Potentially Harmful Elements (As, Sb, Cd, Pb) in Soil Polluted by Historical Smelting Operation in the Upper Silesian Area (Southern Poland)
Abstract
:1. Introduction
2. Historical Background
3. Geological Background of the Sampling Area
4. Materials and Methods
4.1. Optical Microscopy and Scanning Electron Microscope (SEM)
4.2. Electron Probe Microanalysis (EPMA)
4.3. ICP-ES/MS
4.4. pH
5. Results
5.1. Mineral Components
- (1)
- primary, fresh, or partially decomposed ore minerals (Zn-Pb-Fe sulphides and their accessories);
- (2)
- secondary phases formed in the soil environment;
- (3)
- synthetic phases resulting from smelting processes.
5.1.1. Primary Phases
5.1.2. Secondary Phases
6. Discussion
6.1. The Natural Content of PHEs in Topsoil
6.2. Distribution of Selected PHEs in the Topsoil
6.3. Mineral Changes and PHE Migrations
7. Conclusions
- In Upper Silesia, high concentrations of Zn (above 10,000 ppm), Pb (above 10,000 ppm), and Cd (above 50 ppm) are found in topsoil around former Zn smelters (from the 19th and early 20th centuries). In some locations, concentrations of Cu (up to 9345 ppm) and Sn (up to 10,000 ppm) make it possible to identify sites of former alloy (e.g., bronze) and non-ferrous metal production.
- The characteristic geochemical tracers for the studied soils are As, Sb, and Sr; the sources of As (from 1756 to more than 10,000 ppm) and Sb (from 106 to more than 4000 ppm) are Fe minerals. The final product of the geochemical transformations of As is mimetite. In contrast, Sr (125 to 4658 ppm) is mainly bound in Ca carbonates.
- More than 120 years after the end of Zn-Pb smelters, soils still contain unstable Zn, Pb, and Fe sulphides, often rich in Cd, As, and Sb. Under favourable environmental conditions, these minerals can be a source of ions, Pb2+, Zn2+, Cd2+, Tl3+, and AsO33−, readily transferred to the aquatic and biotic environment. In addition, there is evidence of the periodic activation of ions Pb2+, Zn2+, Cd2+, and SO42− present in soils of oxidised phases such as anglesite (PbSO4), mimetite Pb5(AsO4)3Cl, pyromorphite (Pb5(PO4)3Cl), smithsonite (ZnCO3), hemimorphite (Zn4Si2O7(OH)2·H2O), jarosite (KFe3(SO4)2(OH)6), and gypsum (CaSO4·2H2O).
- ICP-ES/MS studies of soils contaminated by metal ore metallurgy made it possible to assess the total HM content; using SEM/EDS studies, it was possible to assess the size, morphology, and chemistry of the microareas. Meanwhile, EPMA made it possible to study and identify phases rich in As, Se, Sb, and Ag, that is, those that affect the total content of these metals.
Supplementary Materials
Author Contributions
Funding
Data Availability Statement
Acknowledgments
Conflicts of Interest
References
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Soil Areas Contaminated by Zn, Pb, Cd, As, Sb | |||
---|---|---|---|
Zn-Pb Ore Mining | Zn-Pb Ore Processing | Zn-Pb Smelting | |
Main gangue components | dolomite (CaMg[CO3]2) 2,3,5 calcite (CaCO3) 2,3,5 ankerite (Ca(Fe,Mg,Mn)(CO3)2) 2 quartz (SiO2) 3 clay minerals 2,3 | quartz (SiO2) 1 dolomite (CaMg[CO3]2) 1,2 calcite (CaCO3) 1 ankerite (Ca(Fe,Mg,Mn)(CO3)2) 1 illite (KAl2(Si,Al)4O10(OH)2) 1 montmorillonite (Al2O3·SiO2·nH2O) 1 kaolinite (Al2(OH)4Si2O5) 1 | quartz (SiO2) 4,7,8 cristobalite (SiO2) 4,8 trydymite (SiO2) 4 diopside (MgCaSi2O6) 8 plagioclase 8 feldspar (e.g. anorthite) 4 mica 8 pyroxene 4,7 calcite (CaCO3) 7,8 |
Primary metalliferous minerals | marcasite (FeS2) 3,5 pyrite (FeS2) 5 sphalerite ((Zn,Fe)S) 2,3,5 galena (PbS) 2,3,5 | marcasite (FeS2) 1,6 pyrite (FeS2) 1,6 sphalerite ((Zn,Fe)S) 1 galena (PbS) 1,2 | sphalerite ((Zn,Fe)S) 8 wurtzite ((Zn,Fe)S) 8 |
Secondary metalliferous minerals | hemimorphite (Zn4Si2O7(OH)2·H2O) 2,3 smithsonite (ZnCO3) 2,3 minrecordite (CaZn(CO3)2) 2 cerrusite (PbCO3) 2,5 barite (BaSO4) 2 anglesite (PbSO4) 2,5 gypsum (CaSO4·2H2O) 2 jarosite (KFe3(SO4)2(OH)6) 2 willemite (Zn2SiO4) 5 goethite (FeO(OH)) 2,3 magnetite (Fe3O4) 2 Mn oxide 3 Fe hydroxide 2 | alluminosilicates 1,2 minrecordite (CaZn(CO3)2) 2 smithsonite (ZnCO3) 1,2 cerrusite (PbCO3) 1,2 Ca phosphates 2 Mn-Fe, Mn oxides 1,2 Fe oxides 2 goethite (FeO(OH)) 1,2 gypsum (CaSO4·2H2O) 1,6 anglesite (PbSO4) 1 bassanite (CaSO4·0.5H2O) 1,6 jarosite (KFe3[(OH)6/(SO4)2]) 1 epsomite (MgSO4·7H2O) 1,6 | cerrusite (PbCO3) 2,7 barite (BaSO4) 2,8 gypsum (CaSO4·2H2O) 7 litharge (PbO) 2 alluminosilicates (e.g. mullite) 2 Pb phosphates 2 Pb arsenate 8 magnetite (Fe3O4) 4,8 hematite (Fe2O3) 7,8 goethite (FeO(OH)) 8 mullite (Al6Si2O13) 4,8 akermanite (Ca2Mg(Si2O)7) 7 melilite (Ca,Na)2(Al,Mg,Fe2+) 7 willemite (Zn2SiO4) 7 zircon (ZrSiO4) 8 Zn-Fe oxide/hydroxide 8 apatite (Ca5(PO4)3(F,Cl,OH)) 4 Fe oxide 7 franklinite (ZnFe3+2O4) 4 zincite ((Zn,Mn)O) 4 birnessite ((Na,Ca)0.5(Mn4+,Mn3+)2O4·1.5H2O) 8 |
Mineral/ Compound | Galena (n = 25) | Sphalerite (n = 19) | Pyrite/Marcasite (n = 34) | |||||||||
---|---|---|---|---|---|---|---|---|---|---|---|---|
Min | Max | Average | SD | Min | Max | Average | SD | Min | Max | Average | SD | |
Fe | 0.20 | 0.54 | 0.42 | 0.13 | 0.08 | 0.09 | 0.08 | 0.01 | 46.80 | 47.30 | 47.11 | 0.16 |
Ni | 0.11 | 0.26 | 0.19 | 0.08 | b.d.l. | b.d.l. | ||||||
Cu | 0.08 | 0.09 | 0.09 | 0.01 | b.d.l. | b.d.l. | ||||||
Zn | 0.09 | 0.43 | 0.22 | 0.12 | 66.17 | 67.15 | 66.67 | 0.25 | 0.08 | 0.11 | 0.10 | 0.02 |
Se | 0.10 | 0.21 | 0.16 | 0.06 | b.d.l. | b.d.l. | ||||||
Pb | 79.90 | 86.71 | 84.92 | 1.64 | 0.10 | 0.15 | 0.12 | 0.02 | 0.10 | 0.13 | 0.12 | 0.02 |
Sb | 0.21 | 0.76 | 0.36 | 0.19 | b.d.l. | b.d.l. | ||||||
Cd | 0.12 | 0.28 | 0.20 | 0.07 | b.d.l. | b.d.l. | ||||||
As | b.d.l. | b.d.l. | 0.06 | 0.11 | 0.08 | 0.02 | ||||||
S | 11.88 | 13.84 | 13.47 | 0.45 | 32.47 | 33.13 | 32.71 | 0.16 | 52.94 | 54.02 | 53.61 | 0.28 |
Total | 99.87 | 99.43 | 100.77 |
Mineral/ Compound | Smithsonite (n = 13) | Barite (n = 9) | Anglesite (n = 15) | Pyromorphite (n = 12) | Mimetite (n = 1) | ||||||||||||
---|---|---|---|---|---|---|---|---|---|---|---|---|---|---|---|---|---|
Min | Max | Avg | SD | Min | Max | Avg | SD | Min | Max | Avg | SD | Min | Max | Avg | SD | ||
Cl | n.a. | n.a. | n.a. | 2.49 | 2.74 | 2.65 | 0.08 | 2.26 | |||||||||
Na2O | n.a. | 0.09 | 0.13 | 0.11 | 0.02 | n.a. | n.a. | n.a. | |||||||||
CaO | 0.92 | 1.60 | 1.35 | 0.19 | 0.00 | 0.19 | 0.08 | 0.07 | n.a. | 0.22 | 0.61 | 0.40 | 0.14 | 0.31 | |||
MnO | 0.10 | 0.13 | 0.10 | 0.02 | 0.00 | 0.06 | 0.02 | 0.02 | b.d.l. | b.d.l. | |||||||
SrO | b.d.l. | 0.10 | 0.20 | 0.14 | 0.04 | 0.00 | 0.05 | 0.01 | 0.01 | n.a. | n.a. | ||||||
BaO | b.d.l. | 65.91 | 68.35 | 67.59 | 0.99 | 0.00 | 0.26 | 0.06 | 0.08 | n.a. | |||||||
Fe2O3 | n.a. | 0.10 | 0.30 | 0.17 | 0.08 | 0.00 | 0.40 | 0.10 | 0.12 | 0.11 | |||||||
FeO | 0.23 | 0.49 | 0.35 | 0.07 | n.a. | n.a. | n.a. | n.a. | |||||||||
ZnO | 59.32 | 62.91 | 61.47 | 1.14 | n.a. | 0.13 | 0.43 | 0.21 | 0.11 | b.d.l. | |||||||
As2O3 | b.d.l. | b.d.l. | 0.00 | 0.14 | 0.06 | 0.05 | 19.51 | ||||||||||
CdO | b.d.l. | b.d.l. | 0.05 | 0.49 | 0.31 | 0.19 | b.d.l. | b.d.l. | |||||||||
Sb2O3 | b.d.l. | b.d.l. | 0.10 | 0.10 | 0.10 | 0.00 | b.d.l. | b.d.l. | |||||||||
PbO | 0.10 | 0.25 | 0.18 | 0.06 | b.d.l. | 72.80 | 73.94 | 73.36 | 0.35 | 78.34 | 81.69 | 80.10 | 1.08 | 75.11 | |||
SiO2 | 0.13 | 0.26 | 0.20 | 0.05 | n.a. | n.a. | 0.00 | 0.97 | 0.33 | 0.33 | 0.69 | ||||||
Al2O3 | n.a. | n.a. | n.a. | 0.00 | 0.40 | 0.14 | 0.14 | b.d.l. | |||||||||
P2O5 | b.d.l. | n.a. | n.a. | 14.97 | 15.55 | 15.29 | 0.18 | 0.34 | |||||||||
SO3 | 0.07 | 0.07 | 0.07 | 0.00 | 32.85 | 34.76 | 33.51 | 0.76 | 26.26 | 27.36 | 26.65 | 0.27 | n.a. | n.a. | |||
CO2 | 35.35 | 38.51 | 36.82 | 0.95 | n.a. | n.a. | n.a. | n.a. | |||||||||
Total | 100.00 | 101.61 | 100.29 | 99.57 | 98.33 |
Compound | an.1 | an.2 | an.3 | an.4 | an.5 | an.6 | an.7 | an.8 | an.9 | an.10 | an.11 | an.12 |
---|---|---|---|---|---|---|---|---|---|---|---|---|
Fe | 0.32 | 0.36 | 0.26 | 0.41 | 0.17 | 0.53 | 0.30 | 0.25 | 0.27 | 1.21 | 1.30 | 1.85 |
Zn | 0.22 | 0.17 | b.d.l | 0.20 | b.d.l | 0.15 | 0.19 | b.d.l | b.d.l | 0.10 | 0.18 | 0.20 |
Se | 16.55 | 17.37 | 18.12 | 19.50 | 21.96 | 16.66 | 18.47 | 9.83 | 17.40 | 2.04 | 3.98 | 4.39 |
Pb | 20.48 | 61.30 | 28.60 | 23.62 | 27.44 | 33.21 | 65.44 | 45.20 | 64.54 | 70.18 | 69.93 | 68.08 |
Ag | 34.59 | 3.43 | 26.43 | 45.11 | 42.14 | 23.06 | 0.82 | 0.70 | 0.93 | b.d.l | 0.27 | 0.12 |
S | 2.34 | 3.44 | 2.77 | 2.01 | 1.82 | 2.94 | 3.90 | 2.47 | 4.04 | 9.91 | 9.30 | 9.41 |
Total | 74.50 | 86.09 | 76.17 | 90.85 | 93.56 | 76.55 | 89.15 | 58.44 | 87.18 | 83.50 | 84.97 | 84.08 |
Crystal chemical formulae recalculated on the basis of 2 Se2− | Crystal chemical formulae recalculated on the basis of sum (Se2− + S2−)1 | |||||||||||
Fe | 0.06 | 0.02 | 0.01 | 0.02 | 0.01 | 0.03 | 0.02 | 0.02 | 0.01 | 0.06 | 0.07 | 0.09 |
Zn | 0.04 | 0.01 | 0.01 | 0.01 | 0.01 | 0.01 | 0.01 | |||||
Pb | 0.94 | 0.90 | 0.44 | 0.37 | 0.40 | 0.53 | 0.89 | 1.08 | 0.90 | 1.01 | 0.99 | 0.94 |
Ag | 2.06 | 0.10 | 0.78 | 1.35 | 1.17 | 0.71 | 0.02 | 0.03 | 0.02 | 0.01 | 0.00 | |
S | 1.05 | 0.33 | 0.27 | 0.20 | 0.17 | 0.30 | 0.34 | 0.38 | 0.36 | 0.92 | 0.85 | 0.84 |
Se | 2.00 | 0.67 | 0.73 | 0.80 | 0.83 | 0.70 | 0.66 | 0.62 | 0.64 | 0.08 | 0.15 | 0.16 |
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Nadłonek, W.; Cabała, J.; Szopa, K. Potentially Harmful Elements (As, Sb, Cd, Pb) in Soil Polluted by Historical Smelting Operation in the Upper Silesian Area (Southern Poland). Minerals 2024, 14, 475. https://doi.org/10.3390/min14050475
Nadłonek W, Cabała J, Szopa K. Potentially Harmful Elements (As, Sb, Cd, Pb) in Soil Polluted by Historical Smelting Operation in the Upper Silesian Area (Southern Poland). Minerals. 2024; 14(5):475. https://doi.org/10.3390/min14050475
Chicago/Turabian StyleNadłonek, Weronika, Jerzy Cabała, and Krzysztof Szopa. 2024. "Potentially Harmful Elements (As, Sb, Cd, Pb) in Soil Polluted by Historical Smelting Operation in the Upper Silesian Area (Southern Poland)" Minerals 14, no. 5: 475. https://doi.org/10.3390/min14050475