Walid Salama

Mineral evolution and processes of ferruginous microbialite accretion – an example from the Middle Eocene stromatolitic and ooidal ironstones of the Bahariya Depression, Western Desert, Egypt

Peritidal ferruginous microbialites form the main bulk of the Middle Eocene ironstone deposits of the Bahariya Depression, Western Desert, Egypt. They include ferruginous stromatolites and microbially coated grains (ferruginous oncoids and ooids). Their internal structures reveal repeated cycles of microbial and Fe oxyhydroxide laminae. The microbial laminae consist of fossilised neutrophilic filamentous iron-oxidising bacteria. These bacteria oxidised the Fe(II)-rich acidic groundwater upon meeting the marine water at an approximately neutral pH. The iron oxyhydroxide laminae were initially precipitated as amorphous iron oxhydroxides and subsequently recrystallised into nanocrystalline goethite during early diagenesis. Organic remains such as proteinaceous compounds, lipids, carbohydrates and carotenoids are preserved and can be identified by Raman spectroscopy. The ferruginous microbialites were subjected to post-depositional subaerial weathering associated with sea-level retreat and subsurface alteration by continued ascent of the Fe(II)-rich acidic groundwater. At this stage, another iron-oxidising bacterial generation prevailed in the acidic environment. The acidity of the groundwater was caused by oxidation of pyrite in the underlying Cenomanian Bahariya formation. The positive iron isotopic ratios and presence of ferrous and ferric iron sulphates may result from partial iron oxidation along the redox boundary in an oxygen-depleted environment.

Spectroscopic characterization of iron ores formed in different geological environments using FTIR, XPS, Mössbauer spectroscopy and thermoanalyses

Application of thermoanalyses, FTIR, XPS and Mössbauer spectroscopic methods can differentiate between iron ores formed in different geological environments. Two types of iron ore are formed in shallow marine environments in the Bahariya Depression, Egypt, yellowish brown ooidal ironstones (type 1) and black mud and fossiliferous ironstones (type 2). Both types were subjected to subaerial weathering, producing a dark brown lateritic (pedogenic) iron ore (type 3). Microscopic investigation indicates goethite is the main mineral in types 1 and 3, while hematite is the main mineral in type 2 and also occurs in type 3. Thermoanalyses indicated the dehydroxylation endothermic peak of goethite of type 1 occurs between 329 and 345°C, while in type 3 occurs between 284 and 330°C. This variation can be attributed to the nanocrystalline nature of the pedogenic goethite. The presence of an exothermic peak at 754°C in type 3 is probably attributed to goethite-hematite phase transformation. FTIR spectroscopy indicated that goethite of type 1 is characterized by the presence of the δ-OH band between 799 and 802cm(-1), the γ-OH between 898 and 904cm(-1) and the bulk hydroxyl stretch between 3124 and 3133cm(-1). Goethite of type 3 is characterized by the absence of the bulk hydroxyl stretch band and the δ-OH and γ-OH are shifted to higher Wavenumbers that can attributed to a relative Al-for Fe-substitution. Hematite is identified by two IR bands; the first is between 464 and 475cm(-1) and at the second is between 540 and 557cm(-1). Quartz is identified in all iron ore types, nitrates are identified in types 1 and 2, but absent in type 3 and Kaolinite is identified in type 2. The Mössbauer spectrum of type 1 is fitted with one magnetic sextet corresponding to goethite with an isomer shift (IS)=0.374mms(-1), a quadruple splitting (QS)=-0.27mms(-1) and a hyperfine magnetic field (BHF)=∼37. The Mössbauer spectrum of type 2 is fitted with one magnetic sextet corresponding to hematite with IS=0.363mms(-1), QS=-0.23mms(-1) and BHF=∼50. The Mössbauer spectrum of type 3 is best fitted with a single doublet corresponding to ferrihydrite and one sextet corresponding to hematite. The XPS survey scans and the high resolution of the Fe 2p3/2 can differentiate between the yellowish-brown and green ooidal laminae of type 1. The XPS survey scans indicate the presence of Fe, O, C, N, Na, Cl, Ca and Si in all laminae, while S, Zn, Ti and P are only restricted to the green laminae. The high resolution of the Fe 2p3/2 indicates that Fe is linked to OH(-) ligand in the yellowish-brown laminae that correspond to goethite, while Fe is linked to SO4(2-) ligand in the green laminae. The XPS survey scans of types 2 and 3 indicate that Fe is linked to O(2-) ligand that corresponds to hematite.

Raman investigations of Upper Cretaceous phosphorite and black shale from Safaga District, Red Sea, Egypt.

The mineral composition of the Upper Cretaceous Duwi phosphorite deposits and underlying Quseir Variegated Shale from Safaga district, Red Sea Range, Egypt, was investigated by dispersive and Fourier transformed Raman spectroscopy. The only phosphorous containing mineral detected in the phosphorite deposits was carbonate fluorapatite. Often carbonate fluorapatite appears associated with calcium sulfate and seldom with calcium carbonate in the investigated samples. Iron is present in the form of goethite and pyrite in the phosphorite layer, while pyrite, marcasite and hematite were identified in the Quseir Shale samples. Also, a high amount of disordered carbon was detected in the black shale layers. The Raman results confirm the hypothesis that the formation of the phosphorites took place in a marine environment. During the formation of black shale, the redox conditions changed, with the pH reaching values of 4 or even lower. Diagenetic and weathering transformations had taken place in the phosphorite deposits, calcium sulfate and goethite being products of these types of processes.