Alpine subduction zone metamorphism in the Paleozoic successions of the Monti Romani (Northern Apennines, Italy)

The hinterland of the Cenozoic Northern Apennines fold-and-thrust belt exposes the metamorphic roots of the chain, vestiges of the subduction-related tectono-metamorphic evolution that led to the buildup of the Alpine orogeny in the Mediterranean region. Like in other peri-Mediterranean belts, the tectono-metamorphic evolution of the Paleozoic continental basement in the Apennines is still poorly constrained, hampering the full understanding of their Alpine orogenic evolution. We report the first comprehensive tectono-metamorphic study of the low-grade metasedimentary (metapsammite/metapelite) succession of the Monti Romani Complex (MRC) that formed after Paleozoic protoliths and constitutes the southernmost exposure of the metamorphic domain of the Northern Apennines. By integrating fieldwork with microstructural studies, Raman spectroscopy on carbonaceous material and thermodynamic modelling, we show that the MRC preserves a D1/M1 Alpine tectono-metamorphic evolution developed under HP-LT conditions (~ 1.0-1.1 GPa at T ~400 °C) during a non-coaxial, top-to-the-NE, crustal shortening regime. Evidence for HP-LT metamorphism is generally cryptic within the MRC, dominated by graphite-bearing assemblages with the infrequent blastesis of muscovite ± chlorite ± chloritoid ± paragonite parageneses, equilibrated under cold paleo-geothermal conditions (~ 10 °C/km). Results of this study allow extending to the MRC the signature of subduction zone metamorphism already documented in the hinterland of the Apennine orogen, providing further evidence of the syn-orogenic ductile exhumation of the HP units in the Apennine belt. Finally, we discuss the possible role of fluid-mediated changes in the reactive bulk rock composition on mineral blastesis during progress of regional deformation and metamorphism at low-grade conditions.

Functionalization of Screen-Printed Sensors with A High Reactivity Carbonaceous Material for Ascorbic Acid Detection in Fresh-Cut Fruit with Low Vitamin C Content

In this study, carbon screen-printed sensors (C-SPEs) were functionalized with a high reactivity carbonaceous material (HRCM) to measure the ascorbic acid (AA) concentration in fresh-cut fruit (i.e., watermelon and apple) with a low content of vitamin C. HRCM and the functionalized working electrodes (WEs) were characterized by SEM and TEM. The increases in the electroactive area and in the diffusion of AA molecules towards the WE surface were evaluated by cyclic voltammetry (CV) and chronoamperometry. The performance of HRCM-SPEs were evaluated by CV and constant potential amperometry compared with the non-functionalized C-SPEs and MW-SPEs nanostructured with multi-walled carbon nanotubes. The results indicated that SPEs functionalized with 5 mg/mL of HRCM and 10 mg/mL of MWCNTs had the best performances. HRCM and MWCNTs increased the electroactive area by 1.2 and 1.4 times, respectively, whereas, after functionalization, the AA diffusion rate towards the electrode surface increased by an order of 10. The calibration slopes of HRCM and MWCNTs improved from 1.9 to 3.7 times, thus reducing the LOD of C-SPE from 0.55 to 0.15 and 0.28 μM, respectively. Finally, the functionalization of the SPEs proved to be indispensable for determining the AA concentration in the watermelon and apple samples.

The thermo-tectonic evolution of the Suckling-Dayman metamorphic core complex, southeastern Papua New Guinea

<p>The Suckling-Dayman metamorphic core complex (SDMCC) in the Woodlark Rift of southeastern Papua New Guinea is being exhumed along the Mai’iu Fault, an active low-angle normal fault dipping ~20-22° northwards at the surface. The spectacularly smooth topography of the Mai’iu Fault footwall clearly is expressive of geologically recent uplift. The precise timing and rates of the exhumation of this continental metamorphic core complex (MCC) have, however, never been studied in detail. This thesis provides the first systematic set of U-Pb, fission track (FT), (U-Th[-Sm])/He and ²⁶Al/¹⁰Be ages from metaigneous and metasedimentary rocks of the footwall of the SDMCC, clasts and a tephra deposit contained within syn-tectonic conglomerates (the Gwoira Conglomerate) in a rider block, and modern stream sediments in the footwall and hanging wall of the Mai’iu Fault. The ages are complemented by whole-rock compositional and thermobarometric data (Al-in-amphibole, Al-in-biotite, Raman spectroscopy of carbonaceous material). Based on these data, the timing of the onset of extension along the Mai’iu Fault, its long-term dip-slip rate and its initial dip were constrained. These data are presented in the context of the evolution of the SDMCC from the Cretaceous to the present. The dominant lithology of the SDMCC, the Goropu Metabasalt, formed in a marginal basin to the northeast of the Australian continent. Two zircon U-Pb ages of 103.0 ± 5.7 and 71.6 ± 3.3 Ma, indicative of maximum depositional ages, from metasedimentary intercalations (the Bonenau Schist) in the Goropu Metabasalt, suggest formation of the oceanic protolith in the Late Cretaceous. Between 60.4 ± 2.5 and 56.6 ± 2.3 Ma (zircon U-Pb), tholeiitic to mildly calc-alkaline gabbroic to tonalitic rocks of the Yau Igneous Complex intruded the Goropu Metabasalt. The age of the Yau Igneous Complex overlaps with the known timing of north-directed subduction of the oceanic lithosphere along the Owen Stanley Fault (OSF) beneath the Cape Vogel Arc and provides a minimum age for the oceanic protolith. A second phase of magmatism, consisting of peraluminous-metaluminous calc-alkaline (Suckling Granite) and high-K (Mai’iu Monzonite, Bonua Porphyry) granitoids and basaltic andesite dikes that were cut by the Mai’iu Fault, was associated with the tectonic inversion of the OSF. Zircons from these syn-extensional intrusions suggest crystallization between 3.8 ± 0.2 and 2.0 ± 0.1 Ma. The oldest age of this range is inferred to mark the time by which the OSF had been re-activated as an extensional structure, the Mai’iu Fault. Al-in-amphibole and -biotite thermobarometry suggests crystallization of the Suckling Granite and Mai’iu Monzonite in a relatively shallow crust (~2-8 km depth) at pressures of ~0.4-2.3 kbar. Inherited zircons in the Plio-Pleistocene granitoids indicate that the Goropu Metabasalt carapace of the SDMCC is underlain by Australian-derived Cretaceous crustal material that is inferred to be the continuation of the Kagi Metamorphics in the central Papuan Peninsula. Further constraints of the timing of unroofing of the SDMCC were determined from three quartz clasts in the Gwoira Conglomerate. ²⁶Al/¹⁰Be burial ages of these samples indicate deposition in the Pliocene between 4.6 ± 2.9 and 3.4 ± 2.1 Ma. A tephra in the upper section of the exposed conglomerates was dated employing U-Pb methods on zircon, combined with apatite, zircon and magnetite (U-Th[-Sm])/He chronometers, yielding a complex age spectrum. An eruption age of 0.6 ± 0.4 Ma was extrapolated for this tephra. FT and (U-Th[-Sm])/He low-temperature thermochronometry details a young (≤3 Ma) and rapid exhumation history. Based on the crystallization ages of the syn-extensional granitoids, the depositional age of the Gwoira Conglomerate, the extensional cooling recorded by low-temperature thermochronometry, and the backwards projection of the published Holocene dip-slip rate of the Mai’iu Fault, the timing of the onset of extension is estimated at ~4 Ma. A minimum dip-slip rate of 8.1 ± 1.3 km/myr has been calculated from the inverse slope of zircon (U-Th)/He (ZHe) ages with slip-parallel distance from Mai’iu Fault trace. This is slightly lower than the >12 km/myr required to restore the intrusion depths (2-8 km) of the syn-extensional granitoids, now exposed 20-25 km south of the Mai’iu Fault trace at elevations up to 3.4 km. Collectively, these constraints suggest that the Mai’iu Fault has moved at cm-per-year rates since ~3 Ma. Evidence for both a fossil zircon FT (ZFT) partial annealing zone (PAZ) and a ZHe partial retention zone (PRZ) on the footwall of the SDMCC is presented. Combining paleo-temperature estimates from the inferred bases of the zircon PAZ and PRZ, peak-metamorphic temperatures inferred from Raman spectroscopy of carbonaceous material (RSCM), and published peak-metamorphic temperature constraints on the extensional shear zone mylonites near the Mai’iu Fault trace, a minimum slip-parallel, down-dip paleo-temperature gradient of 9.7 ± 2.2°C/km has been estimated for the exhumed Mai’iu Fault plane. Assuming that the modern regional geothermal gradient in the Woodlark Rift is a maximum estimate of that which existed prior to extensional exhumation of the SDMCC, the paleo-temperature gradient was used to estimate an average initial dip of the Mai’iu Fault of ~44° for pre-extensional geothermal gradients ranging between 10 to 20°C/km. Presently dipping 20-22° at the surface, the constraints on the initial dip suggest that the Mai’iu Fault may have been back-rotated by >20° since the onset of extension, consistent with a rolling hinge-style evolution of this continental MCC.</p>

The thermo-tectonic evolution of the Suckling-Dayman metamorphic core complex, southeastern Papua New Guinea

<p>The Suckling-Dayman metamorphic core complex (SDMCC) in the Woodlark Rift of southeastern Papua New Guinea is being exhumed along the Mai’iu Fault, an active low-angle normal fault dipping ~20-22° northwards at the surface. The spectacularly smooth topography of the Mai’iu Fault footwall clearly is expressive of geologically recent uplift. The precise timing and rates of the exhumation of this continental metamorphic core complex (MCC) have, however, never been studied in detail. This thesis provides the first systematic set of U-Pb, fission track (FT), (U-Th[-Sm])/He and ²⁶Al/¹⁰Be ages from metaigneous and metasedimentary rocks of the footwall of the SDMCC, clasts and a tephra deposit contained within syn-tectonic conglomerates (the Gwoira Conglomerate) in a rider block, and modern stream sediments in the footwall and hanging wall of the Mai’iu Fault. The ages are complemented by whole-rock compositional and thermobarometric data (Al-in-amphibole, Al-in-biotite, Raman spectroscopy of carbonaceous material). Based on these data, the timing of the onset of extension along the Mai’iu Fault, its long-term dip-slip rate and its initial dip were constrained. These data are presented in the context of the evolution of the SDMCC from the Cretaceous to the present. The dominant lithology of the SDMCC, the Goropu Metabasalt, formed in a marginal basin to the northeast of the Australian continent. Two zircon U-Pb ages of 103.0 ± 5.7 and 71.6 ± 3.3 Ma, indicative of maximum depositional ages, from metasedimentary intercalations (the Bonenau Schist) in the Goropu Metabasalt, suggest formation of the oceanic protolith in the Late Cretaceous. Between 60.4 ± 2.5 and 56.6 ± 2.3 Ma (zircon U-Pb), tholeiitic to mildly calc-alkaline gabbroic to tonalitic rocks of the Yau Igneous Complex intruded the Goropu Metabasalt. The age of the Yau Igneous Complex overlaps with the known timing of north-directed subduction of the oceanic lithosphere along the Owen Stanley Fault (OSF) beneath the Cape Vogel Arc and provides a minimum age for the oceanic protolith. A second phase of magmatism, consisting of peraluminous-metaluminous calc-alkaline (Suckling Granite) and high-K (Mai’iu Monzonite, Bonua Porphyry) granitoids and basaltic andesite dikes that were cut by the Mai’iu Fault, was associated with the tectonic inversion of the OSF. Zircons from these syn-extensional intrusions suggest crystallization between 3.8 ± 0.2 and 2.0 ± 0.1 Ma. The oldest age of this range is inferred to mark the time by which the OSF had been re-activated as an extensional structure, the Mai’iu Fault. Al-in-amphibole and -biotite thermobarometry suggests crystallization of the Suckling Granite and Mai’iu Monzonite in a relatively shallow crust (~2-8 km depth) at pressures of ~0.4-2.3 kbar. Inherited zircons in the Plio-Pleistocene granitoids indicate that the Goropu Metabasalt carapace of the SDMCC is underlain by Australian-derived Cretaceous crustal material that is inferred to be the continuation of the Kagi Metamorphics in the central Papuan Peninsula. Further constraints of the timing of unroofing of the SDMCC were determined from three quartz clasts in the Gwoira Conglomerate. ²⁶Al/¹⁰Be burial ages of these samples indicate deposition in the Pliocene between 4.6 ± 2.9 and 3.4 ± 2.1 Ma. A tephra in the upper section of the exposed conglomerates was dated employing U-Pb methods on zircon, combined with apatite, zircon and magnetite (U-Th[-Sm])/He chronometers, yielding a complex age spectrum. An eruption age of 0.6 ± 0.4 Ma was extrapolated for this tephra. FT and (U-Th[-Sm])/He low-temperature thermochronometry details a young (≤3 Ma) and rapid exhumation history. Based on the crystallization ages of the syn-extensional granitoids, the depositional age of the Gwoira Conglomerate, the extensional cooling recorded by low-temperature thermochronometry, and the backwards projection of the published Holocene dip-slip rate of the Mai’iu Fault, the timing of the onset of extension is estimated at ~4 Ma. A minimum dip-slip rate of 8.1 ± 1.3 km/myr has been calculated from the inverse slope of zircon (U-Th)/He (ZHe) ages with slip-parallel distance from Mai’iu Fault trace. This is slightly lower than the >12 km/myr required to restore the intrusion depths (2-8 km) of the syn-extensional granitoids, now exposed 20-25 km south of the Mai’iu Fault trace at elevations up to 3.4 km. Collectively, these constraints suggest that the Mai’iu Fault has moved at cm-per-year rates since ~3 Ma. Evidence for both a fossil zircon FT (ZFT) partial annealing zone (PAZ) and a ZHe partial retention zone (PRZ) on the footwall of the SDMCC is presented. Combining paleo-temperature estimates from the inferred bases of the zircon PAZ and PRZ, peak-metamorphic temperatures inferred from Raman spectroscopy of carbonaceous material (RSCM), and published peak-metamorphic temperature constraints on the extensional shear zone mylonites near the Mai’iu Fault trace, a minimum slip-parallel, down-dip paleo-temperature gradient of 9.7 ± 2.2°C/km has been estimated for the exhumed Mai’iu Fault plane. Assuming that the modern regional geothermal gradient in the Woodlark Rift is a maximum estimate of that which existed prior to extensional exhumation of the SDMCC, the paleo-temperature gradient was used to estimate an average initial dip of the Mai’iu Fault of ~44° for pre-extensional geothermal gradients ranging between 10 to 20°C/km. Presently dipping 20-22° at the surface, the constraints on the initial dip suggest that the Mai’iu Fault may have been back-rotated by >20° since the onset of extension, consistent with a rolling hinge-style evolution of this continental MCC.</p>

Late Cretaceous upper-crustal thermal structure of the Sevier hinterland: Implications for the geodynamics of the Nevadaplano

Crustal temperature conditions can strongly influence the evolution of deformation during orogenesis. The Sevier hinterland plateau in Nevada and western Utah (“Nevadaplano”) experienced a Late Cretaceous episode of shallow-crustal metamorphism and granitic magmatism. Here, we investigate the thermal history of the Nevadaplano by measuring peak thermal field gradients attained in the upper 10–20 km of the crust along an east-west transect through nine ranges in eastern Nevada and western Utah, by integrating Raman spectroscopy of carbonaceous material thermometry and published conodont alteration indices with reconstructed cross sections. Thermal field gradients of 29 ± 3 °C/km were obtained in the House and Confusion Ranges in westernmost Utah. The Deep Creek, Schell Creek, and Egan Ranges in easternmost Nevada yielded elevated gradients of 49 ± 7 °C/km, 36 ± 3 °C/km, and 32 ± 6 °C/km, respectively. Moving westward, the White Pine, Butte, Pancake, and Fish Creek Ranges exhibit gradients typically between ~20–30 °C/km. The elevated thermal gradients in easternmost Nevada are interpreted to have been attained during ca. 70–90 Ma granitic magmatism and metamorphism and imply possible partial melting at ~18 km depths. Our data are compatible with published interpretations of Late Cretaceous lithospheric mantle delamination under the Sevier hinterland, which triggered lower-crustal anatexis and the resulting rise of granitic melts. The lack of evidence for structures that could have accommodated deep burial of rocks in the nearby Northern Snake Range metamorphic core complex, combined with thermal gradients from adjacent ranges that are ~1.5–3 times higher than those implied by thermobarometry in the Northern Snake Range, further highlights the debate over possible tectonic overpressure in Cordilleran core complexes. Cross-section retro-deformation defines 73.4 ± 4.6 km (76 ± 8%) of extension across eastern Nevada and 15 km of shortening in the Eastern Nevada fold belt.

Metamorphism of metachert from the Southern Alps, New Zealand. A thermodynamic forward modelling study

<p>Scattered, scarce occurrences of garnet- and quartz-rich metamorphic rock, probably derived from Mn- and Fe-rich chert, occur within metamorphosed greywacke sequences worldwide. The metamorphism of such garnetiferous metacherts has not previously been investigated using modern thermodynamic forward modelling techniques due to the lack of appropriate, internally-consistent activity-composition (a–x) models for Mn-bearing minerals. The present study applies thermodynamic forward modelling using the recently-proposed a–x models of White et al. (2014) to investigate the metamorphism of garnetiferous metachert samples from the Southern Alps, New Zealand. Pressure-temperature (P–T) pseudosections are used in combination with results from petrography, element composition mapping using micro X-ray fluorescence (µXRF) and scanning electron microscope (SEM) methods, and garnet composition data from analytical transects by electron probe microanalysis (EPMA), to study metachert metamorphism. All the samples are compositionally layered, so the possibility exists that an input bulk rock composition might not match the effective bulk composition at the site of garnet growth. If a mineral assemblage stability field in a calculated P–T pseudosection matched the mineral assemblage in the rock, this was taken as an initial indication of a permissible input bulk rock composition. In that case, refined constraints on the P–T conditions were sought by comparing calculated and measured garnet compositions. The studied rocks include samples that are carbonate-bearing, which require consideration of the effects of fluid composition in mixed H₂O–CO₂ fluids, as well as a sample in which the garnet is strongly zoned, texturally-complex, and inferred to be of polymetamorphic origin. The effects of element fractionation by that garnet were investigated by recalculating the P–T pseudosection using a new bulk rock composition with the garnet core content removed. In none of the samples did the calculated and observed composition isopleths for the garnet cores match, suggesting that initial garnet nucleation in these Mn-rich rocks was locally controlled. For most samples in which the calculated and observed mineral assemblages matched, successful estimates of the peak metamorphic conditions were obtained. A garnet chert (A12E) from the mylonite zone of the Alpine Fault at Vine Creek, near Hokitika, gave a tight intersection of composition isopleths, indicating peak metamorphic conditions of 510 °C/5.5 kbar, after recalculation to correct for element fractionation by the strongly-zoned garnet. This tight, modern constraint is within error of previously-reported results from traditional geothermobarometry (420–600 °C/5.9–13 kbar) and Raman spectroscopy of carbonaceous material (RSCM T = 556 °C) from nearby sites. A peak metamorphic estimate of 520–550 °C/7–10 kbar was obtained from a dolomite-bearing sample from the garnet zone near Fox Glacier (J34), in good comparison with published temperatures from Raman spectroscopy of carbonaceous material in nearby metagreywacke samples (526–546 °C). The prograde metamorphic P–T path was probably steep, based on growth of the garnet core at ~475535 °C/5–9 kbar. The successful results for these garnet chert samples show that the new a-x models for Mn-bearing minerals extend the range of rock types that are amenable to pseudosection modelling. Results obtained in this study also serve to highlight several possible concerns: a) garnet nucleation and initial growth in very Mn-rich rocks may be subject to local compositional or kinetic controls; b) bulk rock compositions may not always mimic the effective bulk composition; c) the existing a–x models for Mn-bearing minerals and white micas may need refining; and d) some rocks may simply be ill-suited to thermodynamic forward modelling. Items a) and b) may be indicated by the common observation of a mismatch between predicted and measured garnet composition isopleths for garnet cores, and by a mismatch between garnet composition isopleths and the appropriate mineral assemblage field for sample AMS01, from the mylonite zone, Hari Hari, Southern Alps. For item c) every P–T pseudosection calculated using the new a–x models for Mn-bearing minerals showed garnet stable to very low temperatures below 300 °C. In addition, the P–T pseudosection for an oligoclase-zone metachporphyroblasts of Fe-Ti oxides (magnetitert (Sample J36) from Hari Mare stream, Franz Josef - Fox Glacier, indicated that the white mica margarite should be present instead of plagioclase (oligoclase), for a rock in which oligoclase is present and margarite is absent, a problem previously noted elsewhere. Item d) is exemplified by a very garnet-rich ferruginous metachert sample (J35, garnet zone, headwater region, Moeraki River, South Westland) which proved impossible to model successfully due to its complex mineral growth and deformation history. This sample contained multiple generations of carbonate with differing compositions, amphibole (not incorporated for modelling with the new a–x models for Mn-bearing minerals), large e associated with smaller, possibly later-formed ilmenite), and the garnet bands were offset by late deformation. The garnetiferous metachert samples studied here preserve in their textures and compositions clues to their growth mechanism and metamorphic history. The textures in at least two of the samples are consistent with the diffusion controlled nucleation and growth model for garnet. This research has successfully used state of the art thermodynamic modelling techniques in combination with the latest internally consistent a-x models on Mn-rich metachert, for the first time, extracting P–T conditions of the metamorphism of garnetiferous metachert from the Southern Alps.</p>