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Table of contents
I. Chapter 1: State of the Art
1. Interests of sediments in environmental studies
2. Sediment formation processes
3. Particle transport and settling in rivers
3.1. Effects of dams on sedimentation
3.2. Transformations of suspended matter and surface sediments
4. Origin of metallic elements in sediments
4.1. Geochemical background of metals
4.2. Atmospheric deposition of metals
4.2.1. Natural sources of atmospheric depositions
4.2.2. Anthropogenic sources of metals
4.3. Metal release due to mining activities
4.4. Metal input resulting from agricultural activities
5. Sediments: a reservoir of deposited materials and a record of industrial activities
5.1. Contribution of grain sizes on the mineralogical and chemical composition
6. Assessing the age of sediments using 210Pbxs and 137Cs
7. Fate of metals and minerals in river sediments
7.1. Precipitation of metal sulfides in anoxic conditions: sulfidization
7.2. Dissolution of sulfide phases: sulfuricization
7.3. The fate of metals after anoxic sediments are re-oxidized
7.3.1. Resuspension of metal-laden anoxic sediments
8. The case of Fe and Fe bearing minerals
8.1. The formation of iron sulfides under anoxic conditions
8.1.1. The emergence and detection of framboïdal pyrites
8.2. Dissolution of iron sulfides upon oxidation of anoxic sediments
8.3. On the dissolution of sulfides and precipitation of Fe oxy-hydroxides
8.4. Precipitation of Fe oxy-hydroxides
8.5. Iron in the context of mining and steelmaking
9. The case of Zn and Zn bearing minerals
9.1. The fate of zinc in submerged sediments
9.2. The fate of Zn under oxic conditions
9.3. Fate of zinc released from steel industries
10. How to distinguish natural sediments from those that have been impacted by anthropogenic activities?
10.1. Geochemical composition and metal contents in sediments
10.2. Using factors and indices compared to the geochemical background to determine the degree of contaminated sediments
10.2.1. Contamination factor
10.2.2. Enrichment factor
10.2.3. Geoaccumulation index
10.2.4. Pollution load index
10.3. Crystalline minerals as a criterion for lithogenic and anthropogenic matter differentiation
10.4. Microscopic tools used in the investigation of sediment mineralogy at a sub-micrometric scale
10.4.1. Complementarity between various techniques for mineral characterization
11. The parameters to follow to understand metal speciation in remobilized sediments
11.1. Carbonates, period of flooding and pH
11.2. Carbonates, pH and sulfides
11.3. Microbial communities, pH and redox potential
11.4. Redox potential, salinity and sulfur
11.5. Period of resuspension, redox potential and salinity
11.6. Organic matter and size of complex
References
II. Chapter 2: A Review on the Orne Watershed and Steelmaking Processes: Past Activities and Sampling Sites
1. Geology of the Orne Watershed, a tributary of the Moselle River
2. Hydrology and physico-chemical parameters of the Orne River
3. The evolution of iron and steelmaking
4. Industrial development near the Orne River
4.1. Steelmaking facilities and outcome on the Orne River area
5. The production of pig or cast iron
5.1. Coal combustion, coke production, and mineralogical and chemical composition
5.2. Iron ore used in Lorraine steelmaking facilities
6. Processes occurring in blast furnaces
7. Steelmaking: production of steel from pig iron
8. Sources and fate of metals inside the blast furnace
8.1. Iron fate in blast furnaces
8.2. Zinc cycle in blast furnaces
8.3. Lead cycle in blast furnaces
9. The output materials of blast furnaces: composition and fate
9.1. Slag composition and usage
9.2. Dust particles emitted from blast furnaces
9.3. Sludge composition and fate
10. Locations of the sampling sites along the course of the Orne River
11. Context of the study
12. Objectives of the study
References
III. Chapter 3: Chemical and Mineralogical Composition of Surface Sediments: Variation Accounted by Lithology, Land Use and Former Industrial Activities
Abstract
1. Introduction
2. Materials and Methods
2.1. Study area and sampling sites
2.2. Sediment preparation for analyses
2.3. Particle size distribution, water content and pH
2.4. Chemical composition of the sediments
2.5. Mineralogy of sediments
2.5.1. Major and crystalline minerals of bulk sediments and clay-sized particles
2.5.2. Sub-micrometric mineral analyses of Orne sediments
3. Results
3.1. Chemical composition as a function of grain size
3.2. Grain size variation, water content and pH of Orne sediments
3.3. Chemical composition of sediments
3.4. Mineralogy of Orne River sediments
3.4.1. Major crystalline minerals, bulk samples and clay fractions
3.4.2. Micrometric to sub-micrometric investigations of surface sediments (SEM and TEM)
4. Discussion
4.1. Influence of grain size on the chemical and mineralogical composition of sediments
4.2. Particle size properties and water content
4.3. Variation of chemical and mineralogical composition of Orne sediments and possible sources
4.3.1. Detrital elements and clay mineralogy
4.3.2. Carbonates and REEs
4.3.3. Metallic elements and contribution of anthropogenic deposits
4.3.4. Particularity of Fe and Fe bearing phases in Orne sediments
4.3.5. Phosphorous contents and land cover
5. Conclusion
6. Supplementary Material
References
IV. Appendix to Chapter 3: Chemical Composition of Sediments of the Moselle River and Tributaries
1. Introduction
2. Study area and sampling sites
3. Sediment preparation for analyses
4. Chemical composition of sediments of the Moselle River and tributaries
5. Conclusion
References
V. Chapter 4: Iron Mineralogy as a Fingerprint of Former Steelmaking Activities in River Sediments
Abstract
1. Introduction
2. Materials and Methods
2.1. Study area
2.2. Sediment coring
2.3. Sample preparation for analyses
2.4. Physical properties of sediments
2.5. Sediment dating, measurements of 137Cs and excess 210Pb
2.6. Chemical composition of sediments
2.7. Mineralogy of sediments
2.7.1. Bulk and major mineral phases detected by XRD
2.7.2. Millimetric to sub-micrometric analyses: light microscope, SEM and TEM
3. Results
3.1. Visual description, water content and grain size of the sediments
3.2. Dating of Beth sediments
3.3. Chemical composition of sediments as a function of depth
3.4. Mineralogy of sediments
3.4.1. Major crystalline minerals
3.4.2. Identification of main mineral phases using microscopic tools
3.4.3. Iron minerals: crystalline, poorly crystalline and amorphous phases
4. Discussion
4.1. Industrial and natural contributions to the sediment deposits
4.1.1. Natural contributions in Beth sediment deposits
4.1.2. Industrial contributions to the sediments, ferrous and non-ferrous materials
4.2. Evolution of the iron minerals
5. Conclusion
6. Supplementary Materials
References
VI. Appendix to Chapter 4: Sedimentation Upstream the Beth Dam
1. Introduction
2. Recapture of the sediments upstream the Beth dam
3. An insight about Beth deposits
4. Why didn’t 137Cs and 210Pb data provide the age of Beth sediments?
5. Conclusion
References
VII. Chapter 5: Zinc Speciation in Submerged River Sediments Mixed with Steelmaking Wastes in the Orne River, Northeastern France
Abstract
1. Introduction
2. Materials and Methods
2.1. Study area
2.2. Sediment Coring
2.3. Sample preparation for analyses
2.4. Chemical composition of sediments
2.5. Mineralogical composition of sediments
2.6. X ray absorption spectroscopy at the Zn K-edge
3. Results
3.1. Interstitial waters of BETH1402 sediments
3.2. Chemical composition of BETH1402 sediments
3.3. Zn bearing phases revealed by SEM and TEM
3.4. Zn solid speciation using X-ray absorption spectroscopy at the Zn K-edge
3.4.1. Introductory data about XANES spectra and references
3.4.2. XANES spectra of BETH1402 sediments revealing Zn speciation
4. Discussion
4.1. An insight about the sources and fate of Zn in blast furnaces
4.2. Origin and fate of Zn in BETH1402 sediments
4.3. Zn speciation in BETH1402 sediments
4.3.1. Clays as Zn bearing minerals, with focus on Fe-aluminosilicates
4.3.2. Sorption of Zn onto carbonates, ferrihydrite and oxy-hydroxide
4.3.3. Zn sulfides: the predominant Zn species
5. Conclusion
References
VIII. General Discussion, Conclusion and Perspectives
1. General discussion
2. General conclusion
3. Perspectives
3.1. Recommendations on the management of metal rich sediments
