The mineralogy and geochemistry of the Voëlwater banded iron-formation, Northern Cape Province

Banded iron-formations (BIFs) are chemically precipitated sedimentary rocks in which Fe-rich bands or laminae alternate with Fe-poor ones. They formed within a specific time-span of the geological record. Their occurrence is restricted between 2.3 and 1.9 Ga, and characterises virtually all the major Precambrian-aged sedimentary basins of the world. The Precambrian Transvaal Basin in Griqualand West, South Africa, is noted for its well-developed BIF units. The Kuruman and Griquatown BIFs comprising the Asbesheuwels Subgroup (up to 1000m thick) are the best known and thickest of these. As far as metallogenesis is concerned, the Kuruman BIF is of major importance, for it carries the world's largest crocidolite (blue asbestos) deposits. The uppermost, youngest member of iron-formation deposition in the Griqualand West Sequence is represented by the Voëlwater BIF. The direct association between the latter and the giant Mn-deposits of the Kalahari Field, renders the Voëlwater association unusual, if not unique, in the geological record. The Voëlwater BIF represents a typical example of the so-called "Superior-type", and in the area of study it has undergone late-diagennetic to low-grade metamorphic processes. This is evident from the mineralogical composition and textural signature of the various BIF lithologies. Specifically, the minerals that make up the Voëlwater BIF are mainly chert(quartz), Fe-oxides (magnetite and hematite), Fe-silicates (greenalite, stilpnomelane, minnesotaite, riebeckite, Fe-mica), Fe-carbonates (members of the dolomite-ankerite series and siderite), calcite and pyrite. Soft-sediment deformation structures and shear-stress indicators are abundant in carbonate-rich and granular, silicate-rich BIF lithologies respectively. The bulk chemical composition of the study rocks is relatively simple and is characterised by the abundance of essentially three elements, namely Si, Fe, and Ca, which make up more than 90% of the total chemical composition of the Voëlwater BIFs. The detrital component of the study rocks is negligible. Mn-enrichments characterise all the transitional lithologies towards the interbedded Mn-orebodies, as well as the well-developed, hematitic BIF-unit between the Ongeluk lavas and the lower Mn-horizon. In terms of trace element composition, no significant enrichments or depletions, were encountered, except for some unusually high values of Sr and Ba and Co in carbonate-rich and Mn-rich lithologies respectively. Geochemical comparisons on the basis of major, trace and light rare-earth element composition verified the similarity between the Voëlwater BIF and other major Superior-type BIFs of the world (e.g. Kuruman, Griquatown, Sokoman, Biwabik, Gunflint, Mara-Mamba, Brockman, etc.). The processes that led to the formation of the Voëlwater BIFs may have been very similar to the ones described in various genetic models proposed in recent years. They would have involved a combination of: i. hydrothermal processes related to mid-ocean ridge (MOR) or hot-spot activity that acted as major iron suppliers; ii. storm-mixing in stratified oceans (bottom, anoxic, Fe⁺² reservoir-thermo- pycnocline zone-upper, mixed, SiO₂-saturated layer), largely dictated by seasonal changes and contemporaneous volcanism; iii. periodic, convection-driven upwelling mechanisms acting as major Fe-precipitators; and, iv. organic carbon productivity that was responsible for the anoxic diagenesis of the initial sediment. However, the origin of Fe and Mn for the genesis of the Voëlwater sediments was difficult to explain with typical convection-cell models in active mid-ocean ridges, in contrast to previous hypotheses. Instead, large-scale endogenous processes in the form of magma convection, underplating, differentiation and associated degassing, may have played a critical role in the supply of metals for the formation of large amounts of BIFs in the Precambrian. The present study of the Voëlwater BIF also bears strong implications regarding the metallogenesis of Mn in the Precambrian. The common association of Mn with carbonate-bearing sediments, the transitional character of the Voëlwater BIF towards carbonate lithologies (Mooidraai dolomites) and the critical timing of the deposition of the former in terms of the Precambrian atmospheric-lithospheric- hydrospheric evolution, may be important indicators for the exploration of large Mn-deposits in Precambrian sedimentary basins of the world

Petrographic and geochemical constraints on the origin and post-depositional history of the Hotazel iron-manganese deposits, Kalahari Manganese Field, South Africa

The giant Palaeoproterozoic manganese deposits of the Kalahari manganese field (KMF), Northern Cape Province, South Mrica, have been a world renowned resource of manganese ore for many decades. In recent years, the mineralogical composition, geochemistry and genesis of these deposits have been the objects of many geological investigations, yet their origin remains contentious up to the present day. A characteristic feature of the Kalahari deposits is the intimate association of manganese ore and iron-formation of the Superior-type, in the form of three discrete sedimentary cycles constituting the Hotazel Formation. This striking lithological association is an almost unique feature on a global scale. From that point of view, the present study is effectively the first attempt to shed light on the origin and post-depositional history of the Hotazel succession, using as prime focus the petrographic and geochemical characteristics ofthe host iron-formation. Petrographic and whole-rock geochemical information of iron-formation from the southern parts of the KMF, suggests that the Hotazel iron-formation is almost identical to other iron-formations of the world of similar age and petrological character. The rock exhibits essentially no high-grade metamorphic or low-temperature alteration effects. Mineralogically, it contains abundant chert, magnetite, subordinate amounts of silicate minerals (greenalite, minnesotaite, stilpnomelane) and appreciable concentrations of carbonate constituents in the form of coexisting calcite and ankerite. Such mineralogical composition is indicative of processes occurring in a diagenetic" to burial (up to very low-greenschist facies) metamorphic environment. Bulk-rock geochemical data point towards a simple composition with Si02, total Fe-oxide and CaO being the chief major oxide components. Whole-rock rare-earth element data suggest that the iron-formation precipitated from a water column with chemical signatures comparable to modern, shallow oceanic seawater. The virtual absence of positive Eu anomalies is a feature that compares well with similar data from Neoproterozoic, glaciogenic iron-formations of the Rapitan type, and suggests but only a dilute hydrothermal signal, poten!ially derived from distal submarine volcanic activity. Carbon and oxygen isotope data from iron-formation and Mn-bearing carbonates as well as overlying ferriferous limestone of the Mooidraai Formation, compare well with the literature. The former exhibit variable depletion relative to seawater in terms of both BC and 180, while the latter have signatures comparable to normal marine bicarbonate. Isotopic variations appear to be related to fluctuations in the amount of co-precipitated marine carbonate, in conjunction with processes of coupled organic matter oxidation - FelMn reduction in the diagenetic environment. Oxygen isotope data from quartz-magnetite-calcite triplets suggest that crystallisation took place under open-system conditions, with magnetite being the most susceptible phase in terms of fluid-rock isotopic exchange. Data also suggest that the calcite-magnetite pair may constitute a more reliable geothermometer than the quartz-magnetite one, mainly due to the interlinked diagenetic histories between calcite and magnetite. Iron-formation from the northern parts of the KMF can by categorised into three main classes, namely pristine, altered and oxidised. Pristine iron-formation is identical to the one seen in the southernmost parts of the field. Altered iron-formation corresponds to a carbonate-free derivative of intense oxidation and leaching processes at the expense ofpristine iron-formation, and contains almost exclusively binary quartz-hematite mixtures. The rock appears to have lost essentially its entire pre-existing carbonate-related components (i.e., Ca, Mg, Sr, most Mn and Ba) and displays residual enrichments in elements such as Cr, Th, V, Ni and Pb, which would have behaved as immobile constituents during low-temperature alteration. The low temperature origin of altered iron-formation is supported by oxygen isotope data from quartz-hematite pairs which indicate that isotopically light hematite would have derived from oxidation of magneftte and other ferroussilicate compounds in the presence of a low-temperature meteoric fluid, while quartz would have remained isotopically unchanged. Occasional occurrences of acmite-hematite assemblages suggest localised metasomatic processes related to the action ofNaCI-rich fluids at the expense of altered iron-formation. The conditions of acmite genesis are very poorly constrained due to the very broad stability limits of the mineral in environments ranging from magmatic to surface-related. Oxidised iron-formation constitutes a distinct rock-type and shares common attributes with both the pristine and the altered iron-formation. The rock contains hematite as an important constituent while the amount of magnetite is substantially reduced. With regard to carbonate nlinerals, calcite contents are clearly very low or absent, having being replaced in most instances by a single, Mgenriched, dolomite/ankerite:type species. Oxidised iron-formation contains somewhat higher amounts of iron and reduced amounts of Sr and Ba relative to pristine iron-formation, whereas enrichments in elements such as Ni, Th, Pb, Cr, and V are seen, similar to altered iron-formation. Oxidised iron-formation appears to have originated from processes of dissolution-mobilisationreprecipitation of solutes derived primarily from leaching that produced altered iron-formation. It is proposed that the Hotazel iron-formation and associated manganese deposits were formed as a result of episodic sea-level fluctuations in a stratified depositional environment that gradually evolved into a shallow carbonate platform. A critical parameter in the development of manganese sediment may include regional climatic patterns related to a glacial event (Makganyene diamictite) prior to deposition of the Hotazel strata. This suggestion draws parallels with processes that are believed to have led to the formation of worldwide iron-formations and associated manganese deposits subsequent to Neoproterozoic episodes of glaciation. Submarine volcanism related to the underlying Ongeluk lavas appears to have had very little (if any) metallogenic significance, while evidence for a sudden rise in the oxygen contents of the atmosphere and ambient waters is lacking. With regard to later alteration processes, combination of geological and geochemical data point towards the potential influence of surface weathering prior to deposition of rocks of the unconformably overlying Olifantshoek Supergroup, possibly coupled with fault- and/or thrustcontrolled fluid-flow and leaching of the Hotazel succession during post-Olifantshoek times

The role of hydrothermal activity in the formation of karst-hosted manganese deposits of the Postmasburg Mn Field, Northern Cape Province, South Africa

The Postmasburg Manganese Field (PMF), Northern Cape Province, South Africa, once represented one of the largest sources of manganese ore worldwide. Two belts of manganese ore deposits have been distinguished in the PMF, namely the Western Belt of ferruginous manganese ores and the Eastern Belt of siliceous manganese ores. Prevailing models of ore formation in these two belts invoke karstification of manganese-rich dolomites and residual accumulation of manganese wad which later underwent diagenetic and low-grade metamorphic processes. For the most part, the role of hydrothermal processes and metasomatic alteration towards ore formation has not been adequately discussed. Here we report an abundance of common and some rare Al-, Na-, K- and Ba-bearing minerals, particularly aegirine, albite, microcline, banalsite, sérandite-pectolite, paragonite and natrolite in Mn ores of the PMF, indicative of hydrothermal influence. Enrichments in Na, K and/or Ba in the ores are generally on a percentage level for most samples analysed through bulk-rock techniques. The presence of As-rich tokyoite also suggests the presence of As and V in the hydrothermal fluid. The fluid was likely oxidized and alkaline in nature, akin to a mature basinal brine. Various replacement textures, particularly of Na- and K- rich minerals by Ba-bearing phases, suggest sequential deposition of gangue as well as ore-minerals from the hydrothermal fluid, with Ba phases being deposited at a later stage. The stratigraphic variability of the studied ores and their deviation from the strict classification of ferruginous and siliceous ores in the literature, suggests that a re-evaluation of genetic models is warranted. New Ar-Ar ages for K-feldspars suggest a late Neoproterozoic timing for hydrothermal activity. This corroborates previous geochronological evidence for regional hydrothermal activity that affected Mn ores at the PMF but also, possibly, the high-grade Mn ores of the Kalahari Manganese Field to the north. A revised, all-encompassing model for the development of the manganese deposits of the PMF is then proposed, whereby the source of metals is attributed to underlying carbonate rocks beyond the Reivilo Formation of the Campbellrand Subgroup. The main process by which metals are primarily accumulated is attributed to karstification of the dolomitic substrate. The overlying Asbestos Hills Subgroup banded iron formation (BIF) is suggested as a potential source of alkali metals, which also provides a mechanism for leaching of these BIFs to form high-grade residual iron ore deposits

A Holocene "frozen accident": sediments of extreme paleofloods and fires in the bedrock-confined upper Huis River, Western Cape, South Africa

Wildfires and flooding events are common and are forceful intrinsic controls over landscape evolution, biodiversity, and preserved sediment architecture in dryland environments. Charcoal-bearing Holocene flood sediments of the upper Huis River provide a rare perspective on the powerful and episodic sedimentary processes in a bedrock-confined fluvial setting in the tectonically stable SW Cape Fold Belt in South Africa. The sediments described in this paper are associated with high-magnitude, debris-flow-dominated paleofloods, and their charcoal content is linked to a series of radiocarbon-dated Holocene paleofires that occurred from ∼ 2165 ± 37 BP to ∼ 653 ± 35 BP. The five sedimentary facies associations are documented as products of: a) noncohesive pseudoplastic debris flows; b) transitional, high-matrix-strength debris flows with heterogeneous fluid content and flow behavior; c) low-cohesion debris flows; d) hyperconcentrated flows; and e) fluvial channel flow in the upper Huis River. The last is interpreted mainly from massive, subrounded to subangular boulder bars, which provide key evidence for the dramatic scouring of the upper Huis valley. The paleofloods, which not only filled the valley with debris-flow sediments up to 12 m thick, but also subsequently flushed it out nearly to the bedrock, had estimated extreme discharges of few thousands of m3/s. In summary, the upper Huis River sediments are exceptional because they preserve the geological record of recurring fires, and at least three extreme paleofloods (i.e., massive sedimentation events) over a period of ∼ 1500 years in an area typified by the fire-prone and fire-dependent Fynbos Biome. Furthermore, this study provides insights into what the gaps in the commonly fragmented bedrock-confined alluvial stratigraphic record would be like, should there be “more record than gap.

Post-magmatic processes recorded in bimodal chromitites of the East Chalkidiki meta-ultramafic bodies, Gomati and Nea Roda, Northern Greece

The meta-ultramafic bodies of Gomati and Nea Roda are situated in the Serbomacedonian Massif. They demonstrate bimodal character in terms of chromitite chemistry with both Cr- and Al-rich chromitites outcropping in proximity, with no obvious tectonic structure intercepting those two varieties. Based on the trace element abundances in spinel grains, metamorphosis reached amphibolite facies, forming porous spinel. Chromitite-hosted chlorite and garnet chemistry correlates with greenschist facies temperatures and formation of zoned spinel grains. Despite the metamorphic overprint, some of the primary features of the chromitites have been preserved. The PGE contents demonstrate an increase in Pd/Ir ratios in some chromitites pointing to fractionation, whereas low ratios of mostly Cr-rich chromitites point to partial melting being the main mechanism that controls PGE mineralization. The normalized trace element patterns of spinel-group minerals revealed that Al-rich chromitites were generated in spreading settings in a back-arc and the Cr-rich counterparts in SSZ environment. The parental melts of Al-rich and Cr-rich chromitites demonstrate MORB and boninitic affinities, respectively. The meta-ultramafic protoliths were modified within a subduction zone, with significant input of a sedimentary source, as confirmed by the chemistry of serpentinite, diopside and Sb-mineralization. These results suggest common geotectonic processes within the Rhodope and the Serbomacedonian massif, that have affected the ultramafic bodies and chromitite occurrences

The Potential for REE and Associated Critical Metals in Coastal Sand (Placer) Deposits of Greece: A Review

The rare earth elements (REEs) are characterized by the European Union (EU) as critical raw materials with a significant risk of supply because of their broad utility in both traditional and emerging technological applications. The growing demand for REE has caused a flurry in the search for new REE deposits in Europe and elsewhere in the world, and is also linked to rising exploitation efforts in a variety of geological settings. To this end, Greece appears to be a promising candidate to become a leading EU country in terms of REE by virtue of its natural endowment in sedimentary heavy mineral deposits (placers) along its long coastline. The present review focuses on the distribution, abundance, and bulk geochemistry of REEs and other critical metals (Ta, Nb, Co) associated with placer deposits of Greece, and specifically with geologically young heavy mineral sand accumulations developed proximal to felsic plutonic source rocks. These deposits are also enriched in the actinides uranium (U) and thorium (Th), as both of these metals are typically associated with REE-rich minerals such as xenotime, monazite, thorite, allanite, and zircon. Previous studies have employed a variety of analytical techniques down to nano-meter scale with the aim to elucidate the mineralogy and distribution of REE and associated actinides in Greek beach placers. In view of this mineralogically-intensive background, the present review focuses chiefly on bulk geochemical characteristics of the same deposits and the variations thereof between two major geographical regions (northern Greece, southern Aegean) and across individual placer occurrences within them. In this framework, we present comprehensive compositional comparisons between the different deposits, highlighting the geological sub-environments wherein they occur, their distinctive sources and geochemical signatures, and their potential economic significance in terms of REE and other critical metal enrichments where applicable

Carbonate stable isotope constraints on sources of arsenic contamination in Neogene tufas and travertines of Attica, Greece

We presented new C and O isotope data of rockforming calcite in terrestrial carbonate deposits from Neogene basins of Attica (Greece), coupled with standard mineralogical and bulk geochemical results. Whereas both isotope datasets [δ18O from −8.99 to −3.20‰(VPDB); δ13C from −8.17 to +1.40‰(VPDB)] could be interpreted in principle as indicative of a meteoric origin, the clear lack of a statistical correlation between them suggests diverse sources for the isotopic variation of the two elements. On the basis of broad correlations between lower carbon isotope data with increasing Fe and bulk organic carbon, we interpreted the light carbon isotope signatures and As enrichments as both derived mainly from a depositional process involving increased supply of metals and organic carbon to the original basins. Periodically augmented biological production and aerobic cycling of organic matter in the ambient lake waters, would have led to the precipitation of isotopically light calcite in concert with elevated fluxes of As-bearing iron oxy-hydroxide and organic matter to the initial terrestrial carbonate sediment. The terrestrial carbonate deposits of Attica therefore represented effective secondary storage reservoirs of elevated As from the adjacent mineralized hinterland; hence these and similar deposits in the region ought to be regarded as key geological candidates for anomalous supply of As to local soils, groundwater and related human activities

Chemical archeoceanography:

Elemental fluxes to the ocean are expected to increase with the surface area of continental exposure to weathering and atmospheric PCO2. The record of phosphorus in sediments, which has no notable source within the ocean, and the radiogenic strontium isotopes in Archean carbonates indicate that, prior to the Great Oxidation Event (GOE), subaerial expanses represented only about 20% of the modern continental surface area, i.e. 7% of the surface of the Earth. Because these simple first-order observations, in contrast to the low oxygen content of the pre-GOE atmosphere, have so far received only little attention in the appraisal of the marine chemistry of the early Earth, a reassessment of the chemistry of the pre-GOE ocean is warranted. Here we discuss some of the geochemical cycles of the Archean world, including protons, alkalinity, electrons, and other electrolytes, and attempt to build a first conceptual framework for Chemical Archeoceanography

(Table 1) Bulk Fe isotope values and pyrite framboids sizes of Cenomanian-Turonian samples

Organic carbon-rich shales from localities in England, Italy, and Morocco, which formed during the Cenomanian-Turonian oceanic anoxic event (OAE), have been examined for their total organic carbon (TOC) values together with their carbon, nitrogen, and iron isotope ratios. Carbon isotope stratigraphy (d13Corg and d13Ccarb) allows accurate recognition of the strata that record the oceanic anoxic event, in some cases allowing characterization of isotopic species before, during, and after the OAE. Within the black shales formed during the OAE, relatively heavy nitrogen isotope ratios, which correlate positively with TOC, suggest nitrate reduction (leading ultimately to denitrification and/or anaerobic ammonium oxidation). Black shales deposited before the onset of the OAE in Italy have unusually low bulk d57Fe values, unlike those found in the black shale (Livello Bonarelli) deposited during the oceanic anoxic event itself: These latter conform to the Phanerozoic norm for organic-rich sediments. Pyrite formation in the pre-OAE black shales has apparently taken place via dissimilatory iron reduction (DIR), within the sediment, a suboxic process that causes an approximately -2 per mil fractionation between a lithogenic Fe(III)oxide source and Fe(II)aq. In contrast, bacterial sulfate reduction (BSR), at least partly in the water column, characterized the OAE itself and was accompanied by only minor iron isotope fractionation. This change in the manner of pyrite formation is reflected in a decrease in the average pyrite framboid diameter from ~10 to ~7 µm. The gradual, albeit irregular increase in Fe isotope values during the OAE, as recorded in the Italian section, is taken to demonstrate limited isotopic evolution of the dissolved iron pool, consequent upon ongoing water column precipitation of pyrite under euxinic conditions. Given that evidence exists for both nitrate and sulfate reduction during the OAE, it is evident that redox conditions in the water column were highly variable, in both time and space