 10.00 100.00
2 2
conservative mixing (mg/L)
8 Fe 2 O 2 SO 10 H2O Fe 8O 8( OH )6( SO 4 () s ) 14 H
4
Atenuación natural de Fe
Fe2+ + 0.25O2 + H+ Fe3+ + 0.5H2O
d[Fe(II)]
k Fe [Fe(II)] pO2 kFe=10-3.55 a 10-3.75 t1/2= 3.2 to 5.1 hour
dt
8Fe3 SO24 14H2O Fe8O8 (OH)6 SO4 (s) 22H
d[Fe(III)]
k Fe [Fe(II)] pO2 k sch [Fe(III)] [H ]1 at pH 3 t1/2= 19.6 to 60.9 hour
dt
-2
1.5 10
-2
1.2 10
Fe(II) model
Fe(III) model
Fe (molL )
-3
-1
9.0 10
Fe model
TOT
measured Fe(II)
-3
6.0 10 measured Fe(III)
measured Fe
TOT
-3
3.0 10
c February 2008
0.0
0 50 100 150 200 250 300
Distance (m)
Atenuación natural de As
2Fe3 H3 AsO3 H2O 2Fe 2 H2AsO 4 3H
d[As(III)]
k As [As(III)] [Fe(III)] kFe=10-1.20 [Fe(III)+= 0.8 mmol/L t1/2= 0.4 hour
dt
Sch H2 AsO4 Sch As 0.62SO42 0.24H
d[ As( V )]
k As [ As(III)] [Fe(III)] K Dk sch[Fe(III)] [H ]1
dt
As (mol L-1)
Consumo de alcalinidad
100.00
Sc
pH > 7 Y HCO3-
/
μg)
L
10.00 Gd
La
pH<4
1.00
imn
ea
tl(
Fe3+
x
ee
pr
pH>5.5 Al3+
0.10
0.10 1.00 10.00 100.00
pH >6.5 100.00 conservative mixing (μg/L)
pH > 5.5
Al
10.00 Cu
Fe pH<4
8Fe3+ + 22HCO1.300- + SO42- + 5H2O =Fe8O8 (OH)6SO4 +22CO2
m /
g)
L
pH <4
al(
100.00
0.01
pH>5.5
G
Sc
pH > 7 Y
/
μg)
L
10.0 0 Gd
La
pH<4
A
1.0 0
e
ima
n
tl(
B
r
e
C
x
ep
pH>5.5
pH <4
n
t
0.10
x
epr
eim
e
/
μg)
L
10.00 Gd + 2·(Fe(II)+ Zn + Cu + Mn)
La
pH<4
1.00
x
ee
pim
r n
ea
tl(
pH>5.5
0.10
0.10 1.00 10.00 100.00
pH >6.5 100.00 conservative mixing (μg/L)
pH > 5.5
Al
10.00 Cu pH 6.5
Fe pH<4
1.00 pH 5
m /
g)
L
pH <4
al(
0.10
nt
pH 3.5
x
ee
pim
r e
0.01
pH>5.5
pH 2.5
100.00
G
Sc
pH > 7 Y
/
μg)
L
10.0 0 Gd
La
pH<4
A
1.0 0
e
ima
n
tl(
B
r
e
C
x
ep
pH>5.5
pH <4
n
t
0.10
x
epr
eim
e
experimental (mg/L)
Fe
experimental (mg/L)
Zn 10.00
100.00 1.00 cons. Cons.
Sc pH <3.5 pH <3.5
pH > 7 Y 1.00
/
μg)
L
10.00 Gd
La 0.10
pH<4 0.10
1.00 mixing
pH>6.5
pH>6.5
mixing
er
imn
ea
tl(
0.01
p
0.01
x
e
pH>5.5
0.10 0.01 0.10 1.00 10.00 0.01 0.10 1.00 10.00 100.00
0.10 1.00 10.00 100.00 conservative mixing (mg/L) conservative mixing (mg/L)
pH >6.5pH > 5.5 100.00 conservative mixing (μg/L) 100.00 100.0
Al Al Sc
Y
10.00 Cu Cu
experimental (mg/L)
experimental (g/L)
Fe pH<4 10.00 Gd
Cons. La
pH< 3.5 10.0
1.00 cons.
1.00 pH< 3.5
m /
g)
L
pH <4
al(
0.10
m
r n
et
1.0
x
ee
pi
100.00
0.01
pH>5.5 0.10
G
Sc
pH > 7 Y
/
μg)
L
10.00 Gd
La
pH<4
A
1.00
imn
e l(
ta
B
r
C
p
x
ee
pH>5.5
pH>6.5
0.10 1.0 10.00 100.00
pH >6.5pH > 5.5 100.00 conservative mixing (μg/L)
mixing
Al
10.00 Cu
Fe pH<4
1.00
m /
gL
)
pH <4
na
tl(
0.10
x
epim
r
e e
0.01 0.1
G 0.01
A B C 0.01 0.10 1.00 10.00 100.00
conservative mixing (mg/L )
45%
t year-1 t year-1 Zn
Pb 0.6%
As 23 10000
Mn 0.5%
Cd 7 340
Fe 0.2%
Pb 12 2000 0 20 40 60 80 100
EU Water Framework
Directive 2000/60/EC
320 hm3
TRATAMIENTO PASIVO
- reactivo
- permeable
- accesible y barato
- que dure
- poco mantenimiento
800 S-4
S-3
400 S-3-2
S-3-1
0
-6 0 6 12 18 24
Time (months)
1.E+08
bacteria population (cel/g)
1.E+07
1.E+02
0 5 10 15 20
time (months)
Barrera reactiva permeable de Aznalcóllar
100
80
removal (%)
60
40 Zn
Al
Cu
20 acidity
0
-12 0 12 24 36
time (months)
Anoxic Limestone Drains (ALD)
• disolución de caliza
Anoxic Limestone Drains: pruebas
piezometro
descarga
200 L
recarga
Anoxic Limestone Drains: pruebas
.
blindaje:
solo <10% del reactivo
se ha consumido
colmatación:
pérdida de permeabilidad
debido a precipitados
Es la mineralogía, estúpido !
10,000
Net acidity (mg/L CaCO3)
1,000
100
10
1
AnW VFW ALD OLC LSB IPB
– material de soporte
• proporciona mucha
porosidad donde acumular
precipitados antes de la
colmatación
DAS-caliza: experimentos en columna
w
lg
shw
lg
shw
lg
shw
lg
shw
al-s-o
cc
gy
DAS-caliza: conductividad hidráulica
K (cm/s)
0.001 0.01 0.1 1 10
0
4
depth (cm)
10
12
14
16 weeks
28 weeks
42 weeks
65 weeks
DAS-caliza: transporte reactivo
0.05 0 .0 5 0.05
depth (m)
0.1 0 .1 0.1
0.15 0 .1 5 0.15
0.2 0 .2 0.2
(mg/L)
Fe(III)
6 200
mg/L (mg/L)
5 150
concentration
concentration
pH
pH
Al
4 100
3 50
2
0
0 0.2 0.4 0.6 0.8 1
0 0.2 0.4 0.6 0.8 1
distance (m)
distance (m)
3000 1.0
(mol/m3)
formed 3(mol/m3)
0.8
schwertmannite
2000 porosity
porosity
0.6
porosity
mineralformed
mol/m
hydrobasaluminite
0.4
1000 gypsum
mineral
0.2
0 0.0
0 0.2 0.4 0.6 0.8 1 0 0.2 0.4 0.6 0.8 1
distance (m) distance (m)
DAS-calcita: Mina Esperanza I
experimental vs predicho
DAS-caliza: Mina Esperanza I
A= 120 m2
Q= 0.5 L/s
tR= 2.5 d
2500
Net acidity removal
2000
1500
(mg/L CaCO3)
1000
500
pH
3000
5
DAS-caliza: Mina Esperanza II
4 2000
A lk (m g /l C a C O 3 ) 3 1000
2
C a (mg/l)
0
1
800
014 01 5 015 015 01 5 015 01 6 01 6 016 016 016 01 7
/2 /2 /2 /2 /2 /2 /2 /2 /2 /2 /2 /2 700
/ 12 /0 2 /04 /06 /0 9 /11 /0 2 /0 4 /07 /1 0 /12 /0 3 600
15 1 2 07 12 1 1 12 0 5 2 2 21 27 21 2 2 500
350
300
400
250 300
200 200
150 100
100
50 0
Fe (mg/l)
Al (mg/l)
1000
0 160
140
800 120
100
600 80
400 60
40
200 20
0 0
Cu (mg/l)
Zn (mg/l)
20 30
M1 M2
15 25
M4 M6
20
10 15
10
5
5
0 0
0 2 4 6 8 10 12 14 16 18 20 22 24 26 0 2 4 6 8 10 12 14 16 18 20 22 24 26
time (month) time (month)
DAS-caliza: Mina Concepción
Gracias !!
Tests estáticos ácido-base
<4.0 : Acido
pH 4.0<pH< 5.0 tests cinéticos
>5 : No Acido
Reactivo necesario
GARD (Global Acid Rock Drainage) Guide 2014. The International Network for Acid
Prevention (INAP). <http://www.gardguide.com/>.