Mozaan Group Research Articles

Quartz arenites as signatures of cratonisation: examples from the Archaean Stratigraphic Record, southern Africa

Abstract Holocene quartz-rich sands such as in the Orinoco River of Venezuela and Columbia, develop under a unique set of conditions including tectonic stability, intense weathering and long-term storage of sediment prior to burial. This review paper proposes that a similar set of conditions existed on the Mesoarchaean Earth by 3.0 Ga. Compositionally and texturally mature quartz arenites are present in the Mesoarchaean Hospital Hill Subgroup and correlative lower Mozaan Group, in the cover rocks of the Beitbridge Complex in the Limpopo Belt and at Buhwa in southern Zimbabwe as well as the Neoarchaean Manjeri Formation of Zimbabwe. These quartz arenites are interpreted as first-cycle and developed following the formation of stable cratons under conditions of slow subsidence (<10 cm/1 000 years), intense weathering in a hostile chemical environment related to the ambient carbon dioxide-rich atmosphere, long-distance intrabasinal transport by tides and/or waves and microbial processes that influenced the local chemical environment. Similar examples of Mesoarchaean quartz arenites are documented from the Yilgarn Block in Western Australia, the Slave and Superior provinces in Canada and the Dharwar and Singhbhum cratons in India. On a global scale, cratonisation was diachronous with the Kaapvaal Craton stabilised on a regional scale by 3.0 Ga whereas microcontinents existed over the remainder of Earth.

New palaeomagnetic results from the Mesoarchaean Nsuze flood basalts, South Africa

Abstract The Pongola Supergroup is a largely undeformed ca. 2.99 to 2.87 Ga succession of volcanic and sedimentary rocks on the southeastern Kaapvaal Craton. Understanding the palaeogeographic context of the Pongola Supergroup could shed light on the tectonic setting of laterally correlative gold-bearing Witwatersrand Supergroup and have implications for Archaean geodynamics. Two previous studies were limited in spatial coverage and yielded purported primary magnetisations that were strikingly different from one another. Here we report new palaeomagnetic results from volcanic rocks of the Nsuze Group, i.e., the lower Pongola Supergroup, that are based on broad geographic sampling of a total of 57 sites making provision for several stability field tests. We report several directional components of remanent magnetisation, including widespread Karoo (ca. 180 Ma) and sporadic Namaqua-Natal (Mesoproterozoic) remagnetisation; but two additional ancient components are also commonly observed. The first of these is a south down characteristic remanence from 16 sites, of which 14 sites were included in the calculation of a mean, which we interpret as a magnetic overprint associated with intrusion of the 2.65 Ga White Mfolozi dyke swarm based on an inverse baked contact test and poorer clustering upon application of structural corrections to restore bedding to palaeohorizontal. The south down pole is located at 75.4°S and 334.5°E with an A95 of 6.4°. Recorded over a much more geographically widespread area from 15 sites is a west down characteristic remanence. The west down remanence is constrained to be older than 2.65 Ga by the same inverse baked contact test on a White Mfolozi dyke. Clustering of the west down remanence improves when bedding is restored. Fold tests are statistically indeterminate, but best grouping at ~60% unfolding was illustrated from the Amsterdam syncline. The precise age of folding is unknown. Emplacement relationships between the ~2.87 Ga Thole Complex and the folded Mozaan Group suggest that the syncline could be older than 2.87 Ga, but folding has also been ascribed to emplacement of the ca. 2.72 Ga Nhlangano gneiss dome. The age of the west down remanence and pole (15.6°S, 340.2°E and A95 = 9.3°, assuming 60% unfolding of sites at the Amsterdam syncline; or 16.6°S, 338.7°E and A95 = 10.3°, assuming 100% unfolding of sites at the Amsterdam syncline), which could be either syn-folding or pre-folding, is constrained at 2.98 to 2.72 Ga given presently known data.

The paleoenvironmental implications of pre-Great Oxidation Event manganese deposition in the Mesoarchean Ijzermijn Iron Formation Bed, Mozaan Group, Pongola Supergroup, South Africa

The Ijzermijn Iron Formation Bed occurs in the Vlakhoek Member of the basal Sinqeni Formation of the Mesoarchean Mozaan Group of the Pongola Supergroup of southern Africa. It represents the oldest known supracratonic Superior-type iron formation that has significant manganese enrichments. Lithostratigraphic correlation between the Mozaan Group and the Witwatersrand Supergroup indicates that there was a larger Witwatersrand-Mozaan depositional basin on the Kaapvaal Craton during the Mesoarchean. Detailed stratigraphy, mineralogy, petrography, carbonate mineral chemistry, major and trace element geochemistry and carbonate oxygen and carbon isotopes are presented for two drill cores intersecting the Ijzermijn Iron Formation Bed. Drill core PMH 24, which represents a more coast-distal depositional setting, is characterized by manganese-rich siderite, higher Fe2O3 and lower MnO and Al2O3 contents, more prominent europium anomalies, lower GdSN/YbSN values and less depleted δ13CPDB values. Drill core DDN 1, which represents a more coast-proximal depositional setting, is characterized by iron-rich rhodochrosite, lower Fe2O3 and higher MnO and Al2O3 contents, less prominent europium anomalies, higher GdSN/YbSN values and more depleted δ13CPDB values. The presence of early diagenetic magnetite, hematite and 13C-depleted carbonates indicate the iron and manganese, which were sourced from hydrothermal plumes, were deposited by oxidation, with subsequent diagenetic reduction by organic carbon. The most efficient oxidative mechanism would have been biological oxidation. The increase in manganese contents towards the paleocoastline further supports manganese oxidation as it was redox buffered by Fe2+ in the water column and could only be deposited and preserved once Fe2+ had been removed through oxidation further away from the distal hydrothermal plume source. This is supported by previously published iron isotope data, where δ56/54Fe values are more depleted closer to the paleocoastline. Deposition of iron and manganese was restricted to below the photic zone. This implies that microaerophilic chemolithoautotrophs were responsible for iron and manganese oxidation. This requirement of free oxygen in the Ijzermijn Iron Formation Bed has been supported by earlier molybdenum isotope studies. The presented work therefore further supports the idea of pre-Great Oxidation Event marine oxygen oases that did not lead to any appreciable build-up of oxygen in the atmosphere.

U-Pb-Hf isotopes and shape parameters of zircon from the Mozaan Group (South Africa) with implications for depositional ages, provenance and Witwatersrand – Pongola Supergroup correlations

The Mozaan Group represents the youngest unit of the c. 2.9 Ga Pongola Supergroup located along the south-eastern margin of the Kaapvaal Craton. It comprises a ca. 4800 m thick succession of clastic sedimentary rocks intercalated by minor chemical and volcano-sedimentary rocks deposited in shallow marine to fluvial environments, and is stratigraphically correlated with the auriferous Witwatersrand Supergroup. This correlation, however, is speculative, in particular as systematic information about depositional ages and sediment provenances are absent. To address these problems, we present new combined sets of U-Pb ages, Hf isotopes, and shape parameters (width, length, aspect ratios and roundness) of >700 detrital zircon grains from seven samples of the Mozaan type profile in the Hartland area. These data reveal a switch in provenance between the lower and upper Mozaan Group. Zircons in sandstones of the lower Mozaan Group (Sinqeni to Ntombe formations) were supplied from surrounding proto-Kaapvaal Craton, and those in upper Mozaan Group rocks (Delfkom to Ntanyana formations) predominately from a juvenile hinterland, comprising sources as far as the Pietersburg and/or Kimberley blocks, which became amalgamated to the proto-Kaapvaal Craton at 2.97–2.87 Ga. Significant overlap of zircon age spectra, Hf isotope data, and maximum depositional ages (2908 ± 8 Ma to 2866 ± 7 Ma) suggest similar sources for upper Mozaan Group and Central Rand Group sediments of the Witwatersrand Basin. In contrast, sedimentary rocks of the West Rand Group have no counterparts in the Pongola Basin, except for the Orange Grove Formation, which shows good agreement with the Sinqeni Formation. The provenance switch indicated by the age-Hf isotope data is not identified by zircon shape parameters. These rather reflect differences in depositional environment (littoral, fluvial, volcanogenic), related to the duration and energy of sediment transport and reworking, as indicated by specific patterns in grain size vs. roundness diagrams.

A new lithostratigraphic framework for portions of the Pongola Supergroup within the Nkandla sub-basin, southern Kaapvaal Craton, South Africa; insights into Mozaan Group stratigraphy

AbstractA revised lithostratigraphic framework for Mozaan Group-equivalent strata within the Nkandla sub-basin is presented based on new field data, remote sensing and genetic sequence stratigraphic interpretations. Although previous literature has suggested that no Mozaan Group lithologies were deposited within the sub-basin, reinterpretations presented here indicate that 90% of the lithostratigraphy developed within the main basin occurs within the Nkandla and Mhlatuze inliers. Mozaan Group units previously defined as the Vutshini and Ekombe formations are correlated with stratigraphy from the lowermost Sinqeni Formation to the Gabela Formation. Although thinner than units within the type area in the main basin, thicknesses of the Sinqeni Formation are comparable to those observed within the White Mfolozi Inlier. A ~1 000 m composite reference profile is measured within the Mdlelanga Syncline of the Nkandla Inlier. Further profiles were measured for sequences in the Gem-Vuleka Syncline of the Nkandla Inlier, as well as within the Mhlatuze Inlier. These latter profiles, however, host only lower Mozaan Group strata. In all sections the basal portion of the sequence comprises two quartz arenite units, separated by a ferruginous shale, which hosts minor iron formation interbeds. This predominantly coarse-grained lower sequence is overlain by a shale-dominated succession with multiple sandstone interbeds. A prominent coarse-grained quartz arenite unit forms a distinct marker in the middle portion of the sequence. This is overlain by a sequence of shales and sandstones with two prominent igneous units present. Genetic sequence stratigraphic interpretations indicate cyclical deposition of dominantly shallow marine sediments with condensed sections, marked by iron formations or ferruginous shales, denoting periods of marine highstand along the southeastern margin of the Kaapvaal Craton. The evidence of Mozaan Group stratigraphy within the Nkandla sub-basin supports a passive margin tectonic model whereby deposition occurred in an arcuate shallow continental margin which opened to the southeast. The extension of Mozaan Group strata into the Nkandla sub-basin suggests that the Mozaan Basin likely formed a single depository rather than separate sub-basins as previously proposed.

A geochemical study of the Crown Formation and Bird Member lavas of the Mesoarchaean Witwatersrand Supergroup, South Africa

Abstract The ca. 2.97 to 2.80 Ga Witwatersrand Supergroup, South Africa, represents the oldest intracontinental sedimentary basin of the Kaapvaal craton. Two volcanic units occur in this supergroup: the widespread Crown Formation lavas in the marine shale-dominated West Rand Group and the more geographically restricted Bird Member lavas, intercalated with fluvial to fluvio-deltaic sandstone and conglomerate of the Central Rand Group. These units remain poorly studied as they are rarely exposed and generally deeply weathered when cropping out. We report whole-rock major and trace elements, Hf and Nd-isotope whole-rock analyses of the lavas from core samples drilled in the south of the Witwatersrand basin and underground samples from the Evander Goldfield in the northeast. In the studied areas, both the Crown Formation and Bird Member are composed of two units of lava separated by sandstone. Whereas all the Crown Formation samples show a similar geochemical composition, the upper and lower volcanic units of the Bird Member present clear differences. However, the primitive mantle-normalized incompatible trace element concentrations of all Crown Formation and Bird Member samples show variously enriched patterns and marked negative Nb and Ta anomalies relative to Th and La. Despite the convergent geodynamic setting of the Witwatersrand Supergroup suggested by the literature, the Crown Formation and Bird Member are probably not related to subduction-related magmatism but more to decompression melting. Overall, the combined trace element and Sm-Nd isotopic data indicate melts from slightly to moderately depleted sources that were variably contaminated with crustal material. Greater contamination, followed by differentiation in different magma chambers, can explain the difference between the two signatures of the Bird Member. Finally, despite previous proposals for stratigraphically correlating the Witwatersrand Supergroup to the Mozaan Group of the Pongola Supergroup, their volcanic units are overall geochemically distinct.

Alluvial fan to shallow marine sedimentation record in the ~3.0 Ga Keonjhar Quartzite, Singhbhum Craton, India: An example of Phanerozoic style passive margin sedimentation from the Mesoarchean

The arenite-dominant Mesoarchean Keonjhar Quartzite (>700 m) succession unconformably overlies the granitoid-greenstone core of the Singhbhum craton in the north and west of the Keonjhar town in eastern India. The Keonjhar Quartzite is characterized by eleven lithofacies. The lower part of the succession represents proximal subaerial fan association dominated by cohesive and cohesionless mass-flow conglomerates deposited in a falling stage to lowstand systems tracts (FSST-LST). The channelized conglomerates are likely to be incised valley fills (IVF) from the FSST. The differentiated mass-flow deposits interbedded with tractional deposits such as trough cross-stratified sandstone with ubiquitous evidence of wave-reworking represent subaqueous delta front setting. The upper 3/4th of the succession is dominated by mature wavy bedded arenites and is arranged in aggradational stacking pattern representing TST to early stage of HST of a tectonically driven sea level rise cycle. The Keonjhar Quartzite is a rare example of well preserved record of stable siliclastic shelf development during the Mesoarchean time. The arenite-dominated Keonjhar Quartzite is comparable to only a few well studied examples of such Mesoarchean stable siliciclastic shelf sedimentation, for example, the arenite-dominated units of the Mozaan Group of the Pongola Supergroup and its correlatable Westrand and Centralrand Groups of the Witwatersrand Supergroup in the Kaapvaal craton. The presence of thick mature arenite and wave-tide reworking implies existence of Mesoarchean stable shelf depositional setting similar to the modern day passive continental margins at least in the Singhbhum and in the Kaapvaal cratons.

Lithostratigraphy of the Sinqeni Formation, Pongola Supergroup, South Africa

Abstract The Mesoarchaean Sinqeni Formation forms the lowermost unit of the predominantly sedimentary Mozaan Group (Pongola Supergroup) of southern Africa. The formation comprises a dominantly arenaceous succession, which can be subdivided into four members. A laterally discontinuous gold- and uranium-bearing conglomerate package (Denny Dalton Member) is commonly developed at the base of the formation. Overlying the basal conglomerates are two significant quartz arenite packages (Dipka, and Kwaaiman Members) which are separated by a ferruginous shale package (Vlakhoek Member) that locally hosts banded-iron formation. The formation is the most extensively exposed succession of the Mozaan Group, cropping out extensively in the Hartland region, as well as in multiple inliers from Amsterdam in the Mpumalanga to Nkandla in central KwaZulu-Natal, with further exposures in Eswatini. Subeconomic gold and uranium mineralisation occur sporadically within the conglomerates of the Denny Dalton Member, and have previously been mined from multiple occurrences in the White Mfolozi, Mhlatuze and Nkandla Inliers whilst many prospecting trenches are found in the conglomerates of the Hartland and Amsterdam areas. Gold has also briefly been exploited from ferruginous shales and iron formations of the Vlakhoek Member in the Altona area. Litho-correlative equivalents of the formation comprise the Mandeva Formation (White Mfolozi Inlier), Skurwerant Formation (Amsterdam region) and Mkaya Formation (Magudu region).

Life on a Mesoarchean marine shelf \u2013 insights from the world\u2019s oldest known granular iron formation

The Nconga Formation of the Mesoarchean (~2.96–2.84 Ga) Mozaan Group of the Pongola Supergroup of southern Africa contains the world’s oldest known granular iron formation. Three dimensional reconstructions of the granules using micro-focus X-ray computed tomography reveal that these granules are microstromatolites coated by magnetite and calcite, and can therefore be classified as oncoids. The reconstructions also show damage to the granule coatings caused by sedimentary transport during formation of the granules and eventual deposition as density currents. The detailed, three dimensional morphology of the granules in conjunction with previously published geochemical and isotope data indicate a biogenic origin for iron precipitation around chert granules on the shallow shelf of one of the oldest supracratonic environments on Earth almost three billion years ago. It broadens our understanding of biologically-mediated iron precipitation during the Archean by illustrating that it took place on the shallow marine shelf coevally with deeper water, below-wave base iron precipitation in micritic iron formations.

Modern weathering in outcrop samples versus ancient paleoredox information in drill core samples from a Mesoarchaean marine oxygen oasis in Pongola Supergroup, South Africa

There is growing evidence from Mo and Fe stable isotope tracers that shallow-water sediments of the 2.95 Ga Mozaan Group (Pongola Supergroup) in South Africa were deposited under oxidizing conditions, while mineralogical, elemental and S isotopic evidence favors the contemporaneous atmosphere to have remained reducing. In contrast, the first reported Cr-stable isotope data for White Mfolozi riverbed outcrop samples of the Ijzermijn iron formation (IF), Mozaan Group, and drill core samples of the underlying paleosol of the Nsuze Group were interpreted to require oxidative weathering conditions during the time of deposition. More recent Cr-isotope data of at least the Ijzermijn IF samples of the same White Mfolozi riverbed outcrop, however, suggested that modern weathering effects can superimpose oxidative signatures on paleo-redox proxies.This study compares (234U/238U) activity ratios along with stable Mo and Fe isotope data of corresponding drill core and White Mfolozi riverbed outcrop samples in order (i) to test (234U/238U) disequilibria as a potential tool to identify samples affected by modern weathering and (ii) to further investigate weathering effects on outcrop samples, particularly with regard to the stable Mo and Fe isotope systematics. All drill core samples from the Ijzermijn IF have (234U/238U) activity ratios that are within uncertainties of secular equilibrium (i.e. a value of 1), and thus were not significantly affected by modern weathering-related U gain or loss or other sub-recent rock-water interaction. By contrast, the outcrop IF and shale samples from the White Mfolozi riverbed show very strong deviations from the secular equilibrium (234U/238U) activity ratio. Furthermore, these deviations are accompanied by the observations that (i) outcrop samples have on average heavier δ56/54Fe values (−0.96‰) than drill cores (−1.59‰), and (ii) positive correlations in drill core samples between log[Fe/Mn] and δ98/95Mo or δ56/54Fe are disrupted by inclusion of the outcrop samples, as are negative correlations between log[MnO] and δ98/95Mo. However, δ56/54Fe and δ98/95Mo of our outcrop samples do not correlate with the extent of (234U/238U) disequilibria. As such, (234U/238U) activity ratios fail to act as a direct identification tool for modern weathering effects on stable Fe and Mo isotopes in outcrop samples. Overall, this study confirms the adsorption of isotopically light Mo onto MnO2 particles in oxic surface water conditions in the epicontinental Pongola Sea. Reduction of the Mn-oxides together with microbial Fe reduction in the reduced sediment pile of the Pongola basin led to the formation of Mn- and Fe-carbonates during early diagenesis storing the observed stable Fe and Mo isotopic signatures. We thus extend the so-called MnO2-shuttle first proposed for the Neoarchean 2.46 Ga old Koegas IF to late Mesoarchean shallow-marine depositional settings.

Limited oxygen production in the Mesoarchean ocean

The Archean Eon was a time of predominantly anoxic Earth surface conditions, where anaerobic processes controlled bioessential element cycles. In contrast to "oxygen oases" well documented for the Neoarchean [2.8 to 2.5 billion years ago (Ga)], the magnitude, spatial extent, and underlying causes of possible Mesoarchean (3.2 to 2.8 Ga) surface-ocean oxygenation remain controversial. Here, we report δ15N and δ13C values coupled with local seawater redox data for Mesoarchean shales of the Mozaan Group (Pongola Supergroup, South Africa) that were deposited during an episode of enhanced Mn (oxyhydr)oxide precipitation between ∼2.95 and 2.85 Ga. Iron and Mn redox systematics are consistent with an oxygen oasis in the Mesoarchean anoxic ocean, but δ15N data indicate a Mo-based diazotrophic biosphere with no compelling evidence for a significant aerobic nitrogen cycle. We propose that in contrast to the Neoarchean, dissolved O2 levels were either too low or too limited in extent to develop a large and stable nitrate reservoir in the Mesoarchean ocean. Since biological N2 fixation was evidently active in this environment, the growth and proliferation of O2-producing organisms were likely suppressed by nutrients other than nitrogen (e.g., phosphorus), which would have limited the expansion of oxygenated conditions during the Mesoarchean.

Aerobic iron and manganese cycling in a redox-stratified Mesoarchean epicontinental sea

Redox conditions in the marine realm prior to the Great Oxidation Event (GOE; ∼2.46–2.32 Ga ago), during which the atmospheric oxygen level rose dramatically for the first time, are still debated. Here, we present C, O, Fe, and Mo stable isotope systematics of Fe-, Mn-, and carbonate-rich shales, deposited at different water depths in association with iron formations (IFs) of the Mesoarchean Mozaan Group, Pongola Supergroup, South Africa. δ13C values between −22.3 and −13.5‰ VPDB, and δ18O values between −21.1 and −8.6‰ VPDB for Fe–Mn-rich carbonate minerals indicate their precipitation out of equilibrium with seawater. Instead, early diagenetic reduction of Fe–Mn-oxyhydroxide precursor minerals, along with microbially induced oxidation of organic matter (OM), formed these carbonates. δ56FeIRMM-014 values between −1.27 and 0.14‰ and δ98MoNIST3134+0.25 values between −0.46 and 0.56‰ co-vary with Mn concentrations and inferred water depth of deposition. This suggests that, despite the diagenetic origin of the Fe–Mn carbonates, the primary light Fe and Mo isotopic signature of Fe–Mn-oxyhydroxides that originally precipitated from seawater is still preserved. While isotopically light Mo implies that Mn(II) was oxidized to Mn(IV) due to the availability of free, photosynthetically produced O2, Mn enrichment suggests that the water column was redox stratified with a Mn-redoxcline situated at a depth below the storm wave base. A trend to highly negative δ56Fe values with increasing Mn/Fe ratios and decreasing depositional depth suggests progressive oxidation of Fe(II) as deep-waters upwelled across a redoxcline towards shallow, locally oxygenated waters where Mn(IV) oxyhydroxides precipitated. Combined δ56Fe and δ98Mo data indicate pervasive oxygenation of seawater with the O2 content in the photic zone likely reaching levels higher than the maximum value of 10 μM proposed for Archean oxygen oases. Since abiotic Mn(II) oxidation is kinetically very slow in marine environments, it is likely that Mn-oxidizing microorganisms catalyzed Mn-oxidation in the oxygenated Pongola surface waters during deposition of IFs. This implies that aerobic metabolism had evolved before the GOE in shallow, aquatic habitats, where it exerted a first-order control on the deposition of shallow-marine, Mn-rich iron formations.

Modern rather than Mesoarchaean oxidative weathering responsible for the heavy stable Cr isotopic signatures of the 2.95 Ga old Ijzermijn iron formation (South Africa)

Previously reported stable Cr isotopic fractionation in Archaean paleosols and iron formations (IFs) have been interpreted as a signature of oxidative weathering of Cr(III) to Cr(VI) in soils, and delivery of isotopically heavy Cr(VI) into the oceans. One of the oldest reported fingerprints of this process is isotopically heavy Cr preserved in the 2.95 Ga old Ijzermijn IF, Sinqeni Formation of the Mozaan Group (Pongola Supergroup), South Africa and could suggest that atmospheric free oxygen was present ca. 600 million years earlier than the Great Oxidation Event (GOE). However, fractionated stable Cr isotopic signatures have only been found to date in surface outcrop samples of the White Mfolozi Inlier exposed along the White Mfolozi River Gorge. In this study, the latter outcrop was resampled along with two drill cores of the Ijzermijn IF and a drill core of the Scotts Hill IF to represent multiple exposures of Mozaan Group IFs with different states of preservation. A detailed geochemical comparison on bulk samples of different units was undertaken using stable Cr isotopes coupled with trace and major elements. Outcrop iron-rich mudstones (Fe - lutites) show very low LOI [wt] %, and very low Fe(II)/Fetot ratios, and lower Ca and Mg relative to equivalent facies in drill cores, indicating the effects that oxidative recent surface weathering had on Fe/Mn-rich carbonate minerals of the IF. Overall rare earth element and yttrium (REE + Y) mixing models agree well with previous studies, confirming that they were minimally disturbed by weathering and are consistent with a high magnitude of continental solutes delivered in a near–shore depositional environment, with a minor contribution of hydrothermally derived fluids that upwelled into shallower depositional setting. Importantly, all drill core samples of this study revealed δ53/52Cr values within the igneous inventory, despite variable amounts of detrital Cr input that includes nearly detritus-free, chert/jasper-rich units. By contrast, a specific group of Fe-lutite samples near the base of White Mfolozi River outcrop bear fractionated Cr isotopic signatures with δ53/52Cr values up to 0.418‰. These outcrop samples also display unusually high U/Th ratios (max. 12.6) as well as enrichments of other elements (W, Tl, As, MREE) that far exceed that observed in correlative drill core units. These observations together with the lack of Cr isotopic fractionation in drill core samples lead us to propose that the heavy δ53/52Cr values of Fe-lutites from outcrop Ijzermijn IF samples reported here and in a previous study are the product of modern oxidative weathering rather than an indicator for Mesoarchaean oxidative weathering at ca. 2.95 Ga.

U-Pb and Hf isotopes of detrital zircons from the Pongola Supergroup: Constraints on deposition ages, provenance and Archean evolution of the Kaapvaal craton

The c.3.0–2.9 Ga Pongola Supergroup located on the south-eastern margin of the Kaapvaal Craton preserves some of the most pristine Archean successions but the timing of volcanic and sedimentary processes, and sediment sources remain relatively poorly known. Combined zircon U-Pb ages and Hf isotope data of sandstones from the Nsuze and Mozaan Groups are presented from key locations of the Northern, Central and Southern Domains of the 270 km long belt. These data indicate important lateral and temporal variations and therefore changes in source areas. The basal Pongola sedimentary rocks (Mantonga Formation) in the Northern Domain were derived from the c.3.4 Ga basement, and also most likely from reworked Moodies Group sedimentary rocks of the Barberton greenstone belt. Zircon detritus in Nsuze and lower Mozaan Groups sandstones shows similar age-Hf isotope spectra, and a remarkable overlap with data from magmatic and (meta)sedimentary rocks of the southeastern Kaapvaal craton. The data point to a proximal source for Nsuze sandstones in the Northern Domain and a different provenance for the Southern Domain sandstones. A possible signature of the extensive 3.10–3.07 Ga Mpuluzi granite is seen only in the Nsuze sandstones and basal Mozaan of the Central Domain. The data indicate for the first time that Cr-rich sandstones of the Ndikwe Thrust Segment of the Southern Domain were deposited at <2.92 Ma, and therefore belong to the uppermost Mozaan Group. Furthermore, they reveal a significant switch in provenance from the lower to upper Mozaan Group from a reworked Archean basement towards a more juvenile hinterland with εHft = +0.9 to +6.3 between 3.07 and 2.92 Ga; similar to the source previously reported for the Central Rand Group of the Witwatersrand Basin. The juvenile zircon detritus in the upper Mozaan Group requires sources as far as the Pietersburg and/or Kimberley Blocks, which became amalgamated to the central block of the Kaapvaal Craton at 2.97–2.87 Ga, but perhaps also a source outside of the present day Kaapvaal Craton, and possibly as far as the Pilbara Craton.

Unusual manganese enrichment in the Mesoarchean Mozaan Group, Pongola Supergroup, South Africa

An unusual sediment-hosted manganese deposit is described from the Mesoarchean Mozaan Group, Pongola Supergroup, South Africa. MnO contents up to 15wt.% were observed in marine clastic and chemical sedimentary rocks. Mn enrichment is interpreted to have resulted from the hydrothermal alteration of manganiferous shale and BIF parent rocks, the primary MnO contents of which are as high as 8.5wt.%. A detailed mineralogical and petrographic study shows that these parent rocks are characterized by manganoan siderite, ferroan rhodochrosite and other Mn–Fe-rich mineral phases, such as kutnohorite and Fe–Mn-chlorite. Their hypogene alteration gave rise to a diversification of mineral assemblages where ferroan tephroite, calcian rhodochrosite, rhodochrosite, pyrochroite, pyrophanite, cronstedtite, manganoan Fe-rich chlorite and manganoan phlogopite partially or totally replaced the previous mineral assemblage. Thermodynamic modeling performed on chlorite phases associated with the described mineral assemblages illustrates a decrease of average crystallization temperatures from ca. 310°C during early metamorphic stages to ca. 250°C during a hydrothermal stage. Mineral transformation processes were thus related to retrograde metamorphism and/or hydrothermal alteration post-dating metamorphism and gave rise to progressive Mn enrichment from unaltered parent to altered rocks. The timing of hypogene alteration was constrained by 40Ar/39Ar dating to between about 1500 and 1100Ma ago, reflecting tectonic processes associated with the Namaqua-Natal orogeny along the southern Kaapvaal Craton margin. Manganiferous shale and BIF of the Mozaan Group may represent the oldest known examples of primary sedimentary Mn deposition, related to oxidation of dissolved Mn(II) by free oxygen in a shallow marine environment. Oxygenic photosynthesis would have acted as a first-order control during Mn precipitation. This hypothesis opens a new perspective for better constraining secular evolution of sediment-hosted mineral deposits linked to oxygen levels in the atmosphere-hydrosphere system during the Archean Eon.

Precise U-Pb baddeleyite age dating of the Usushwana Complex, southern Africa – Implications for the Mesoarchaean magmatic and sedimentological evolution of the Pongola Supergroup, Kaapvaal Craton

The Usushwana Complex of the south-eastern Kaapvaal Craton (South Africa and Swaziland), intrudes the ca. 3.6–3.1Ga basement of the craton, as well as the Mesoarchaean volcanic and sedimentary cover succession of the Pongola Supergroup. New high-precision U-Pb dating of gabbros belonging to the Piet Retief Suite of the Usushwana Complex yield ages of 2989±1Ma, 2990±2Ma and 2978±2Ma. The Piet Retief Suite represents part of an intricate magmatic feeder to a major volcanic event which gave rise to the oldest known continental flood basalts on Earth, the Nsuze volcanic rocks. Broadly coeval SE-trending dolerite dykes of the Barberton-Badplaas Dyke Swarm in the larger region of the south-eastern Kaapvaal Craton formed along the same structural trend as the Usushwana Complex. One such dyke is dated herein to 2980±1Ma. Using the high-precision U-Pb geochronological data, the Nsuze volcanic rocks can now be resolved into at least two magmatic episodes which can be correlated with parts of the Pongola Supergroup. The first episode at ca. 2.99–2.98Ga is broadly coeval with the Pypklipberg (Nhlebela) volcanic rocks, whereas the second at ca. 2.97–2.96Ga was near synchronous to the Agatha volcanic rocks. A dolerite sill intruding into the Mozaan Group of the Pongola Supergroup, thought to be part of the Usushwana Complex, was dated to 2869±5Ma, and is instead coeval with the Hlagothi Complex further to the south, and provides a new minimum age for deposition of the Mozaan Group.

A trace element and Pb isotopic investigation into the provenance and deposition of stromatolitic carbonates, ironstones and associated shales of the ∼3.0 Ga Pongola Supergroup, Kaapvaal Craton

Major and trace element, and Pb isotopic data for chemical and clastic sedimentary rocks of the Mesoarchaean Pongola Supergroup are employed to infer aspects of the provenance and depositional environment, including ambient seawater composition. Stromatolitic carbonates of the Nsuze Group were formed in a tidal-flat setting, whereas ironstones of the Mozaan Group were deposited in an outer-shelf setting during marine transgression. Geochemical criteria, employed to test for crustal contamination and diagenetic/metamorphic overprinting, demonstrate that carbonates and ironstones preserved their primary chemical signature. In comparison to other documented Precambrian stromatolites, shale-normalised REE+Y patterns for Nsuze carbonates show pronounced enrichment in middle REE, but lack strong elemental anomalies (La, Gd, Y) that are diagnostic for derivation from open marine waters. In contrast, normalised REE+Y for ironstones exhibit distinct positive La, Gd and Y anomalies. Both rock types are devoid of normalised Ce anomalies and show only minor enrichment in Eu, suggesting deposition in anoxic environments (with respect to the Ce3+/Ce4+ redox couple) accompanied by minor high-temperature hydrothermal input. Trace element geochemical data are most consistent with deposition of Nsuze carbonates in a shallow-water epicontinental basin with restricted but variable exchange to the open-ocean and dominant fluvial input, whereas ironstone precipitated in a deeper-water, epicontinental sea. Estuarine fractionation and organic complexation due to microbial activity is possibly indicated by MREE enrichment of the carbonates, also consistent with a restricted environment.Shales belonging to the Mozaan Group are characterised by high concentrations of Al and K relative to Ca, Na and Sr, indicative of pronounced in-situ weathering, coupled with K-metasomatism. The provenance is mixed, comprising (ultra)mafic and granitic source rocks.Pb isotope regression for Nsuze carbonates documents a widespread, tectono-thermal or fluid percolation event at around 2.4Ga. Two-stage modelling of Pb isotope data, in association with published Sr and Nd isotope data, requires a source for Nzuse carbonates that was derived from evolved continental crust with an elevated U/Pb ratio (μ-value) and an approximate crustal residence time of ∼100–600Ma.

Pressure, temperature, and timing of mineralization of the sedimentary rock-hosted orogenic gold deposit at Klipwal, southeastern Kaapvaal Craton, South Africa

Gold mineralization in the Klipwal Shear Zone (KSZ) at the Klipwal Gold Mine is confined to laminated quartz-carbonate lodes, stringers, and associated alteration in sandstone and siltstone of the Delfkom Formation in the upper Mozaan Group of the Mesoarchaean Pongola Supergroup. The moderately dipping brittle-ductile KSZ strikes N-S with an oblique-reverse, sinistral sense of shear. The deformational events that are recognized include an early phase that produced anastomosing shears defined by shear fabrics with numerous shear-parallel laminated quartz-carbonate fault-fill veins and, in places, extensional quartz vein stockworks, and a late brittle reactivation phase that produced fault breccias, displacing earlier extensional veins. Three closely spaced economic reefs (lodes) are developed: the main R-reef constitutes the KSZ, while the J- and H-reefs represent footwall splays. Alteration comprises chlorite, muscovite, epidote, feldspar, and carbonates along with pyrite, arsenopyrite, and chalcopyrite +/- pyrrhotite. An inner alteration zone is dominated by laminated quartz-carbonate veins with alternating quartz-carbonate-rich and muscovite-chlorite-rich laminae, whereas the proximal zone is characterized by alteration halos of K-feldspar, albite, epidote, chlorite, and muscovite along with carbonates and associated quartz veins. Chlorite thermometry from the inner and proximal zones yielded temperatures of 267 to 312 A degrees C. Arsenopyrite compositions provide temperatures in the same range, 255 to 318 A degrees C. Fluid inclusion microthermometry and Raman spectrometry of quartz veins in the mineralized reefs reveal the presence of metamorphogenic aqueous-gaseous fluid with an average salinity of 6.5 wt% NaCl equiv. Fluid compositions and estimated pressure-temperature (P-T) range (1.1 to 2.5 kbar at 255 to 318 A degrees C) are typical of orogenic gold deposits. Devolatilization during the regional facies metamorphism of the Pongola Supergroup is considered the likely fluid-forming event with fluid flow focused into a compressional jog of the KSZ. Shear-induced pressure fluctuations generated a phase separation of the initial aqueous-gaseous fluid, producing a gaseous and low-salinity aqueous fluid. This, together with fluid-rock interaction, and a decrease in fO(2) lead to sulfide and gold precipitation at Klipwal. Re-Os data from six sulfide samples constrain the age of sulfide precipitation and, by inference, gold mineralization, to 2563 A +/- 84 Ma, with an initial Os-187/Os-188 = 0.29 A +/- 0.08 (MSWD = 0.38). This age is distinctly younger than the post-Pongola granites (2863-2721 Ma), ruling out the association of granite emplacement with mineralization. This would suggest that mineralization is linked to the regional D-3 folding event which reactivated the KSZ after emplacement of the post-Pongola granites and that final brittle, post-mineralization reactivation is related to Karoo age faulting. Low initial Os values suggest that ore fluid interacted with mafic rocks, leaching non-radiogenic Os, the likely source being the deeper seated Nsuze Group volcanics and/or the greenstone belts that underlie the Pongola Supergroup.

The Nhlangano gneiss dome in south-west Swaziland – A record of crustal destabilization of the eastern Kaapvaal craton in the Neoarchaean

The Nhlangano granite-gneiss in south-west Swaziland, dated at 2.98Ga, forms an elliptical dome of remobilised, migmatitic crust. Strongly deformed supracrustal rocks wrap around or form synformal keels infolded with subdomes of Nhlangano Gneiss and represent Mesoarchaean Pongola Supergroup strata at amphibolite- to granulite-facies metamorphic grade. Amphibolites represent the metamorphosed equivalents of Nsuze Group basalts and andesites on the basis of similar trace element and Nd isotope data. Garnetiferous Mahamba Gneiss, dated at c. 2.96Ga, represents the metamorphosed equivalents of felsic to intermediate volcanic rocks and minor pelitic interflow sedimentary units of the Nsuze Group. Quartzites and associated metamorphosed iron formations are part of the lower Mozaan Group (Sinceni Formation) as indicated by the presence of detrital zircons as young as 3.07Ga and matching geochemical provenance characteristics. Ar-Ar analysis of hornblende separates dates amphibolite-facies metamorphism and associated dome emplacement at c. 2.72Ga. Exhumation took place during NW-SE crustal extension and was facilitated by partial melting of the mid-crustal rocks. Exhumation took place below a southeastward-dipping detachment fault, giving rise to NW-SE oriented elliptical gneiss domes due to vertical and lateral flow of partially molten rocks. The Nhlangano gneiss dome has features in common with migmatite-cored metamorphic core complexes. Its emplacement points to tectonic instability of the eastern part of the Kaapvaal Craton in the Neoarchaean.

High-grade metamorphism of ironstones in the Mesoarchaean of southwest Swaziland

A sequence of high-grade rocks collectively referred to as Mkhondo Valley Metamorphic Suite is exposed around the Nhlangano Gneiss Dome in southwest Swaziland and also less extensively further north. Meta-ironstones are part of this sequence and have been studied specifically with two main objectives in mind, firstly, to test the hypothesis of the high-grade metamorphic sequence correlating with lower-grade Pongola-age rocks nearby, and secondly, to assess the potential of these meta-ironstones for retrieving P-T conditions of metamorphism. The studied ironstones contain substantial Al due to terrigenous clastic input and also include Mn-rich varieties. Three compositional groups of meta-ironstones can be distinguished: garnet-orthopyroxene-bearing ones, garnet-bearing, orthopyroxene-free ones, and a garnet-poor to garnet-free type. A comparison of bulk rock compositions between these high-grade meta-ironstones and low-grade Mn-poor to Mn-rich ironstones from the Mozaan Group supports a stratigraphic correlation. Pseudosection modelling demonstrates that aluminous meta-ironstones provide useful P-T constraints at high peak temperatures as they do not tend to produce significant amounts of melt, if any. The presence of Al is critical for introducing garnet to amphibolite and granulite-facies assemblages, which also allows to apply conventional thermobarometers. The combination of pseudosection modelling and conventional thermobarometry yielded peak metamorphic conditions of 850–890 °C at 7 to 8 kbar. These data are compatible with the ones obtained from associated metapelitic gneisses, except that the latter indicate decompression to lower pressure granulite-facies conditions. The petrological, structural and geochronological data from southwest Swaziland confirm major orogenic activity in the eastern Kaapvaal Craton during the Neo-Archaean.