Potentially toxic elements in ultramafic rocks and soils: A case study from the Voltri Massif (NW Italy)

openHigh concentrations of potentially toxic elements (PTEs) in surface and near-surface environment may be attributed to both anthropogenic sources, including industrial and agricultural activity, and geogenic source, mainly due to natural weathering of rocks. Considering the geogenic sources, ultramafic rocks (e.g., dunite, peridotite, pyroxenite, and serpentinites) are among the most critical from the environmental point of view; in fact, they are characterized by high contents of Cr, Ni, Co, and other PTEs which can have potential harmful impact on ecosystems and human health if released into soils and waters during weathering and pedogenic processes. As a matter of the fact, weathering of ultramafic rock produces ultramafic soil containing high concentration of PTEs, including Cr, Ni, and Co compared to soils derived from non-ultramafic bedrock. Although ultramafic rocks and relative soils cover approximately 1% of the Earth’s surface, they are distributed worldwide and are commonly associated with ophiolite complexes; for this reason, they play an important role in environmental management. The main objective of this PhD thesis was to determinate the mineralogy and the chemistry of PTEs of ultramafic soil profiles from the Voltri Massif and to evaluate how lithological, textural, and structural properties of the ultramafic bedrock with various degree of serpentinization and deformation may affect the PTEs re-distribution and the fate in the soils during pedogenesis, as well as to assess their environmental implications in the ecosystem. The multidisciplinary and multiscale approach, used in this PhD thesis, has allowed to highlight a series of considerations that led to the following conclusions: • In the studied rocks, Cr, Ni, and, subordinately, Co are invariably the PTEs with the highest concentrations; in addition, V, Cu, and Zn are generally found in high concentrations. The main factors controlling the PTEs distribution within the studied ultramafic rocks appeared to be the serpentinization degree and the deformation style and intensity. The main source of the PTEs are spinel-group minerals. Moreover, PTEs-bearing phases are also represented by the other rock-forming minerals (such as serpentines, olivines, pyroxenes, and chlorites) and some accessory phases (e.g., ilmenite and other oxides, sulfides). • The studied ultramafic soil profiles vary in thickness from 35 to 80 cm and are characterized by weakly developed A and C horizons and a very thin O horizon (up to 5-10 cm). In general, in the soils the mineralogy of the skeleton (sandy and silty fractions) is closely related to bedrock mineralogy as expected for primitive A-C soils (in order of abundance: antigorite, chlorite, spinel-group minerals, pyroxenes, authigenic phases, quartz, olivine, and tremolite). The clay fraction is mainly composed by amorphous or low-crystalline Fe-oxyhydroxides, serpentines, smectite and illite/smectite mixed-layer clay, and clinochlore. Cr and Ni values have very variable concentrations over a wide range. Cr and Ni decrease according to serpentinization degree of bedrock. Co, Zn, and Cu do not show a clear correlation with bedrock serpentinization. V increase with the serpentinization of the bedrock. The PTEs concentrations in the studied ultramafic soil profiles are linked both to the primary minerals, inherited by bedrocks (e.g., serpentines, spinel-group minerals, pyroxenes, chlorites), and to their stable authigenic products (Fe-oxyhydroxides and clay minerals). The PTEs leached from the primary minerals is mainly scavenge by goethite, and subordinate by clay. • The results evidence that Cr, Ni, and, Co systematically exceed (up to one order of magnitude) the residential and industrial threshold values (CSC) according to Italian law (D.M. 471/1999; D.Lgs 152/2006) both in rocks and soils. However, combining all my results, I have demonstrated that the critical PTEs concentrations in the studied profiles have a geogenic origin and are linked both to the primary minerals, inherited by bedrocks, and to their stable authigenic products. Considering the high stability of authigenic products in supergenic environment, it is evident that this mineral species are effective and often permanent traps for the most important PTEs of ultramafic soils and bedrocks, thus reducing its bioavailability. A study of this kind that combine the bulk chemistry of outcropping rocks and the relative soil profiles with their geological, structural, mineralogical, and crystallochemical data, can be also a useful tool in environmental concerns to determine the PTEs distribution, to evaluate their potential mobility and bioavailability as well as to discriminate the natural geochemical background from possible source of contamination.openXXXI CICLO - SCIENZE E TECNOLOGIE PER L'AMBIENTE E IL TERRITORIO (STAT) - Scienze della terraCOMODI, PAOLA (Università di Perugia)Fornasaro, Silvi

Primary and authigenic minerals in serpentine soils under temperate climate conditions: source or trap for potentially toxic elements (PTEs)

In this study, we have analysed the mineralogy and the crystal chemistry of serpentine soils from ultramafic rocks of the metaophiolitic Voltri Massif (Liguria, Italy), in order to determine the primary and authigenic mineral species controlling the distribution and the mobility of PTEs during pedogenic processes. These serpentine soils were characterised by PTEs contents commonly exceeding the concentration limits laid down by environmental agencies, particularly for Cr (1200-2500 mg/kg) and Ni (1000-4200 mg/kg). With these hazardous PTEs concentrations, the knowledge of the distribution of PTEs-bearing minerals is of paramount importance for understanding their origin and their fate during the development of serpentine soil profiles and can allow to evaluate their effective bioavailability. All the studied soil profiles were restricted in depth (10-50 cm) and showed a low degree of maturity with weakly developed A-C horizons. Soil samples were subdivided into three aliquots in order to separate the soil skeleton (2 mm-63 \u3bc m) from the silt (63-2 \u3bc m) and clay fraction (<2 \u3bc m). Quantitative mineralogical analyses were performed in all aliquots by using XRPD data collected with synchrotron sources at the MCX beamline (ELETTRA - Synchrotron, Trieste, Italy) and refined with EXP-GUI GSAS software. Trace metals were determined with energy and wavelength electron microscopy. The mineralogy of the coarse and silty fractions was closely related to bedrock mineralogy. The following minerals were detected in decreasing order of abundance: antigorite, chlorite, tremolite, magnetite, Cr-rich spinel, chrysotile, ilmenite, clinopyroxenes, olivine. Allochthonous quartz and albite were always present as minor to trace constituents. The clay fraction was mainly composed by Fe-oxides and -oxyhydroxides (mainly hematite and goethite) with subordinate amounts of mixed-layer clay minerals (chlorite-smectite, chlorite-vermiculite). These authigenic secondary minerals were characterised by poor crystallinity, intimate intergrowths, and fine-scale heterogeneities. PTEs were hosted mainly in the residual primary minerals deriving from the underlying parent material and subordinately in secondary authigenic phases. Cr was mainly contained within spinels (magnetite, Cr-magnetite, ferrichromite, picotite, and hercynite), antigorite, diopside and augite. Nonnegligible amounts of Cr was also present in authigenic hematite (up to 0.1 wt%) and goethite (up to 0.15 wt%). The main Ni-bearing minerals were olivine and antigorite but significant Ni concentration was also detected in authigenic hematite (up to 2.8 wt%) and goethite (up to 4.2 wt%) which thus represented effective traps for Ni leached through mineral weathering to the soils solution. These results are the preliminary step for the evaluation of the role of mineral species in controlling the PTEs mobility during the evolution of serpentine soil profiles. Quantitative mineralogical data will be further used to perform mass balance calculations as well as to interpret and model the results of batch leaching experiments that will be conducted on the different soil fractions

Potentially Toxic Elements in Ultramafic Soils: A Study from Metamorphic Ophiolites of the Voltri Massif (Western Alps, Italy)

Ultramafic soils are characterized by severe edaphic conditions induced by a low content of essential nutrients, an adverse Ca/Mg ratio, a low water-holding capacity, and high contents of geogenic potentially toxic elements (PTEs), in particular Cr, Ni, and Co. These metals commonly exceed the content limits set by environmental agencies and governments, representing serious environmental risks for ecosystems and human health. In alpine environments, ultramafic soils are characterized by modest thickness and poor horizon differentiation. Several studies on ultramafic soils have shown that their properties may be directly related to the characteristics of the parent rocks, but most of these studies deal with soil chemistry, metal availability, isotopic composition, and pedological characterization. The aim of this research is to investigate how much the geotectonic characteristics of ultramafic bedrocks, such as the degree of serpentinization, metamorphic imprint, and deformation, may affect the mineralogical and chemical variations of ultramafic soils, including the occurrence and potential mobility of the PTEs. Using a multiscale and multi-analytical approach, we fully characterize the properties and mineralogical composition of soil profiles with different ultramafic parent rocks, i.e., partially serpentinized peridotite, massive serpentinites, and foliated serpentinites, sampled within the Voltri Massif High Pressure\u2013 Low Temperature (HP\u2013LT) metaophiolite (Western Alps, Italy). Our results, related to soils located at comparable latitude, altitude, landscape position, and pedological environment, outline that the degree of serpentinization, the metamorphic imprint, and the deformation history of the ultramafic parent rocks are key factors influencing soil evolution, mineralogy, and chemistry, as well as PTEs distribution and mobility. Moreover, this study shows that the high content of Cr, Ni, and Co in the studied ultramafic soils has to be considered of geogenic origin and highlights the need for new approaches and methods to obtain indications on the potential contamination of natural or anthropogenic soils

On the possibility of low cost, adherent therapeutic drug monitoring in oncology

A frequent quantification of drugs concentrations in plasma of patients subject to chemotherapy is seldom performed, mostly because the standard methods (Gas or Liquid Chromatography coupled with Mass Spectroscopy) are expensive and time consuming. In this paper we report the approach pursued in one of the research units of the EU project RAMAN4CLINICS to tackle the problem of a low cost, time adherent quantification of drugs used for oncological patients using a Surface Enhanced Raman Scattering (SERS) spectroscopy. More specifically, the issues concerning the repeatability of the nanostructured substrates will be presented and some promising results to increase the selectivity of the measures toward specific drugs will be discussed, with examples concerning one cytotoxic agent, Irinotecan and one kinase inhibitor, Sunitinib

Potentially toxic elements distribution in the serpentinized and deformed ultramafic rocks from the Voltri Massif (NW, Italy)

The aim of the work is to assess the role of local-scale lithological, textural, and structural factors in the distribution of potentially toxic elements (PTEs) in different ultramafic rocks from the high-pressure ophiolitic Voltri Massif (Central Liguria, NW Italy). The results evidenced that Cr (up to 4183 ppm), Ni (up to 3900 ppm), and Co (up to 334 ppm) are invariably the PTEs with the highest concentrations; in addition, V, Cu, and Zn are systematically found in non-negligible amounts. Spinel-group minerals (chromium spinel, ferrian chromite, chromium magnetite, and magnetite) are by far the main potential source of the PTEs. Nevertheless, several PTEs are also present within serpentines, olivines, pyroxenes, chlorites, as well as within accessory phases (e.g., ilmenite and Ni-sulphides) and within authigenic minerals formed in the early stages of rock weathering (cryptocrystalline to amorphous Fe-oxides and -oxyhydroxides). The result obtained allowed to evidence that the main factors controlling the PTEs distribution within the rocks resulted to be the serpentinization degree and the deformation style and intensity which, in turn, strictly control the mineral assemblages and the mineral chemistry

The propylitic alteration in the Ponce Enriquez Gold Mining district, Azuay province, Ecuador: genetic constraints from a mineral chemistry and fluid inclusions study

Wide areas of the Southern sector of Ecuador are characterized by Cretaceous mafic volcanic rocks, pervasively altered by a propylitic mineralogical assemblage with epidote, chlorite, and quartz with minor titanite, illite and prehnite. These propylitically altered rocks host significant gold mineralization in veins, deeply exploited in the last decades. Porphyry Au-Cu deposits also occur in the area. This work focuses on the study of this propylitic alteration to assess the genetic conditions and the relation with the distance from the porphyry system, through the chemical composition of the secondary minerals (particularly trace elements in epidote and chlorite) and fluid inclusion data. The aim is to improve knowledge of the trace element geochemistry of secondary minerals in propylitic alteration and their relationship to the causative porphyry systems. The results of this work indicate that alteration affecting the rocks of the Pallatanga Fm. can be related to the propylitic hydrothermal alteration halo of porphyry copper deposits. Fluid inclusion investigation in quartz veins associated with epidote and chlorite evidenced at least two pulses of hydrothermal fluids characterized by temperature around 345°C for the first one and around 305°C for the second one. The salinity of the fluids is always low (around 1.5 wt% NaClequiv.) suggesting a dominantly meteoric component. Evidence of boiling processes have not been observed. We hypothesize that the hydrothermally altered “green rocks” of the Ponce Enriquez Mining District could be envisaged as the propylitic halo of the Miocene hornblende-bearing Au-Cu porphyry deposits of Gaby-Papa Grande, and discuss the epidote and chlorite trace element composition in this scenario. The results help improving the general knowledge of the propylitically altered rocks in southern Ecuador and add new data for the use of trace element chemistry of epidote and chlorite in mineral exploration elsewhere

Lawsonite-bearing eclogite from a tectonic me\u301lange in the Ligurian Alps: new constraints for the subduction plate-interface evolution

Lawsonite eclogites are rare rocks and have been described from only a few localities in the world. Lawsonite-bearing assemblages are highly unstable and physico-chemical processes linked to exhumation may destroy them; only aggregates interpreted as pseudomorphs after lawsonite could be often recognized. In this paper, we present a detailed structural and petrological study of an area in the northwestern sector of the metaophiolitic high-pressure Voltri Massif (Ligurian Western Alps, Italy). The study area is characterized by a lawsonite-bearing eclogitic metagabbro associated with carbonated serpentinites and glaucophanic metasediments. The metagabbro body reached eclogitic metamorphic peak conditions at T = 465\u2013477 \ub0C and P = 20.9\u201324.4 kbar, with H2 O continuously supplied to the system. H2O under-saturated conditions, with the occurrence of both lawsonite and epidote, characterized the exhumation path. Both the low temperature recorded by the body and the occurrence of variously carbonated serpentinites led us to interpret this area as a portion of the top of the subducted slab, coupled with a \u2018cool\u2019 mantle wedge, where both aqueous fluids and carbonate- rich fluids were present. The occurrence of rocks belonging to different paleogeographic domains (e.g. continent versus ocean) and the multiple deformations recorded by the metagabbro suggest that this area was nearby the slab\u2013mantle interface. This sector was thus affected by a shear regime that acted in a low-viscosity serpentinite channel, bringing these high-pressure rocks back to the surface

Lawsonite-bearing eclogite from a tectonic mélange in the Ligurian Alps: new constraints for the subduction plate-interface evolution

Lawsonite eclogites are rare rocks and have been described from only a few localities in the world. Lawsonite-bearing assemblages are highly unstable and physico-chemical processes linked to exhumation may destroy them; only aggregates interpreted as pseudomorphs after lawsonite could be often recognized. In this paper, we present a detailed structural and petrological study of an area in the northwestern sector of the metaophiolitic high-pressure Voltri Massif (Ligurian Western Alps, Italy). The study area is characterized by a lawsonite-bearing eclogitic metagabbro associated with carbonated serpentinites and glaucophanic metasediments. The metagabbro body reached eclogitic metamorphic peak conditions at T = 465–477 °C and P = 20.9–24.4 kbar, with H2 O continuously supplied to the system. H2O under-saturated conditions, with the occurrence of both lawsonite and epidote, characterized the exhumation path. Both the low temperature recorded by the body and the occurrence of variously carbonated serpentinites led us to interpret this area as a portion of the top of the subducted slab, coupled with a ‘cool’ mantle wedge, where both aqueous fluids and carbonate- rich fluids were present. The occurrence of rocks belonging to different paleogeographic domains (e.g. continent versus ocean) and the multiple deformations recorded by the metagabbro suggest that this area was nearby the slab–mantle interface. This sector was thus affected by a shear regime that acted in a low-viscosity serpentinite channel, bringing these high-pressure rocks back to the surface

Trace and ultratrace elements in spinel subgroup minerals of ultramafic rocks from the Voltri Massif (NW Italy): the influence of microstructure and texture

An innovative multi-analytical approach comprising mineralogical, minero-chemical, and microstructural analyses as well as an indirect machine learning-based statistical method was applied to investigate the mineralogy and the mineral chemistry of spinel subgroup minerals (SSMs) of different ultramafic rocks from the high-pressure metaophiolites of the Voltri Massif (Central Liguria, NW Italy). The study was focused on the correlation between the compositional variations of SSMs and their texture, microstructure, and the degree of serpentinization of the host rock. The SSM occurs with three main textures and microstructures linked to the progressive serpentinization and deformation of ultramafic rocks during the Alpine orogenic events: (i) Cr-spinel porphyroclasts with various degrees of recrystallization (up to magnetite porphyroblasts) within partially serpentinized peridotite and massive serpentinite; (ii) magnetite crystals associated with pseudomorphic and non-pseudomorphic serpentine textures (e.g., mesh, hourglass, ribbon, and interpenetrating textures) in partially serpentinized peridotite and massive serpentinites; and (iii) magnetite crystals re-oriented along the foliations developed in serpentine schist. The chemical composition of SSMs varies systematically within the textures and microstructures. These processes also affected the chemical composition of SSMs, the availability of Mn, Zn, Ni, and Co in solution, and their consequent incorporation in the lattice of chromian spinel due to olivine breakdown, the major repository of these elements in ultramafic rocks. At a general scale, the trace and ultratrace variability is primarily related to the petrologic and tectonic evolution but, at a local scale, also the mineralogical, lithological, structural, and textural features correlated to the degree of serpentinization and/or deformation. These significantly influence the distribution and concentration of trace and ultratrace elements in SSMs. The results of the present work were also confirmed by an innovative indirect statistical method performed through the Weka Machine Learning Workbench

Geodynamic evolution of a subduction plate interface: constraints from the study of lawsonite-bearing eclogite in the mélange of the Voltri Massif (Ligurian Alps, Italy)

Lawsonite (lws) blueschists and eclogites are expected to be the prevailing lithotypes developing during deep subduction of the oceanic crust and should therefore be quite abundant in exhumed subduction complexes. Nevertheless, lws-bearing eclogites have been described only from few localities in the world. Moreover the occurrence of lws- bearing high-pressure metamorphic rocks, associated with eclogite facies rocks, could give important constraints on the coupling mechanisms between different tectonometamorphic slivers in subduction zones and on the interaction with fluids along the subducting slab. Here we present the structural and petrological study of a lws-bearing eclogitic metagabbro, cropping out in the north-western sector of the metaophiolitic Voltri Massif (Ligurian western Alps, Italy). The Voltri Massif occurs at the eastern end of the western Alps and in the study area is characterised by ocean-, continental- and mantle-derived slices of tectonometamorphic units, involved in the Alpine orogenesis. The metagabbro body is a 20-m sized lens and shows a peculiar alternation of Na-amphibole-rich blue and Na- pyroxene-rich green layers, with a mylonitic texture. Both layers include isoclinal intrafoliar folds, which are the oldest recognizable deformation. The metagabbro was affected by a superimposed folding event, testified by isoclinal folds, deforming all the previous structures and causing the alternating green and blue banding. This body is in contact with glaucophane-bearing metasediment and both are interlayered with serpentine schists. Ophicalcites and serpentinites with a variable degree of carbonation (till their complete transformation into listvenites) also crop out in the area. The thermodynamic modelling suggests that the metagabbro body reached metamorphic peak conditions at relatively low temperature (T = 465-477°C, P = 20.9-24.4 kbar), in a setting where H2O was continuously provided to a cold system. H2O under-saturated conditions, with the occurrence of both lawsonite and epidote, characterised the exhumation path. The occurrence of carbonated serpentinites suggests that an intense and long-lasting circulation of CO2-rich fluids affected the area. Further evidence of this circulation comes from an adjoining outcrop (La Pesca locality) some hundreds meters far; we therefore compared the two areas to constrain the timing of CO2 fluid circulation and its role in the lawsonite preservation. The metamorphic peak conditions recorded by the metagabbro body and the occurrence of variously carbonated serpentinites suggest that this area can be interpreted as a portion of the top of the subducted slab, coupled with a “cool” mantle wedge, where both H2O- and CO2-rich fluids were present; in particular we think that this area was nearby the slab-mantle interface. This sector was thus involved in a low viscosity serpentinite channel, where it was affected by a shear regime that brought these high-pressure rocks back to the surface