Land use management in mountainous areas: combining ground-based and EO (Earth Observation) data to investigate the shallow landsliding susceptibility in the Duron valley (Trento, Italy).

Throughout the alpine domain, shallow landslides represent a serious geologic hazard, often causing severe damages to infrastructures, private properties, natural resources and in the most catastrophic events, threatening human lives. Landslides are a major factor of landscape evolution in mountainous and hilly regions and represent a critical issue for mountainous land management, since they cause loss of pastoral lands. In several alpine contexts, shallow landsliding distribution is strictly connected to the presence and condition of vegetation on the slopes. With the aid of high-resolution satellite images, it's possible to divide automatically the mountainous territory in land cover classes, which contribute with different magnitude to the stability of the slopes. The aim of this research is to combine EO (Earth Observation) land cover maps with ground-based measurements of the land cover properties. In order to achieve this goal, a new procedure has been developed to automatically detect grass mantle degradation patterns from satellite images. Moreover, innovative surveying techniques and instruments are tested to measure in situ the shear strength of grass mantle and the geomechanical and geotechnical properties of these alpine soils. Shallow landsliding distribution is assessed with the aid of physically based models, which use the EO-based map to distribute the resistance parameters across the landscape.

Uso del gnss per applicazioni di monitoraggio glaciologico in Antartide

Studio relativo alle correlazioni tra sisma e icestream nella zona antartica della terra Vittoria. Si presentano inoltre due studi approfonditi relativi a due reti gps presenti nei pressi di Talos Dome e Dome Concordia. Inoltre è presente anche una descrizione completa del sistema gps e di tutti gli strumenti utilizzati in campagna

Analisi fluidodinamica di reattori utilizzati per la produzione di biogas

Il lavoro riguarda la caratterizzazione fluidodinamica di un reattore agitato meccanicamente utilizzato per la produzione di biogas. Lo studio è stato possibile attraverso l’impiego della PIV (Particle Image Velocimetry), tecnica di diagnostica ottica non invasiva adatta a fornire misure quantitative dei campi di velocità delle fasi all’interno del reattore. La caratterizzazione è stata preceduta da una fase di messa a punto della tecnica, in modo da definire principalmente l’influenza dello spessore del fascio laser e dell’intervallo di tempo tra gli impulsi laser sui campi di moto ottenuti. In seguito, il reattore è stato esaminato in due configurazioni: con albero in posizione centrata e con albero in posizione eccentrica. Entrambe le geometrie sono state inoltre analizzate in condizione monofase e solido-liquido. Le prove in monofase con albero centrato hanno permesso di identificare un particolare regime transitorio del fluido nei primi minuti dopo la messa in funzione del sistema di agitazione, caratterizzato da una buona efficienza di miscelazione in tutta la sezione di analisi. In condizioni di regime stazionario, dopo circa 1 ora di agitazione, è stato invece osservato che il fluido nella zona vicino alla parete è essenzialmente stagnante. Sempre con albero centrato, le acquisizioni in condizione bifase hanno permesso di osservare la forte influenza che la presenza di particelle di solido ha sui campi di moto della fase liquida. Per l’assetto con albero in posizione eccentrica, in condizione monofase e regime di moto stazionario, è stata evidenziata una significativa influenza del livello di liquido all’interno del reattore sui campi di moto ottenuti: aumentando il livello scalato rispetto a quello usato nella pratica industriale è stato osservato un miglioramento dell’efficienza di miscelazione grazie al maggior lavoro svolto dal sistema di agitazione. In questa configurazione, inoltre, è stato effettuato un confronto tra i campi di moto indotti da due tipologie di giranti aventi stesso diametro, ma diversa geometria. Passando alla condizione bifase con albero eccentrico, i risultati hanno evidenziato la forte asimmetria del reattore: è stato evidenziato, infatti, come il sistema raggiunga regimi stazionari differenti a seconda delle velocità di rotazione e delle condizioni adottate per il raggiungimento della stabilità. Grazie alle prove su piani orizzontali del reattore in configurazione eccentrica e condizioni bifase, è stato concluso che i sistemi in uso inducano un campo di moto prettamente tangenziale, non ottimizzato però per la sospensione della fase solida necessaria in questa tipologia di processi.

Characterization of fold-related fractures in the carbonate rocks of the Cingoli anticline, northern Apennines, Italy

Thrust fault-related folds in carbonate rocks are characterized by deformation accommodated by different structures, such as joints, faults, pressure solution seams, and deformation bands. Defining the development of fracture systems related to the folding process is significant both for theoretical and practical purposes. Fracture systems are useful constrains in order to understand the kinematical evolution of the fold. Furthermore, understanding the relationships between folding and fracturing provides a noteworthy contribution for reconstructing the geodynamic and the structural evolution of the studied area. Moreover, as fold-related fractures influence fluid flow through rocks, fracture systems are relevant for energy production (geothermal studies, methane and CO2 , storage and hydrocarbon exploration), environmental and social issues (pollutant distribution, aquifer characterization). The PhD project shows results of a study carried out in a multilayer carbonate anticline characterized by different mechanical properties. The aim of this study is to understand the factors which influence the fracture formation and to define their temporal sequence during the folding process. The studied are is located in the Cingoli anticline (Northern Apennines), which is characterized by a pelagic multilayer characterized by sequences with different mechanical stratigraphies. A multi-scale analysis has been made in several outcrops located in different structural positions. This project shows that the conceptual sketches proposed in literature and the strain distribution models outline well the geometrical orientation of most of the set of fractures observed in the Cingoli anticline. On the other hand, the present work suggests the relevance of the mechanical stratigraphy in particular controlling the type of fractures formed (e.g. pressure solution seams, joints or shear fractures) and their subsequent evolution. Through a multi-scale analysis, and on the basis of the temporal relationship between fracture sets and their orientation respect layering, I also suggest a conceptual model for fracture systems formation.

Il risparmio delle risorse alla scala abitativa e di insediamento. Tecnologie non convenzionali e valutazione ambientale attraverso metodologia LCA.

Nel corso del mio lavoro di ricerca mi sono occupata di identificare strategie che permettano il risparmio delle risorse a livello edilizio e di approfondire un metodo per la valutazione ambientale di tali strategie. La convinzione di fondo è che bisogna uscire da una visione antropocentrica in cui tutto ciò che ci circonda è merce e materiale a disposizione dell’uomo, per entrare in una nuova era di equilibrio tra le risorse della terra e le attività che l’uomo esercita sul pianeta. Ho quindi affrontato il tema dell’edilizia responsabile approfondendo l’ambito delle costruzioni in balle di paglia e terra. Sono convinta che l’edilizia industriale abbia un futuro molto breve davanti a sé e lascerà inevitabilmente spazio a tecniche non convenzionali che coinvolgono materiali di semplice reperimento e posa in opera. Sono altresì convinta che il solo utilizzo di materiali naturali non sia garanzia di danni ridotti sull’ecosistema. Allo stesso tempo ritengo che una mera certificazione energetica non sia sinonimo di sostenibilità. Per questo motivo ho valutato le tecnologie non convenzionali con approccio LCA (Life Cycle Assessment), approfondendo gli impatti legati alla produzione, ai trasporti degli stessi, alla tipologia di messa in opera, e ai loro possibili scenari di fine vita. Inoltre ho approfondito il metodo di calcolo dei danni IMPACT, identificando una carenza nel sistema, che non prevede una categoria di danno legata alle modifiche delle condizioni idrogeologiche del terreno. La ricerca si è svolta attraverso attività pratiche e sperimentali in cantieri di edilizia non convenzionale e attività di ricerca e studio sull’LCA presso l’Enea di Bologna (Ing. Paolo Neri).

Speleogenesis and secondary cave minerals in quartz-sandstone and quartzite environment

The main objective of this research is to improve the comprehension of the processes controlling the formation of caves and karst-like morphologies in quartz-rich lithologies (more than 90% quartz), like quartz-sandstones and metamorphic quartzites. In the scientific community the processes actually most retained to be responsible of these formations are explained in the “Arenisation Theory”. This implies a slow but pervasive dissolution of the quartz grain/mineral boundaries increasing the general porosity until the rock becomes incohesive and can be easily eroded by running waters. The loose sands produced by the weathering processes are then evacuated to the surface through processes of piping due to the infiltration of waters from the fracture network or the bedding planes. To deal with these problems we adopted a multidisciplinary approach through the exploration and the study of several cave systems in different tepuis. The first step was to build a theoretical model of the arenisation process, considering the most recent knowledge about the dissolution kinetics of quartz, the intergranular/grain boundaries diffusion processes, the primary diffusion porosity, in the simplified conditions of an open fracture crossed by a continuous flow of undersatured water. The results of the model were then compared with the world’s widest dataset (more than 150 analyses) of water geochemistry collected till now on the tepui, in superficial and cave settings. All these studies allowed verifying the importance and the effectiveness of the arenisation process that is confirmed to be the main process responsible of the primary formation of these caves and of the karst-like superficial morphologies. The numerical modelling and the field observations allowed evaluating a possible age of the cave systems around 20-30 million of years.

Water footprint e modalità di risparmio idrico nell'industria agroalimentare

Ci rendiamo conto del valore dell’acqua solamente quando scarseggia. Fino ad oggi il problema poteva sembrare limitato ai Paesi più poveri di tale risorsa, ma le cose potrebbero cambiare perché l’acqua “di qualità” – ossia dolce e non inquinata – rappresenta solo una minima percentuale delle nostre riserve. E noi ne usiamo sempre di più: sia perché aumenta la popolazione della Terra, sia perché il maggiore benessere raggiunto da molti Paesi spinge la popolazione a consumare (e sprecare) più acqua. Un consumo che va esaminato non solo in termini “reali” (calcolando le quantità che si usano per la cura personale, per la cucina o per la pulizia della casa), ma anche “virtuali” (in termini di impronta idrica), stimando cioè tutta l’acqua che è stata utilizzata lungo l’intero ciclo di vita di un qualunque prodotto o servizio acquistato. Basti pensare che se si modificasse il proprio stile alimentare, passando ad esempio a prediligere una dieta più ricca di frutta, verdura e cereali, limitando la quantità di proteine animali, sarebbe possibile ridurre anche in modo significativo i consumi di acqua “virtuale”. 
Quindi, se da un lato la domanda cresce e dall’altro le risorse si riducono, anche per colpa dell’inquinamento e del cambiamento climatico, è sicuro che il valore economico dell’acqua aumenterà e le disuguaglianze, già oggi presenti, potranno portare nuovi attriti. Per questi motivi diventa fondamentale il concetto di Water Footprint, ossia l’analisi delle quantità di acqua utilizzata all’interno di tutta la filiera che porta alla produzione di un prodotto finito. Visto il mio corso di studi in ingegneria gestionale, ho deciso di concentrarmi principalmente sul concetto di Water Footprint all’interno dell’ambito industriale, analizzando in particolare il caso di un’azienda dell’Emilia Romagna. Ho scelto questo argomento perché sono sempre stato interessato all’ambiente e alla sua salvaguardia. Trattare nella tesi tale tema mi è sembrato utile per approfondire e diffondere concetti come quelli dell’impronta idrica e dell’acqua virtuale che, pur discussi a livello internazionale ormai da anni, tardano ancora ad essere affrontati in maniera ampia in Italia, che è il terzo Paese importatore netto di acqua virtuale al mondo.

Nanoscale surface properties and interaction with fundamental biomolecules of chlorite and phlogopite

The surface properties of minerals have important implications in geology, environment, industry and biotechnology and for certain aspects in the research on the origin of life. This research project aims to widen the knowledge on the nanoscale surface properties of chlorite and phlogopite by means of advanced methodologies, and also to investigate the interaction of fundamental biomolecules, such as nucleotides, RNA, DNA and amino acid glycine with the surface of the selected phyllosilicates. Multiple advanced and complex experimental approaches based on scanning probe microscopy and spatially resolved spectroscopy were used and in some cases specifically developed. The results demonstrate that chlorite exposes at the surface atomically flat terraces with 0.5 nm steps typically generated by the fragmentation of the octahedral sheet of the interlayer (brucitic-type). This fragmentation at the nanoscale generates a high anisotropy and inhomogeneity with surface type and isomorphous cationic substitutions determining variations of the effective surface potential difference, ranging between 50-100 mV and 400-500 mV, when measured in air, between the TOT surface and the interlayer brucitic sheet. The surface potential was ascribed to be the driving force of the observed high affinity of the surface with the fundamental biomolecules, like single molecules of nucleotides, DNA, RNA and amino acids. Phlogopite was also observed to present an extended atomically flat surface, featuring negative surface potential values of some hundreds of millivolts and no significant local variations. Phlogopite surface was sometimes observed to present curvature features that may be ascribed to local substitutions of the interlayer cations or the presence of a crystal lattice mismatch or structural defects, such as stacking faults or dislocation loops. Surface chemistry was found similar to the bulk. The study of the interaction with nucleotides and glycine revealed a lower affinity with respect to the brucite-like surface of chlorite.

Techniques for Lagrangian modelling of dispersion in geophysical flows

Basic concepts and definitions relative to Lagrangian Particle Dispersion Models (LPDMs)for the description of turbulent dispersion are introduced. The study focusses on LPDMs that use as input, for the large scale motion, fields produced by Eulerian models, with the small scale motions described by Lagrangian Stochastic Models (LSMs). The data of two different dynamical model have been used: a Large Eddy Simulation (LES) and a General Circulation Model (GCM). After reviewing the small scale closure adopted by the Eulerian model, the development and implementation of appropriate LSMs is outlined. The basic requirement of every LPDM used in this work is its fullfillment of the Well Mixed Condition (WMC). For the dispersion description in the GCM domain, a stochastic model of Markov order 0, consistent with the eddy-viscosity closure of the dynamical model, is implemented. A LSM of Markov order 1, more suitable for shorter timescales, has been implemented for the description of the unresolved motion of the LES fields. Different assumptions on the small scale correlation time are made. Tests of the LSM on GCM fields suggest that the use of an interpolation algorithm able to maintain an analytical consistency between the diffusion coefficient and its derivative is mandatory if the model has to satisfy the WMC. Also a dynamical time step selection scheme based on the diffusion coefficient shape is introduced, and the criteria for the integration step selection are discussed. Absolute and relative dispersion experiments are made with various unresolved motion settings for the LSM on LES data, and the results are compared with laboratory data. The study shows that the unresolved turbulence parameterization has a negligible influence on the absolute dispersion, while it affects the contribution of the relative dispersion and meandering to absolute dispersion, as well as the Lagrangian correlation.

Origin and variability of PM10 and atmospheric radiotracers at the WMO-GAW station of Mt. Cimone (1998-2011) and in the central Po Valley

Particulate matter is one of the main atmospheric pollutants, with a great chemical-environmental relevance. Improving knowledge of the sources of particulate matter and of their apportionment is needed to handle and fulfill the legislation regarding this pollutant, to support further development of air policy as well as air pollution management. Various instruments have been used to understand the sources of particulate matter and atmospheric radiotracers at the site of Mt. Cimone (44.18° N, 10.7° E, 2165 m asl), hosting a global WMO-GAW station. Thanks to its characteristics, this location is suitable investigate the regional and long-range transport of polluted air masses on the background Southern-Europe free-troposphere. In particular, PM10 data sampled at the station in the period 1998-2011 were analyzed in the framework of the main meteorological and territorial features. A receptor model based on back trajectories was applied to study the source regions of particulate matter. Simultaneous measurements of atmospheric radionuclides Pb-210 and Be-7 acquired together with PM10 have also been analysed to acquire a better understanding of vertical and horizontal transports able to affect atmospheric composition. Seasonal variations of atmospheric radiotracers have been studied both analysing the long-term time series acquired at the measurement site as well as by means of a state-of-the-art global 3-D chemistry and transport model. Advection patterns characterizing the circulation at the site have been identified by means of clusters of back-trajectories. Finally, the results of a source apportionment study of particulate matter carried on in a midsize town of the Po Valley (actually recognised as one of the most polluted European regions) are reported. An approach exploiting different techniques, and in particular different kinds of models, successfully achieved a characterization of the processes/sources of particulate matter at the two sites, and of atmospheric radiotracers at the site of Mt. Cimone.

Late Quaternary geological evolution of the Montenegro and Northern Albania continental margins

The object of this work has been the analysis of natural processes controlling the geological evolution of the Montenegro and Northern Albania Continental Margin (MACM) during the Late Quaternary. These include the modern sediment dispersal system and oceanographic regime, the building and shaping of the shelf margin at the scale of 100 kyr and relative to the most recent transition between glacial and interglacial periods. The analysis of the new data shows that the MACM is a shelf-slope system formed by a suite of physiographic elements, including: an inner and an outer continental shelf, separated by two tectonically-controlled morphological highs; a lobated drowned mid-shelf paleodelta, formed during the last sea level fall and low stand; an upper continental slope, affected by gravity-driven instability and a system of extensional faults with surficial displacement, featuring an orientation coherent with the regional tectonics. The stratigraphic study of the MACM shows a clear correspondence between the Late Pleistocene/Holocene mud-wedge and the low reflectivity sectors of the inner shelf. Conversely, most of the outer shelf and part of the continental slope expose deposits from the last sea level low stand, featuring a general sediment starving condition or the presence of a thin postglacial sediments cover. The MACM shows uplift in correspondence of the Kotor and Bar ridges, and subsidence in the outer shelf and upper slope sectors. In fact, seaward of these tectonic ridges, the sparker seismic profile show the presence of four well-defined seismo-stratigraphic sequences, interpreted as forced regression deposits, formed during the last four main glacial phases. In this way, the MACM records the 100 kyr scale sea level fluctuations on its seismo-stratigraphic architecture over the last 350 kyr. Over such time range, through the identification of the paleoshoreline deposits, we estimated an average subsidence rate of about 1.2 mm/yr.

Transform Tectonics and Non-Volcanic Oceanic Islands

Oceanic islands can be divided, according to their origin, in volcanic and tectonic. Volcanic islands are due to excess volcanism. Tectonic islands are mainly formed due to vertical tectonic motions of blocks of oceanic lithosphere along transverse ridges flanking transform faults at slow and ultraslow mid-ocean ridges. Vertical tectonic motions are due to a reorganization of the geometry of the transform plate boundary, with the transition from a transcurrent tectonics to a transtensive and/or transpressive tectonics, with the formation of the transverse ridges. Tectonic islands can be located also at the ridge–transform intersection: in this case the uplift is due by the movement of the long-lived detachment faults located along the flanks of the mid-ocean ridges. The "Vema" paleoisland (equatorial Atlantic) is at the summit of the southern transverse ridge of the Vema transform. It is now 450 m bsl and it is capped by a carbonate platform 500 m-thick, dated by 87Sr/86Sr at 10 Ma. Three tectonic paleoislands are on the summit of the transverse ridge flanking the Romanche megatrasform (equatorial Atlantic). They are now about 1,000 m bsl and they are formed by 300 m-thick carbonate platforms dated by 87Sr/86Sr, between 11 and 6 Ma. The tectonic paleoisland “Atlantis Bank" is located in the South-Western Indian Ridge, along the Atlantis II transform, and it is today 700 m bsl. The only modern example of oceanic tectonics island is the St. Paul Rocks (equatorial Atlantic), located along the St. Paul transform. This archipelago is the top of a peridotitic massif that it is now a left overstep undergoing transpression. Oceanic volcanic islands are characterized by rapid growth and subsequent thermal subsidence and drowning; in contrast, oceanic tectonic islands may have one or more stages of emersion related to vertical tectonic events along the large oceanic fracture zones.

Ab initio quantum mechanical investigation of structural and chemical-physical properties of selected minerals for minero-petrological, structural ceramic and biomaterial applications

The purpose of this thesis is the atomic-scale simulation of the crystal-chemical and physical (phonon, energetic) properties of some strategically important minerals for structural ceramics, biomedical and petrological applications. These properties affect the thermodynamic stability and rule the mineral-environment interface phenomena, with important economical, (bio)technological, petrological and environmental implications. The minerals of interest belong to the family of phyllosilicates (talc, pyrophyllite and muscovite) and apatite (OHAp), chosen for their importance in industrial and biomedical applications (structural ceramics) and petrophysics. In this thesis work we have applicated quantum mechanics methods, formulas and knowledge to the resolution of mineralogical problems ("Quantum Mineralogy”). The chosen theoretical approach is the Density Functional Theory (DFT), along with periodic boundary conditions to limit the portion of the mineral in analysis to the crystallographic cell and the hybrid functional B3LYP. The crystalline orbitals were simulated by linear combination of Gaussian functions (GTO). The dispersive forces, which are important for the structural determination of phyllosilicates and not properly con-sidered in pure DFT method, have been included by means of a semi-empirical correction. The phonon and the mechanical properties were also calculated. The equation of state, both in athermal conditions and in a wide temperature range, has been obtained by means of variations in the volume of the cell and quasi-harmonic approximation. Some thermo-chemical properties of the minerals (isochoric and isobaric thermal capacity) were calculated, because of their considerable applicative importance. For the first time three-dimensional charts related to these properties at different pressures and temperatures were provided. The hydroxylapatite has been studied from the standpoint of structural and phonon properties for its biotechnological role. In fact, biological apatite represents the inorganic phase of vertebrate hard tissues. Numerous carbonated (hydroxyl)apatite structures were modelled by QM to cover the broadest spectrum of possible biological structural variations to fulfil bioceramics applications.

Paleosol-based stratigraphy of late Quaternary deposits from the Po basin, between Bologna and the Po river (Northern Italy)

Stratigraphic studies carried out over the last decades in Italy and elsewhere testify a growing interest in Quaternary deposits and in the influence of climate change on their architecture. The subsurface of the Po Plain, in its topmost portion, is made up of alluvial deposits organized in depositional cycles at different scales. This PhD thesis provides millennial-scale stratigraphic reconstruction of the Late Pleistocene-Holocene deposits beneath the southern Po Plain, based on basin-scale correlation of laterally-extensive buried soil horizons. Far from the aim of characterizing palaeosols from a mineralogical and geochemical point of view, we focused on the physical and stratigraphic significance of these horizons. In the Bologna urban area, which hosts an abundance of stratigraphic data, the correlation between seventeen continuously-cored boreholes led to the identification of five vertically-stacked palaeosol-bounded sequences within the 14C time window. In a wide portion of the alluvial plain north of Bologna, far away from the Apenninic margin and from the Po River, where subsurface stratigraphic architecture is dominated by markedly lenticular sediment bodies, palaeosols revealed to be the only stratigraphic marker of remarkable lateral continuity. These horizons are characterized by peculiar resistance values, which make them easily identifiable via pocket penetration tests. Palaeosols reveal specific geometric relationships with the associated alluvial facies associations, allowing reliable estimates of soil development as a function of alluvial dynamics. With the aid of sixty new radiocarbon dates, a reliable age attribution and likely time intervals of exposure were assigned to each palaeosol. Vertically-stacked palaeosols delimitate short-term depositional cycles, likely related to the major episodes of climatic change of the last 40 ky. Through integration of stratigraphic data with 750 archaeological reports from the Bologna area, the impact of human settlements on depositional and pedogenic processes during the late Holocene was investigated.

A 300 million year-long history. The metamorphic evolution of the Northern Apennine Variscan basement

The Variscan basement of Northern Apennines (Northern Italy) is a polymetamorphic portion of continental crust. This thesis investigated the metamorphic history of this basement occurring in the Cerreto Pass, in the Pontremoli well, and in the Pisani Mountains. The study comprised fieldwork, petrography and microstructural analysis, determination of the bulk rock and mineral composition, thermodynamic modelling, conventional geothermobarometry, monazite chemical dating and Ar/Ar dating of muscovite. The reconstructed metamorphic evolution of the selected samples allowed to define a long-lasting metamorphic history straddling the Variscan and Alpine orogenesis. Some general petrological issues generally found in low- to medium-grade metapelites were also tackled: (i) With middle-grade micaschist it is possible to reconstruct a complete P-T-D path by combining microstructural analysis and thermodynamic modelling. Prekinematic white mica may preserve Mg-rich cores related to the pre-peak stage. Mn-poor garnet rim records the peak metamorphism. Na-rich mylonitic white mica, the XFe of chlorite and the late paragenesis may constrain the retrograde stage. (ii) Metapelites may contain coronitic microstructures of apatite + Th-silicate, allanite and epidote around unstable monazite grains. Chemistry and microstructure of Th-rich monazite relics surrounded by this coronitic microstructure may suggest that monazite mineral was inherited and underwent partial dissolution and fluid-aided replacement by REE-accessory minerals at 500-600°C and 5-7 kbar. (iii) Fish-shaped white mica is not always a (prekinematic) mica-fish. Observed at high-magnification BSE images it may consist of several white mica formed during a mylonitic stage. Hence, the asymmetric foliation boudin is a suitable microstructure to obtain geochronological information about the shearing stage. (iv) Thermodynamic modelling of a hematite-rich metasedimentary rock fails to reproduce the observed mineral compositions when the bulk Fe2O3 is neglected or determined through titration. The mismatch between observed and computed mineral compositions and assemblage is resolved by tuning the effective ferric iron content by P-XFe2O3 diagrams.