Reconstruction of 16th–17th Century Lead Smelting Processes on the Basis of Slag Properties: A Case Study from Sławków, Poland
Abstract
:1. Introduction
2. Location and Ore Exploitation
3. Materials and Methods
3.1. Sampling
3.2. Furnace Experiments
3.3. Geochemical and Petrological Analyses
3.4. Software
4. Results
4.1. Slag Types at Sławków Landfill
4.2. Phase Composition and Chemistry of Phases
4.2.1. Glassy Slag
4.2.2. Crystalline Slag
4.2.3. Weathered Slags
4.3. Chemical Composition of Slags
4.4. Melting Point of Slags
5. Discussion
5.1. Furnace Construction
5.2. Temperature Estimates
5.3. Ores and Additions
5.4. Atmosphere
5.5. Viscosity
6. Conclusions
Supplementary Materials
Author Contributions
Funding
Acknowledgments
Conflicts of Interest
References
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Glassy Slag | |||||||
---|---|---|---|---|---|---|---|
px | px | wlm | ol | PbO | glsp | glsr | |
SiO2 | 53.90 | 45.40 | 27.34 | 39.56 | 0.17 | 38.55 | 30.89 |
TiO2 | bd | 0.12 | na | bd | bd | 0.17 | 0.11 |
Al2O3 | 1.24 | 2.08 | bd | bd | bd | 2.27 | 2.71 |
As2O3 | bd | bd | bd | bd | bd | bd | 0.17 |
Fe2O3 | 0.00 | 0.00 | 0.00 | 0.00 | 0.00 | 21.27 | 11.46 |
FeO | 7.31 | 19.28 | 18.29 | 15.10 | 0.37 | 0.00 | 0.00 |
MnO | 0.12 | 0.29 | 0.23 | bd | bd | 0.21 | 0.17 |
ZnO | bd | 7.34 | 50.10 | bd | 0.40 | 12.61 | 4.92 |
PbO | na | 0.28 | bd | na | 98.18 | 8.88 | 39.51 |
BaO | na | na | na | na | na | bd | 0.56 |
MgO | 21.00 | 5.46 | 2.34 | 44.48 | bd | 3.07 | 0.12 |
CaO | 16.14 | 17.67 | 0.12 | 0.50 | bd | 11.15 | 3.19 |
K2O | bd | bd | na | bd | bd | 1.20 | 2.53 |
Na2O | bd | 0.35 | na | bd | bd | 0.56 | 0.45 |
P2O5 | na | 0.57 | 0.22 | na | bd | 0.74 | 0.77 |
SO3 | na | na | na | na | na | 0.43 | 0.27 |
Total | 99.71 | 98.84 | 98.64 | 99.64 | 99.12 | 101.11 | 97.83 |
a.p.f.u. (atoms per formula unit) | |||||||
Si | 1.96 | 1.88 | 0.98 | 1.00 | |||
Ti4+ | 0.00 | 0.00 | 0.00 | 0.00 | |||
Al | 0.05 | 0.10 | 0.00 | 0.00 | |||
As3+ | 0.00 | 0.00 | 0.00 | 0.00 | |||
Fe3+ | 0.00 | 0.00 | 0.00 | 0.00 | |||
Fe2+ | 0.22 | 0.67 | 0.55 | 0.32 | |||
Mn | 0.00 | 0.01 | 0.01 | 0.00 | |||
Zn | 0.00 | 0.22 | 1.33 | 0.00 | |||
Pb | 0.00 | 0.00 | 0.00 | 0.00 | |||
Ba | 0.00 | 0.00 | 0.00 | 0.00 | |||
Mg | 1.14 | 0.34 | 0.13 | 1.67 | |||
Ca | 0.63 | 0.78 | 0.00 | 0.01 | |||
K | 0.00 | 0.00 | 0.00 | 0.00 | |||
Na | 0.00 | 0.03 | 0.00 | 0.00 | |||
P5+ | 0.00 | 0.02 | 0.01 | 0.00 | |||
S6+ | 0.00 | 0.00 | 0.00 | 0.00 | |||
O2- | 6.00 | 6.00 | 4.00 | 4.00 |
Crystalline Slag | ||||||||||||||
---|---|---|---|---|---|---|---|---|---|---|---|---|---|---|
wo | wo | mll | mll | mll | rnk | pl | kfs | spl | hem | hem | gls | gls | gls | |
SiO2 | 53.50 | 50.85 | 39.28 | 37.74 | 23.14 | 41.04 | 43.61 | 60.31 | na | na | na | 77.48 | 67.45 | 74.59 |
TiO2 | bd | 0.10 | bd | bd | bd | bd | bd | bd | 7.74 | 7.93 | 0.52 | 0.17 | bd | 0.11 |
Al2O3 | 0.83 | 0.11 | 1.36 | 3.16 | 27.43 | bd | 33.03 | 24.09 | 13.24 | 3.28 | 11.57 | 4.38 | 24.69 | 1.22 |
FeO | 11.17 | 0.43 | - | - | - | 0.67 | 1.04 | 0.62 | 27.68 | - | - | - | - | - |
Fe2O3calc | - | - | 9.28 | 8.33 | 6.25 | - | - | - | 24.45 | 83.96 | 76.46 | 6.38 | 0.62 | 11.14 |
Cr2O3 | bd | bd | bd | bd | bd | bd | bd | bd | 10.91 | 0.10 | bd | bd | bd | bd |
V2O3 | bd | bd | bd | bd | bd | bd | bd | bd | 2.76 | 1.92 | bd | bd | bd | bd |
MnO | 0.27 | bd | bd | 0.17 | bd | bd | bd | bd | 0.19 | 0.65 | 0.77 | bd | bd | 0.23 |
ZnO | 2.31 | bd | 11.92 | 8.90 | 1.15 | 0.13 | 0.45 | bd | 10.95 | 0.99 | 6.60 | 3.74 | 0.14 | 4.10 |
PbO | 0.20 | bd | 0.60 | bd | bd | 0.11 | 0.22 | bd | na | na | na | 1.55 | bd | 0.84 |
MgO | 1.57 | bd | 0.68 | 2.42 | 0.63 | bd | bd | bd | 0.26 | bd | 2.50 | 0.20 | bd | 0.24 |
CaO | 27.72 | 47.40 | 35.43 | 36.98 | 39.41 | 56.82 | 18.14 | 0.89 | 1.16 | 1.12 | 0.62 | 1.67 | 0.24 | 2.62 |
K2O | 1.02 | bd | 0.17 | 0.23 | bd | bd | 0.42 | 13.18 | na | na | na | 2.80 | 6.15 | 3.24 |
Na2O | 0.10 | bd | 0.73 | 0.33 | bd | bd | 0.43 | bd | na | na | na | 0.30 | 0.14 | 0.31 |
Total | 98.69 | 98.89 | 99.45 | 98.26 | 98.01 | 98.77 | 97.34 | 99.09 | 99.34 | 99.95 | 99.04 | 98.67 | 99.43 | 98.64 |
a.p.f.u. (atoms per formula unit) | ||||||||||||||
Si | 3.15 | 2.99 | 2.01 | 1.92 | 1.11 | 2.00 | 2.09 | 2.79 | na | na | na | |||
Ti4+ | 0.00 | 0.00 | 0.00 | 0.00 | 0.00 | 0.00 | 0.00 | 0.00 | 0.21 | 0.15 | 0.01 | |||
Al | 0.06 | 0.01 | 0.08 | 0.19 | 1.55 | 0.00 | 1.86 | 1.31 | 0.56 | 0.10 | 0.35 | |||
Fe2+ | 0.55 | 0.02 | 0.00 | 0.00 | 0.00 | 0.03 | 0.04 | 0.02 | 0.83 | 0.00 | 0.00 | |||
Fe3+ | 0.00 | 0.00 | 0.36 | 0.32 | 0.22 | 0.00 | 0.00 | 0.00 | 0.66 | 1.61 | 1.47 | |||
Cr3+ | 0.00 | 0.00 | 0.00 | 0.00 | 0.00 | 0.00 | 0.00 | 0.00 | 0.31 | 0.00 | 0.00 | |||
V3+ | 0.00 | 0.00 | 0.00 | 0.00 | 0.00 | 0.00 | 0.00 | 0.00 | 0.08 | 0.04 | 0.00 | |||
Mn | 0.01 | 0.00 | 0.00 | 0.01 | 0.00 | 0.00 | 0.00 | 0.00 | 0.01 | 0.01 | 0.02 | |||
Zn | 0.10 | 0.00 | 0.45 | 0.33 | 0.04 | 0.00 | 0.02 | 0.00 | 0.29 | 0.02 | 0.12 | |||
Pb | 0.00 | 0.00 | 0.01 | 0.00 | 0.00 | 0.00 | 0.00 | 0.00 | na | na | na | |||
Mg | 0.14 | 0.00 | 0.05 | 0.18 | 0.05 | 0.00 | 0.00 | 0.00 | 0.01 | 0.00 | 0.10 | |||
Ca | 1.75 | 2.98 | 1.94 | 2.01 | 2.03 | 2.96 | 0.93 | 0.04 | 0.04 | 0.03 | 0.02 | |||
K | 0.08 | 0.00 | 0.01 | 0.02 | 0.00 | 0.00 | 0.03 | 0.78 | na | na | na | |||
Na | 0.01 | 0.00 | 0.07 | 0.03 | 0.00 | 0.00 | 0.04 | 0.00 | na | na | na | |||
O2- | 9.00 | 9.00 | 7.00 | 7.00 | 7.00 | 7.00 | 8.00 | 8.00 | 4.00 | 3.00 | 3.00 |
Glassy Slag | Crystalline Slag | Weathered Slag | ||
---|---|---|---|---|
SiO2 | wt.% | 34.58 | 46.50 | 26.18 |
TiO2 | wt.% | 0.11 | 0.15 | 0.10 |
Al2O3 | wt.% | 1.81 | 3.50 | 1.17 |
Fe2O3 | wt.% | 21.65 | 9.81 | 22.83 |
MnO | wt.% | 0.20 | 0.18 | 0.25 |
MgO | wt.% | 3.39 | 0.99 | 4.31 |
CaO | wt.% | 11.19 | 30.39 | 4.48 |
K2O | wt.% | 1.19 | 1.69 | 0.28 |
Na2O | wt.% | 0.11 | 0.11 | 0.04 |
P2O5 | wt.% | 0.74 | 0.22 | 0.21 |
TOT/C | wt.% | 0.08 | 0.43 | 0.30 |
TOT/S | wt.% | 0.62 | 0.15 | 0.90 |
LOI | wt.% | −1.40 | 2.00 | 0.00 |
Ag | ppm | 2 | 6 | 10 |
As | ppm | 330 | 83 | 303 |
Ba | ppm | 1424 | 273 | 672 |
Cr | ppm | 48 | 67 | 208 |
Cu | ppm | 108 | 25 | 87 |
Pb | ppm | >100,000 | 10,707 | >100,000 |
Sr | ppm | 384 | 109 | 120 |
Sb | ppm | 415 | 6 | 101 |
V | ppm | 52 | 137 | 18 |
Zn | ppm | 132,504 | 28,276 | 214,973 |
Zr | ppm | 73 | 73 | 151 |
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Warchulski, R.; Szczuka, M.; Kupczak, K. Reconstruction of 16th–17th Century Lead Smelting Processes on the Basis of Slag Properties: A Case Study from Sławków, Poland. Minerals 2020, 10, 1039. https://doi.org/10.3390/min10111039
Warchulski R, Szczuka M, Kupczak K. Reconstruction of 16th–17th Century Lead Smelting Processes on the Basis of Slag Properties: A Case Study from Sławków, Poland. Minerals. 2020; 10(11):1039. https://doi.org/10.3390/min10111039
Chicago/Turabian StyleWarchulski, Rafał, Monika Szczuka, and Krzysztof Kupczak. 2020. "Reconstruction of 16th–17th Century Lead Smelting Processes on the Basis of Slag Properties: A Case Study from Sławków, Poland" Minerals 10, no. 11: 1039. https://doi.org/10.3390/min10111039