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TABLE 2.1 Comparison of chemical and phase composition of copper rich metallurgical slags collected from several industrial areas.
Slag type
Location of
disposal site/
Period of
waste
generation
Chemical composition
Phase composition
References
Major compounds
Minor compounds
Cu-slags
USA
The Penn Mine
California
XIX
th
- XX
th
century
n.d.
Cu: 0.18-6.4%
(1800-64 000 ppm)
Pb: 0.02-11%
(161-110 000 ppm)
Zn: 3.2-28%
(32 000-280 000
ppm)
Glassy matrix
SILICATES: Zn-fayalite, willemite, feldspar, quartz, pyroxene
SPINEL: gahnite, franklinite
OXIDES: magnetite, hematite
SULFIDES: pyrite, chalcopyrite, sphalerite, galena, bornite, covellite,
cubanite, wurtzite
SECONDARY PHASES: barite, cerussite, chalcanthite, hydrozincite,
malachite, hydrous ferric oxides
Parsons et al.,
(2001)
Cu-slags
ITALY
Campigilia
Marittima
district:
Capattoli Valley
XI
th
-XIII
th
century
CaO-rich slags
SiO
2
: 20.06-30.06 wt.%
FeO : 42.53-52.17 wt.%
Al
2
O
3
: 2.93-5.06 wt.%
CaO: 8.26-15.62 wt.%
MgO: 0.72-0.90 wt.%
K
2
O: 0.74-1.20 wt.%
Na
2
O: 0.02-0.07 wt.%
CaO-poor slags
SiO
2 :
27.64-35.33 wt.%
FeO : 42.74-49.79 wt.%
Al
2
O
3
: 4.19-6.02 wt.%
CaO: 5.60-7.65 wt.%
MgO: 0.79-1.02 wt.%
K
2
O: 0.70-1.08 wt.%
Na
2
O: 0.01-0.08 wt.%
CaO-rich slags:
Cu: 0.22-0.31 wt.%
(2200-3100 ppm)
Zn: 2.22-6.07 wt.%
(22200-60700 ppm)
Pb: 0.53-1.56 wt.%
(5300-15600 ppm)
CaO-poor slags:
Cu: 0.25-0.31 wt.%
(2500-3100 ppm)
Zn: 1.62-3.52 wt.%
(16200-35200 ppm)
Pb: 1.70-3.40 wt.%
(17000-34000 ppm)
Glassy matrix
SILICATES:
olivine:
(fayalite,
kirschsteinite),
pyroxene:
(hedenbergite), quartz
SULFIDES: galena, sphalerite
Manasse et al.,
(2001)
Cu-Pb-Ag
historical slags
ITALY,
Massa
Marittima
district :
Marsiliana
Arialla
Rochette
Pannoccheschi
SiO
2
: 19.21-45.08 wt.%
FeO : 24.32-51.59 wt.%
Al
2
O
3
: 4.05-10.5 wt.%
CaO: 5.13-29.14 wt.%
MgO: 0.73-4.63 wt.%
K
2
O: 0.85-2.05 wt.%
Na
2
O: up to 0.22 wt.%
Cu: 0.07-1.23 wt.%
Zn: 0.31- 5.26 wt.%
Pb: 0.01-1.95 wt.%
Marsiliana:
Glassy matrix
SILICATES: Pyroxenes, leucite
SULFIDES: sphalerite, galena, chalcopyrite
INTERMETALLIC: FeS, metallic lead, copper prills
SPINELS
Arialla:
Glassy matrix
Ca-SILICATES (mellilite, kirschsteinite), mellilite,
PURE METALS: Pb, Sb, Fe and METAL ALLOYS: (Cu-Sb, Fe-As)
Manasse &
Mellini,
(2002)
CHAPTER 2: COPPER METALLURGICLA SLAGS- CURRENT KNOWLEDGE AND FATE:
A REVIEW
19
XIII
th
- XIV
th
century
Rochette Pannocchieschi:
Glassy matrix
SILICATES: kirchteinite
Fe-OXIDES: (magnetite, wüstite)
SULFIDES: chalcopyrite and pyrrhotite prills
Metallic grains, Cu-Sb, Fe-As alloys
Historical
Ag/Au/Cu/Pb slags
AUSTRALIA,
North
Queensland
XIX
th
- XX
th
century
SiO
2
:
28.70-35.77%
FeO: 31.46-43.66%
Al
2
O
3
:
3.12-5.41%
CaO: 9.12-15.53 wt.%
MgO: 0.37-1.72 wt.%
K
2
O: <0.05-1.16 wt.%
Na
2
O: 0.04-0.26 wt.%
Cu: 0.14-0.86%
(1410-8586 ppm)
Zn: 1.23-5.86%
(12266-58560 ppm)
Pb: 0.009-5.16%
(90-51620 ppm)
As: 0.002-0.064%
(24-635 ppm)
Ag: 0.0002-0.03%
(2-284 ppm)
Cd: 0.001-0.002%
(13-24 ppm)
Ni: up to 0.003%
(up to 25 ppm)
Glassy matrix
SILICATES: fayalite, wollastonite, mellilite, iscorite, grossular
kirschsteinite, hedenbergite, Fe-wollastonite
OXIDES: magnetite, chromium oxides (relict phase)
SULFIDES: pyrrhotite, bornite, galena, sphalerite, wurtzite
ALLOYS (Ag, Cu, Sb, Pb): Cu
3
Sn, CuSb, SbS, SbAgPb
SECONDARY PHASES: Carbonates (cerussite, malachite, azurite,
magnesite)
chlorides
(atacamite),
Fe-(oxy)hydroxides,
Sufates
(gypsum, scorodite, eugsterite, syngenite)
Lottermoser,
(2002)
Cu-slags
SPAIN,
Huelva
Province,
Cabezo Jure
3000 B. C.
SiO
2
:
13.81-68.71 wt.%
Fe
2
O
3
: 6.72-50.6 wt.%
Al
2
O
3
: 0.01-14.99 wt.%
CaO: 0.2-7.85 wt.%
MgO: 0.2-2.78 wt.%
K
2
O: 0.01-3.05 wt.%
Na
2
O: 0.11-1.25 wt.%
Cu: 0.14-28.06%
(1400-280600)
Zn: 0.006-0.14%
(58-1423 ppm)
Pb: 0.002-0.46%
(16-4562 ppm)
As: 0.006-0.86%
(58-8628 ppm)
Cr: 0.01-0.065%
(118-653 ppm)
Ni: 0.005-0.02%
53-217 ppm
Glassy matrix
SILICATES: Olivine (Fe-tephorite – Mn fayalite), Pyroxene
(diopside-hedenbergite), ferrobustamite, pyroxmangite, titanite
OTHERS: quartz, Ca-rich plagioclase
OXIDES: magnetite, maghemite, cuprite, delafossite, fluorapatite,
cassiterite, ulvöspinel
SULFIDES : chalcocite and COPPER PHASE
SECONDARY PHASES: Fe-Mn oxides, chrosocolla, conichalcite,
copper chloride
Sāez et al., (2003)
CHAPTER 2: COPPER METALLURGICLA SLAGS- CURRENT KNOWLEDGE AND FATE:
A REVIEW
20
Cu historical slags
USA
Vermont/
Tennessee
XIX
th
- XX
th
century
Si: 14.5-20.28 wt.%
Fe: 21-37 wt.%
Al: 1-4.9 wt.%
Ca: 0.83-4.1 wt.%
Mg: 0.62-2 wt.%
K: 0.23-1.2 wt.%
Na: 0.1-1.9 wt.%
Cu: 0.19-1.35%
(1900-13500 ppm)
Zn: 0.23-1.02%
2310-19700 ppm
Pb: 0.0008-0.0047%
(8.1-47 ppm)
As: up to 0.000.2%
(< 0.5- 2 ppm)
Cr: (0.004-0.028%
(40-276 ppm)
Cd: 0.00043-
0.00034%
(0.43-3.4 ppm)
Ni: 0.0003-0.003%
(2.8-27 ppm)
Glassy matrix
SILICATES: Fayalite-forsterite, quartz
Fe-Al-Ca rich glass
OXIDES: spinels, hematite
SULFIDES: pyrrhotite, Cu-Fe sulfides and pure metals
SECONDARY PHASES: amorphous Fe,Al-oxyhydroxides
Crystalline chalcanthite, siderotil, jarosite, brochantite, gypsum
Piatak et al.,
(2004)
Cu/Pb historical
slags
NAMIBIA,
Tsumeb
XX
th
- XXI
st
century
SiO
2
:
9.82-35.5 wt.%
Fe
2
O
3
+FeO:
8.42-64.22
wt.%
Al
2
O
3
:
2.82-18.5 wt.%
CaO: 2.29-17.44 wt.%
MgO: 0.69-5.10 wt.%
K
2
O: 0.10-0.93 wt.%
Na
2
O: 0.25-1.87 wt.%
Cu: 0.49-12.19 wt.%
(4963-121850)
Zn: 2.8-12.09 wt.%
(28188-120850)
Pb: 0.97-18.38 wt.%
(9763-183800)
As: 0.09-7.59 wt.%
(930-75865)
Cr: 0.02-0.16%
(201-1576 ppm)
Sb: 0.007-0.22%
(67-2175 ppm)
Glassy matrix
SILICATES: fayalite, pyroxene (monticellite), melilite, anorthite
OXIDES: spinels, wuestite, delafossite-mcconnelite
SULFDES: galena, wurtzite, sphalerite, chalcopyrite, pyrrhotite,
cubanite, covellite
Metallic Pb and Cu
OTHER PHASES: domeykite, Cu
5
Sb, Cu
3
(Sn,Sb), Fe
2
As, FeAs, Ca-
Pb arsenates
SECONDARY PHASES: matrix arsenates (lammerite Cu
3
(AsO
4
)
2,
bayldonite Cu
3
Pb(AsO
4
)
2
(OH)
2
, olivenite, lavendulan) and hydrated
Cu-oxides, hydrocerussite, anglesite, gypsum
Ettler et al.,
(2009)
CHAPTER 2: COPPER METALLURGICLA SLAGS- CURRENT KNOWLEDGE AND FATE:
A REVIEW
21
Cu-historical &
modern slags
PORTUGAL
Sao Domingos
District
800 B.C.-
410 A.D.
XIX
th
century
HISTORICAL SLAG:
Fe: 33 wt.%
MODERN SLAG:
Fe: 41 wt.%
HISTORICAL
SLAG:
Cu: 0.09% (926 ppm)
Zn: 0.03% (341 ppm)
Pb: 0.05% (449 ppm)
As: 0.0002% (2 ppm)
Cr: 0.006% (63 ppm)
Sb: 0.009% (85 ppm)
MODERN SLAG:
Cu: 0.27%(2739
ppm)
Zn: 0.89%(8940
ppm)
Pb: 0.51%(5051
ppm)
As: 0.04% (431 ppm)
Cr: 0.02% (164 ppm)
Sb: 0.01% (121 ppm)
Glassy matrix
SILICATES: Olivine, quartz
OXIDES grains
SULFIDES: pyrite, chalcopyrite, galena, arsenopyrite, pyrrhotite
Intermetallic phases: Fe-Cu-Pb
SECONDARY PHASES: jarosite
Álvarez-Valero et
al., (2009)
Cu-historical &
modern slags
PORTUGAL
Sao Domingos
District
800 B.C –
410 A.D
XX century
ROMAN SLAG:
SiO
2
:
37.70 wt.%
Fe
2
O
3
: 52.86 wt.%
Al
2
O
3
:
3.93 wt.%
CaO: 1.14 wt.%
MgO: 0.40 wt.%
K
2
O: 1.04 wt.%
Na
2
O: 0.25 wt.%
MODERN SLAG:
SiO
2
:
28.48-34.44
wt.%
Fe
2
O
3
: 58.15-58.52 wt.%
Al
2
O
3
:
1.51-1.97 wt.%
CaO: 4.95-6.28 wt.%
MgO: 0.46-0.70 wt.%
K
2
O: 0.22-0.26 wt.%
Na
2
O: 0.02-0.15 wt.%
ROMAN SLAG:
Cu: 0.03% (252 ppm)
Zn: 0.008% (83 ppm)
Pb: >0.5% (>5000
ppm)
As: up to 0.17%
(1730 ppm)
Sb: 0.23%
(up to 2310 ppm)
MODERN SLAG:
Cu: up to 0.33%
(3280 ppm)
Zn: up to >1%
(>10000 ppm)
Pb: up to >0.5%
(> 5000 ppm)
As: up to 0.02%
(180 ppm)
Sb: up to 0.05%
(492 ppm)
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