Geochemistry as a Clue for Paleoweathering and Provenance of Southern Apennines Shales (Italy): A Review

The southern Apennines (Italy) chain is a fold-and-thrust belt mainly derived from the deformation of the African–Apulian passive margin where shallow-water, basinal, and shelf-margin facies successions, including fine-grained sediments, occur. Here, we provide a review of the geochemistry of Meso–Cenozoic shales from the Lagonegro basin to elucidate provenance and paleoweathering. The different suites of these shales are dominated by 2:1 clay minerals and are Fe shales and shales. An R-mode factor analysis suggests Ti, Al, and LREE (F1) and K2O-MgO (F2) covariance, likely related to the illite → smectite → kaolinite evolution during weathering. HREE and Y are distributed by phosphate minerals, suggesting LREE/HREE fractionation. The CIA paleoweathering proxy rules out non-steady-state weathering conditions and indicates that the source area was affected by moderate to intense weathering. The paleoprecipitation values derived from the CIA-K and CALMAG indices show median values in the 1214–1610 mm/y range. The Eu/Eu*, Sm/Nd, and Ti/Al provenance ratios point toward a UCC-like source excluding any mafic supply and suggest that the Lagonegro basin was connected, through a southern area, with the African cratonic area. However, the Eu/Eu* median value of the southern Apennine shales is quite similar to the value of the Archean shales, possibly indicating a less differentiated component. This is consistent, in many samples, with the value of the (Gd/Yb)ch ratio, suggesting that the shales likely incorporated ancient sediments derived from African Archean terranes through a cannibalistic proces

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REEs in the North Africa P‐Bearing Deposits, Paleoenvironments, and EconomicPerspectives: AReview

AreviewofthecompositionalfeaturesofTunisia,Algeria,andMoroccophosphoritesisproposedinordertoassessandcomparethepaleoenvironmentalconditionsthatpromotedthede‐positformationaswellasprovideinformationabouttheireconomicperspectiveinlightofgrowingworldwidedemand.Sincethesedepositsshareaverysimilarchemicalandmineralogicalcomposi‐tion,theattentionwasfocusedonthegeochemistryofrareearthelements(REEs)andmostlyonΣREEs,CeandEuanomalies,and(La/Yb)and(La/Gd)normalizedratios.TheREEsdistributionsrevealseveraldifferencesbetweendepositsfromdifferentlocations,suggestingmostlythattheTu‐nisianandAlgerianphosphoritesprobablywerepartofthesamedepositionalsystem.There,sub‐reducingtosub‐oxicconditionsandamajorREEsadsorptionbyearlydiagenesiswererecorded.Conversely,intheMoroccanbasins,sub‐oxictooxicenvironmentsandaminordiageneticalterationoccurred,whichwaslikelyduetoadifferentseawatersupply.Moreover,thedrasticenvironmentalchangesassociatedtothePaleocene–EoceneThermalMaximumeventprobablyinfluencedthecom‐positionofNorthernAfricanphosphoritesthataccumulatedthehighestREEsamountsduringthatspanoftime.BasedontheREEsconcentrations,andconsideringtheoutlookcoefficientofREEcomposition(Koutl)andthepercentageofcriticalelementsin ΣREEs(REEdef),thestudieddepositscanbeconsideredaspromisingtohighlypromisingREEoresandcouldrepresentaprofitableal‐ternativesourceforcriticalREEs

REEs and other critical raw materials in Cretaceous Mediterranean-type bauxite: the case of the Sardinian ore (Italy)

Mediterranean-type bauxite deposits in Sardinia formed during the Upper Cretaceous (Cenomanian–Turonian) due to the emergence of the south European margin of the Alpine Tethys in an area affected by monsoonal climate. The deposits were controlled by the structural frame formed in a transpressive tectonic regime and unconformably overlie carbonate rocks of different age and composition, which led to the formation of different bauxite types. In general, in the Sardinian bauxite deposits, boehmite is the main Al-phase, kaolinite is the main Si-rich mineral, and hematite as well as goethite are the Fe-rich phases. Secondary authigenic anatase and detrital rutile control the Ti contents. Eu/Eu* anomalies show that the bauxite types were derived from the Variscan basement. However, there are differences in Al2O3 and SiO2 contents, which suggest there was localised variability in the extent of epigenetic replacement of kaolinite by boehmite. R-mode factor analysis suggests that most critical raw materials (as defined by the devoted European Union working group), such as Sc, Ga, Nb, Hf, Ta, and W, covary with Al2O3 contents. In the Si-poor bauxite, these metals of economic interest are likely controlled by boehmite, whereas in the Si-rich bauxite they are mostly controlled by weathering-resistant minerals. Rare earth element (REE)-rich minerals, including fluorocarbonates and cerianite, are concentrated in the basal, illuvial horizon, especially in the silica-rich bauxite (ΣREE = 1006–2034 ppm). Cerianite formation required Ce oxidation, whereas fluorocarbonate formation involved mobilisation of trivalent REEs and further fluoride complexation. Both REE-rich mineral phases precipitated under alkaline pH conditions near to the carbonate bedrock. Our evaluation of the critical raw materials distribution in the Sardinian bauxite, coupled with the “economic importance” and “supply risk” parameters, indicate the ore contains large amounts of metals characterised by a “supply risk”, such as light and heavy REEs, and metals of “economic importance”, such as V and W. In this way, the Sardinian bauxite deposits could be reconsidered as a potential source of critical raw materials

Mineralogy and heavy metal assessment of the Pietra del Pertusillo reservoir sediments (Southern Italy)

The Pietra del Pertusillo freshwater reservoir is a major artificial lake of environmental, biological, and ecological importance located in the Basilicata region, southern Italy. The reservoir arch-gravity dam was completed in 1963 for producing hydroelectric energy and providing water for human use, and nearby there are potential sources of anthropogenic pollution such as urban and industrial activities. For the first time, the minero-chemistry of the lake and fluvio-lacustrine sediments of the reservoir have been evaluated to assess the environmental quality. Moreover, the composition of fluvial sediments derived from the peri-lacual zone of the reservoir and of local outcropping bedrock were also studied to understand the factors affecting the behavior of elements in the freshwater reservoir, with particular attention paid to heavy metals. In Italy, specific regulatory values concerning the element threshold concentration for lake and river sediments do not exist, and for this reason, soil threshold values are considered the standard for sediments of internal waters. The evaluation of the environmental quality of reservoir sediments has been performed using enrichment factors obtained with respect to the average composition of a reconstructed local upper continental crust. We suggest this method as an innovative standard in similar conditions worldwide. In the studied reservoir sediments, the trace elements that may be of some environmental concern are Cr, Cu, Zn, As, and Pb although, at this stage, the distribution of these elements appears to be mostly driven by geogenic processes. However, within the frame of the assessment and the preservation of the quality of aquatic environments, particular attention has to be paid to As (which shows median value of 10 ppm, reaching a maximum value of 26 ppm in Quaternary sediments), constantly enriched in the lacustrine samples and especially in the fine-grained fraction (median = 8.5 ppm)

U-Pb detrital zircon ages and Hf isotope from Sardinia and Adria Cretaceous bauxite (Italy): Constraints on the Alpine Tethys paleogeography and tectonic evolution

Bauxite deposits in Italy mainly distribute in Sardinia and Adria regions within Cretaceous carbonate sequences. Parental affinity of Italian bauxite deposits has long been a controversial problem. At least four potential sources have been proposed: (1) Cretaceous debris and autochthonous marlstones; (2) alluvial sheets from the weathered Variscan basement; (3) weathering materials from North Africa and (4) Cretaceous bimodal volcanism in the Dinaric and Carpatho-Balkan orogenic belts. In this study, a total of 374 detrital zircon U-Pb ages and 86 Hf isotope values have been acquired from Cretaceous bauxites of Sardinia and Adria regions. Combining with the published geochemical data, provenances of Cretaceous bauxite deposits in Sardinia and Adria regions have been discussed. In bauxite deposits of Sardinia, dominant Early Paleozoic aged zircon grains (main age peaks at 291 – 295 Ma, 454 – 465 Ma, and 582 – 639 Ma) and their various Hf isotope compositions (εHf(t) = +9.61 to −5.66) indicate a parental affinity of Variscan metasedimentary basement. As a contrast, bauxite deposits in Adria show abundant Jurassic – Cretaceous (93 – 178 Ma) zircon grains with negative εHf(t) values (-13.75 to −4.61), demonstrating significant supply from coeval volcanic materials. Cretaceous bauxite samples from Sardinia and Adria shed light on paleogeographic restoration and tectonic evolution of Alpine Tethys. Began in Early Cretaceous, Sardinia was affected by uplift due to the subduction between Ligurian oceanic crust and the Iberia plate. The Mesozoic carbonate sequence were eroded and the underlying Variscan basement was exposed in the area from Sardinia to the Massif Meridional, provided weathering materials for bauxitization. Late Cretaceous witnessed the further NNE-trending subduction of the Adria Plate to the West Vardar oceanic plate, where calcalkaline igneous rocks and volcanic ashes from Dinarides supplied windborne weathering materials to carbonate platforms in Adria. Particularly, provenance difference between the bauxite of central-southern Apennine and Sardinian reveals that the hosting carbonate sequence in Apennine was not located on the Sardinia shelf before the Cenozoic tectonism in the south Mediterranean realm. Diversity of provenances in bauxite deposits from Sardinia and Adria may cause differences in geochemical composition and further influence qualities of bauxite ore in two regions

Petrography and Geochemistry of the Leucocratic Rocks in the Ophiolites from the Pollino Massif (Southern Italy)

In the Tethyan realm, leucocratic rocks were recognized as dikes and layers outcropping in the ophiolitic rocks of the Western Alps, in Corsica, and in the Northern Apennines. Several authors have suggested that the origin of leucocratic rocks is associated with partial melting of cumulate gabbro. Major and trace elements composition and paragenesis provided information about the leucocratic rocks genetic processes. This research aims at disclosing, for the first time, the petrographical and geochemical features of Timpa delle Murge leucocratic rocks, Pollino Massif (southern Italy), in order to discuss their origin and geodynamic significance through a comparison with other Tethyan leucocratic rocks. These rocks are characterized by high amounts of silica with moderate alumina and iron-magnesium contents showing higher potassium contents than plagiogranites, due to plagioclase alteration to sericite. Plagioclase fractionation reflects negative Eu anomalies indicating its derivation from gabbroic crystal mushes. The chondrite normalized REEs patterns suggest the participation of partial melts derived from a metasomatized mantle in a subduction environment. The results reveal some similarities in composition with other Tethyan leucocratic rocks, especially those concerning Corsica and the Northern Alps. These new data provide further clues on the origin of these leucocratic rocks and the Tethyan area geodynamic evolutio