Influence of pore system characteristics on limestone vulnerability: a laboratory study

Hyblean limestone of Oligo-Miocene age was widely used as a construction material in the architectural heritage of Eastern Sicily (Italy). Among them, the so-called Pietra Bianca di Melilli (Melilli limestone) and Calcare di Siracusa (Syracuse limestone) were prized for their attractive appearance, ease of quarrying, and workability. Syracuse limestone shows general weathering, whereas Melilli limestone is better preserved, and only differential erosion or superficial exfoliation can be detected in monuments. The cause of the different behavior of these two limestones was investigated from the petrographic and petrophysical points of view. The saturation coefficient is higher in Melilli limestone, and ultrasound measurements indicate that it is less compact than Syracuse limestone, so that Melilli limestone could deteriorate more easily than Syracuse limestone. However, pore interconnections and the size of very small pores play the main role in the durability of both materials. The “irregularity” of the Syracuse pore system and its greater number of micropores hinder water flow through the exterior, promote stress in pore structure, and favor the development of scaling, as confirmed by salt crystallization tests. In Melilli limestone, the low concentration of micropores and fast water evaporation allow solutions to reach the surface more easily, resulting in less damaging efflorescence.     

Glacial conglomerates of the Appalachian Plateau,New York

Three generations of Quaternary conglomerates formed by cementation of glacial gravels are found in drift of the Appalachian Plateau in south-central New York. Postglacial conglomerates have been locally cemented by carbonate minerals within limestone-bearing (erratic-rich) gravels of Late Wisconsin (Woodfordian) age. Conglomerates cemented during the Mid-Wisconsin interstade occur as numerous fragments in erratic-rich Late Wisconsin drift, and as a single in situ mound near Syracuse. Mid-Wisconsin conglomerate contains fragments of a still older conglomerate believed to be of possible pre-Wisconsin (Sangamon) age. Both postglacial and Mid-Wisconsin conglomerates were cemented in the same manner, as a result of diagenetic processes in the vadose zones of limestone-bearing terraces. Information gleaned from conglomerate fragments indicates that Early Wisconsin drift was similar to Late Wisconsin drift; the Early and Late Wisconsin glaciations and deglaciations of the plateau probably proceeded in much the same fashion.     

Environmental geology of ancient Greek cities

Man-environment relations in the ancient Greek world, as now, were complex interactions. To understand them, we need to study a range of physical features and man's impact on the setting. The underlying geological reality of this area is karst, which is widely distributed, dominating Greece, the southern half of Turkey, and southern Italy and Sicily, where the Greco-Roman cities that we study were located. Year-round water from karst springs was important because of scarce rainfall, intense evaporation, and infertile soil—none under human control. Examples from the Greek mainland (Corinth), an Aegean island (Rhodes), Turkey (Priene), and Sicily (Syracuse) are selected and described to suggest the way that karst water potential played an important role in site selection and development. A wider look at criteria for urban location and a new classification of urban patterns help to revise conventional understandings of these ancient cities. In conclusion, some modern findings about the interaction between city and setting suggest new research agendas for geologists and engineers, ancient historians and archaeologists, and water policy makers—preferrably working together.     

The geographic distribution of metals in urban soils: the case of Syracuse,NY

A paucity of literature currently exists pertaining to the high-resolution geographic distribution of metal contaminants across urban areas. Thousands of soil samples were collected across Syracuse, NY to secure empirical evidence about such geographic distributions. Metal measurements were made with XRF technology, with quality assessments based upon replicate samples as well as ICP technology summarized here. Both metal covariations and their spatial structure are described, followed by mapping of selected metal measurements based upon sample points, as well as census block group and census tract aggregates. A simple comparison is presented between certain of these empirical results and a selected non-urban landscape (a river floodplain). Finally, implications drawn from the empirical evidence presented include covariation assessments with selected census data that serve as surrogates for poverty.     

Origin of halite brine in the Onondaga Trough near Syracuse,New York State,USA: modeling geochemistry and variable-density flow

Halite brine (saturation ranging from 45 to 80%) lies within glacial sediments that fill the Onondaga Trough, a bedrock valley deepened by Pleistocene glaciation near Syracuse, New York State, USA. The most concentrated brine occupies the northern end of the trough, about 10 km downgradient of the northern limit of halite beds in the Silurian Salina Group, the assumed source of salt. The chemical composition of the brine and its radiocarbon age suggest that the brine originally formed about 16,700  years ago through dissolution of halite by glacial melt water and later mixed with saline bedrock water. Two hypotheses regarding the formation of the brine pool were tested through variable-density flow simulations using SEAWAT. Simulation results supported the first hypothesis that the brine pool was derived from a source in the glacial sediments and then migrated to its current position, where it has persisted for over 16,000  years. A second hypothesis that the brine pool formed through steady accumulation of brine from upward flow of a source in the underlying bedrock was not supported by simulation results, because the simulated age distribution was much younger than the age estimated from geochemical modeling.     

Building stone employed in the historical monuments of Eastern Sicily (Italy). An example: the ancient city centre of Catania

An archaeometric study of the stone materials employed in the Late Baroque historical monuments of the ancient city centre of Catania was carried out. Lithological maps of a selection of monuments, transferred to a digital format, revealed that the stone materials are both magmatic and sedimentary rocks, the colours of which are matched in a peculiar type of bichromy. Particular attention focused on sedimentary rocks, which consist of various types of limestone quarried near the city of Syracuse (Hyblean Plateau, south-eastern Sicily). Carbonate rocks were characterised in terms of mineralogy, petrography and geochemistry, by studying rock samples from both monuments and historical extraction sites. Results showed that, although only one name was historically attributed to the above lithotypes (i.e. “Pietra di Siracusa‘’), they were quarried from many locations and, as they belong to various geological formations, they therefore exhibit great variety. In order to examine the durability of Hyblean limestones employed in works of cultural heritage interest, salt crystallisation tests were carried out according to standard procedure norms (UNI EN 12370 (1999) Determination of resistance to crystallisation of salts, 6p). Results are consistent with the forms of deterioration observed in the monuments, and highlight the close relationship between textural characteristics and damage. Our purpose is to provide a basic tool, which may be useful both for conserving monuments of cultural heritage and for their restoration.     

Citywide distribution of lead and other element in soils and indoor dusts in Syracuse,NY

Associations between Pb, Zn, Fe and Mn in soils and indoor dusts in urban Syracuse, NY have been investigated at different levels of spatial aggregation. The concentrations of these elements of interest (EOI) in 3566 soil samples were mapped across the city to investigate variations in concentration potentially associated with specific city locations. Indoor floor dust loadings for the EOI determined at 433 residences were mapped in a similar fashion. Pearson product correlation coefficients at different levels of soil sample aggregation (individual sampling points, block group averages, and census tract (CT) averages), consistently demonstrated a strong correlation between soil Pb and Zn concentrations. Correlations between Pb and both Fe and Mn soil concentrations were also significant. However, the correlation between the Fe and Mn floor dust loadings was much stronger than that for soil, as were the correlations between the Pb and both the Fe and Mn dust loadings. The correlation between the Fe and Zn floor dust loadings was far less significant. Surprisingly, most of the correlations between the paired EOI in the dusts and soils at the individual homes were mostly not statistically significant. The two correlations of any significance, and these were between the Pb in soil and the Pb in the dust, and between Pb in dust and Zn in soil.     

The nature of deformation within the outer limits of the central appalachian foreland fold and thrust belt in New York state

Residual strain, a self-equilibrating recoverable strain that remains in rocks even after external forces and moments are removed, is found NNW of the folded Appalachian plateau in the Devonian Onondaga limestone and the Silurian Lockport dolomite and Grimsby sandstone of western New York. This residual strain is manifest upon overcoring by a NNW directed maximum expansion of the limestone and sandstone and a random maximum expansion of the dolomite. Strains, recorded with strain gauge rosettes bonded to outcrops, are as high as 200 με (microstrain). Double overcoring of the sandstone and dolomite relieves smaller strains of the same orientation as the initial overcore. X-ray analysis of the Grimsby sandstone shows that the elastic residual strain locked in quartz grains is characterized by a NE principal extension of 60 με and a 10–30 με NW principal compression oriented 30° counterclockwise from the NNW compression indicated by overcoring. Sonic velocity tests on samples in the lab indicate that Grimsby sandstone is anisotropic with a NNW maximum P-wave velocity of 4.05 km/sec. This anisotropy correlates with the residual strain in Grimsby sandstone. Mechanical twinning of calcite within both the Onondaga limestone and Grimsby sandstone indicates that the rock contains a permanent compressive strain of less than 2% in the NNW direction. The permanent strain becomes progressively smaller in a series of samples from Syracuse to Buffalo, New York. The development of solution cleavage in Onondaga limestone also indicates a NNW compression. No evidence of permanent strain was found in the dolomite. The NNW compression of the limestone and sandstone is normal to the fold axes of the Appalachian foreland fold and thrust belt. This geometric relationship indicates that the residual strain well beyond the outermost Appalachian folds was caused by the same tectonic stresses responsible for folding, the Appalachians during the late Paleozoic. Strain within the Appalachian plateau below the Silurian salt horizon suggests either the presence of a second décollement in, perhaps, Ordovician shales or a general NNW shortening of the crust under the Appalachian plateau.     

Alpine metamorphic evolution of Ligurian Alps (North-West Italy): chemography and petrological constraints inferred from metamorphic climax assemblages

The up-to-date petrological and microtextural information on the Ligurian Alps indicates that the metamorphic rocks from the oceanic lithosphere and the paleo-European continental margin underwent an alpine-type metamorphic evolution characterized by low dT/dP gradients. In particular, rocks from the Ligurian-Piedmontese oceanic lithosphere underwent an alpine metamorphism typical of alpine-type blueschist rocks. The distribution of the alpine metamorphic facies in paleo-European continental margin is closely related to the structural position of the different tectonic units. The prograde evolution frequently preserves paragenetic and textural relics of the earlier parageneses. If relics of the earlier parageneses are preserved, the rock exhibits continuous prograde reactions confirmed by strong compositional zoning of the metamorphic minerals. Therefore, these reactions lead to chemical and microtextural equilibrium relations, between the minerals, in limited domains of the rocks (microtextural sites). The main compositional aspect of coronitic textures is the mineral zoning, particularly when the minerals of the coronas are the consequence of a wide range of solid solutions. In such cases, the reacting minerals are armored and the kinetics are lowered. The prograde metamorphic evolution, which involved the rocks from the oceanic lithosphere and the paleo-European continental margin, is quite consistent with a subduction-type geodynamic process in different ages during alpine times.Mineral Abbreviations Ab albite - Acm acmite - Alm almandine - Amp amphibole - Ant antigorite - Act actinolite - Bt biotite - Ced celadonite - Chl chlorite - Chlrm chloromelanite - Chltd chloritoide - Cpx clinopyroxene - Di diopside - Ep epidote - Fo forsterite - Gl glaucophane - Gnt garnet - Gro grossular - Hed hedenbergite - Hor hornblende - Jd jadeite - Kfld K-feldspar - Lau laumontite - Lw lawsonite - Ma margarite - Mu muscovite - Omp omphacite - Pa paragonite - Ph phengite - Pl plagioclase - Py pyrope - Pyr pirophyllite - Prh prehnite - Pump pumpellyite - Qz quartz - Rieb riebeckite - Rut rutile - Tchu titanclinohumite - Tc talc - Tr tremolite - Zeo zeolites - Zo zoisite - Wm white mica     

Cenomanian oysters from the Sergipe Basin, Brazil

Cenomanian (mid Cretaceous) oysters from the Sergipe Basin in northeastern Brazil are described, with revisions of previously described forms. Nine genera and subgenera, including eleven species, are distinguished: Rastellum diluvianum (Linné, 1767), Amphidonte (Ceratostreon) reticulata (Reuss, 1846), A. (Ceratostreon) flabellata (Goldfuss, 1833), Exogyra (Costagyra) olisiponensis Sharpe, 1850, Ilymatogyra (Afrogyra) africana (Lamarck, 1801), Rhynchostreon (Rhynchostreon)mermeti (Coquand, 1862), R. (Laevigyra) obliquatum (Pulteney, 1813), R. (Laevigyra) sp., Pycnodonte (Phygraea) vesiculosa (J. Sowerby, 1823), Curvostrea rouvillei (Coquand, 1862) and Ambigostrea sp. No undoubted Turonian oysters are known from Sergipe, althoughR. (R.) mermeti possibly straddles the Cenomanian–Turonian boundary. This is in sharp contrast with the situation in the more northerly Brazilian basins, from where several Turonian but no Cenomanian forms have been described. Well-preserved material from Sergipe confirms the close relationship between Exogyra (Costagyra) Vialov andVultogryphaea Vialov. The palaeobiogeographical affinity of the oyster fauna is typically Tethyan with many taxa that are known particularly from the southern Tethys. The inferred palaeoenvironment as implied by the oysters is that of a shallow shelf.     

Discovery of Radiolarian Fossils from the Aiketik Group at the Western End of the South Tianshan Mountains of Chinaand Its Implications

The Aiketik Group, distributed at the western end of the South Tianshan Mountains, China, is an important lithostratigraphic unit involved in the South Tianshan orogen. It is separated from the adjacent rocks by faults. Generally, the geologists ascribed it to the Upper Carboniferous according to Pseudostaffella sp., Profusulinella sp. and Fusulinella sp. found from the limestone and sandy limestone of Aiketik. Our radiolarian fossils were obtained from the chert samples collected from the Haladaok section located at the upper Tuoshihan River. The fossils mainly include Albaillella undulata Deflandre, Albaillella paradoxa Deflandre, Albaillella sp. aff. A. paradoxa Deflandre, Albaillella sp. cf. A. deflandrei Gourmelon, Albaillella sp., Albaillella excelsa Ishiga, Kito and Imoto (?), Belowea variabilis (Ormiston et Lane), Callella cf. C. parvispinosa Won, Entactinia cf. E. tortispina Ormiston et Lane, Entactinia aff. E. tortispina Ormiston et Lane, Entactinia variospina Won, Entactinia sp., Eostylodicty     

Ammonites from the Pawpaw Shale (Upper Albian) in northeast Texas

The lower part of the Pawpaw Shale in northeast Texas yields an abundance of diminutive limonitic ammonites, the assemblage being: Tetragonites sp. juv., Engonoceras serpentinum (Cragin, 1900), Conlinites wrighti gen. et sp. nov., Cantabrigites wenoensis (Adkins, 1920), Neophlycticeras (Neophlycticeras) sp., Neophlycticeras (Paradolphia) occidentalis sp. nov., Stoliczkaia (Stoliczkaia) clavigera Neumayr, 1875, Stoliczkaia (Lamnayella) worthense (Adkins, 1920), Stoliczkaia (Shumarinaia) asiatica Matsumoto and Inoma, 1975, Enigmaticeras riceae gen. et sp. nov., Flickia simplex Pervinquière, 1907, Ficheuria pernoni Dubourdieu, 1953, Ficheuria americana sp. nov., Anisoceras armatum (J. Sowerby, 1817), Hamites venetzianus Pictet, 1847, Mariella (Mariella) worthensis (Adkins and Winton, 1920), Mariella (Mariella) asper sp. nov., Lechites (Lechites) comanchensis (Adkins, 1920), Worthoceras worthense (Adkins, 1920), and Scaphites hilli Adkins and Winton, 1920.This assemblage is correlated with the Mortoniceras (Subschloenbachia) rostratum Subzone of the European sequence on the basis of the occurrence of that species in the underlying Weno Limestone, in the passage beds between the Pawpaw Shale and the succeeding Main Street Limestone, and the lower part of the Main Street.Some previous authors have interpreted the diminutive limonitic ammonites of the Pawpaw as being “dwarf” or “stunted”. The overwhelming majority of individuals are nuclei of much larger ammonites, with smaller numbers of adults of small species that occur in other facies and geographic locations, together with a smaller number still of paedomorphic dwarfs. The fauna is interpreted as a preservational one, where diagenetic pyrite formed in relatively small voids, either the early phragmocone chambers of larger ammonites, or the phragmocone and body chambers of genuinely diminutive species which oxidised to limonite during the weathering process.     

The assemblage stilpnomelane–chlorite–phengitic mica: a geothermobarometer for blueschist and associated greenschist terranes

Two anhydrous equilibria can be written among the components of stilpnomelane, chlorite, white mica and quartz, namely 89 daphnite+131 Fe-celadonite+190 quartz=96 stilpnomelane+71 muscovite, and amesite+Mg-celadonite=muscovite+clinochlore. We assume that the free energy change of reaction, ΔG=ΔG^o+ΣRT lna_i^j, is approximated by ΔG=A?BT +C(P?1)+ΣRT lna_i^j, where ΔG^o is the free energy change of the end-member components at temperature T and pressure P, a_i is the activity of component i whose coefficient in the equilibrium is j, and A, B and C are constants to be determined. Values of C can be approximated by the change in volume on reaction, namely C=406.517 J/bar for the first reaction and C=0.613 J/bar for the second reaction. Constants A and B were determined by using six occurrences of the assemblage stilpnomelane–chlorite–white mica for which P–T have been otherwise estimated. Using solution models from the literature, linear regression gives for the first equation A=?6118.269 kJ, B=?4584.09 J/K, and for the second equation A=19.397 kJ, B=66.72 J/K. These values predict P–T within 0.5 kbar and 25 K for all occurrences, and appear reasonably robust relative to probable analytical errors. P–T are determined by intersection of the curves generated by given compositions in P–T space. Fine-grained and/or zoned chlorite and white mica make application of the geothermobarometer difficult in some instances, but our work in the Bathurst region of New Brunswick suggests that, with patience and care, useful analyses can be obtained, and the database for the geothermobarometer greatly expanded.     

The ammonite family Parahoplitidae in the Sanganeh Formation of the Kopet Dagh Basin, north-eastern Iran

The Iranian part of the Kopet Dagh Basin is located in north-eastern Iran, where sedimentation was continuous throughout Jurassic to Tertiary times. The ammonite content of the Sanganeh Formation (Lower Cretaceous) has been studied. The following parahoplitid forms have been recorded: Acanthohoplites cf. aschiltaensis, A. cf. bigoureti, A. sp. 1, A. sp. 2, A. spp., Colombiceras sp., Hypacanthoplites cf. anglicus, H. cf. clavatus, H. cf. elegans, H. cf. subrectangulatus, H. uhligi, H. sp., Parahoplites cf. campichii and P. cf. maximus.     

Heinrich Georg Bronn: Ein Brief von 1855 zur Evolutionstheorie vor Darwins Werk von 1859.

Karl Dietrich Adam/Ludwigsburg; Jens Klein–Dieter Becker-Platen/Hannover; Gerhard W. Brümmer/ Bonn; Walter Carlé (+)/Stuttgart; Claus Duphorn ^* Kiel; Peter von Egan-Krüger/Heidelberg; Hans Ehrenberg/Mainz; Heinrich Karl Erben/Bonn; Helmut W. Flügel/Graz; Klaus Gallwitz/Karlsruhe; Helmut Haunschild/München; Hans-Georg Herbig/K?ln; Heinrich Hiltermann/Bad Laer; Helmut H?lder/Stuttgart; Andreas Hoppe/Wiesbaden; Günter Hoppe/Berlin; Rolf Kohring/Berlin; Karl Otto Kopp/München; Wolfhart Langer/Bonn; Gaston Mayer/Karlsruhe; Georg Matthess/ Kiel; Gert Michel/Krefeld; Ursula Patzke ^* Ahrensburg; Fritz A. Pfaffl/Zwiesel; Werner Prange/ Kiel; Ilse Rabien/Hochheim; Ernst Reiner/Gummersbach; Siegfried Ritzkowski/G?ttingen; Peter Rothe/Mannheim (Nachlassteile Ludwig und Pauline Rüger und Nachlass Ilse Plewe); Wolfgang Schirmer/ Düsseldorf; Horst Schneider/Freiburg; Erich Schroeder ^* Berlin; Max Schwab/Halle (Nachlass Rudolf Hohl); Eberhard Sittig ^* Rheinstetten; Walter Steiner/Weimar; Alexander Tollmann/Wien; Rudolf Trümpy/Küsnacht; Ida Valeton ^* Braunschweig; Freek R. van Veen/Delft; Ehrhard Voigt/Hamburg; Helmut Weiler/Mainz; Gerd Wiesemann/Isernhagen; Eugen Wirth/Erlangen; Zobel Barbara/Hannover. Da schon Missverst?ndnisse vorgekommen sind, sei darauf hingewiesen, dass es sich bei dem im Nachrichtenblatt der Deutschen Geologischen Gesellschaft (59, 4, Quartal 1996, S. 30) erw?hnten “Geologenarchiv” um das Freiburger Archiv handelt.     

Late Pliocene and Pleistocene small mammal chronology in the Italian peninsula

The abundant documentation of small mammals in the Italian peninsula, collected over recent years, furnishes a detailed biochronological sequence mainly from the Late Pliocene onwards. An updated stratigraphic framework is here presented, based on the European small mammal biozonation. The Early Villanyian is characterized by Mimomys hassiacus, M. stehlini, and, later, poorly documented M. polonicus. The Late Villanyian localities are well characterized with M. pliocaenicus, M. pitymyoides and M. tigliensis. The older part of the Early Biharian is documented by assemblages containing Microtus (Allophaiomys) ex gr. pliocaenicus, M. pusillus, M. cf. ostramosensis and M. tornensis, while the later part of the Early Biharian, is characterized by advanced Microtus (Allophaiomys) species occurring together with M. pusillus or M. blanci. In the Late Biharian M. savini, Microtus hintoni-gregaloides, Microtus (Iberomys) ex gr. huescarensis-brecciensis and Terricola arvalidens occur. The Early Toringian with A. mosbachensis, Allocricetus bursae, Pliomys episcopalis and small-sized Microtus brecciensis, and the Late Toringian with A. terrestris in diversified associations are quoted. The most important faunal events are calibrated by independent chronological controls, thanks to the record of small mammals from lacustrine deposits. Several figures illustrate the most significant rodent species occurring in the succession of selected Italian localities.     

云南保山地区中-晚三叠世Budurovignathus及Pseudofurnishius牙形类动物群的发现及意义

Budurovignathus和Pseudofurnishius牙形类动物群是世界上具有重要地层研究价值且比较稀有的牙形类动物群,迄止目前,在滇西保山地区发现:Budurovignathus hungaricus(Kozur et Vigh)、B.mungoensis(Diebel)、B.aff.mungoensis(Diebel)or B.baoshanensis sp.nov.、B.diebeli(Kozur et Mostler)、Pseudofurnishius socioensis(Gullo et Kozur),P.murcianus(Van Den Boogaard)和Pseudofurnishius sp.A等重要的属种,本次发现,为云南保山地区中—晚三叠世地层提供有力的生物年代约束,拓展了三叠世牙形石生物带,同时也丰富了中国这两个牙形类动物群的资料。     

Permo-Carboniferous Radiolarians from the Wupata＇erkan Group, Western South Tianshan, Xinjiang, China

The Wupata‘erkan Group, also called Wupata‘erkan Formation, distributed in the South Tianshan, Xinjiang,China, mainly consists of gray and dark gray fine-grained clastic rocks, interlayered with volcanic rocks, carbonates and cherts. Some ultra-basic rocks (blocks) punctuate the formation. The formation was variously assigned to Silurian-Middle Devonian, Silurian-Lower Devonian, and pre-Devonian, mainly based on Atrypa bodini Mansuy, Hypothyridina parallelepipedia (Brour.) and Prismatophyllum hexagonum Yoh collected from the limestone interlayers, respectively.However, radiolarian fossils obtained from 24 chert specimens of the Wupata‘erkan Group, mainly include Albaillella sp.cf. A. undulata Deflandre, Albaillella sp. cf. A. paradoxa Deflandre, Albaillella cf. A. deflandrei Gourmelon, Albaillella sp. cf. A. indensis Won, Albaillella sp. cf. A. excelsa Ishiga, Kito and Imoto, Albaillella sp. and Latentifistulidae gen. et. sp.indet., are earliest Carboniferous and Late Permian. The earliest Carboniferous assemblage is characterized by Albaillella sp. cf. A. undulata Deflandre, Albaillella sp. cf. A. paradoxa Deflandre, Albaillella cf. A. deflandrei Gourmelon and Albaillella sp. cf. A. indensis Won, and the Late Permian assemblage by Albaillella sp. cf. A. excelsa Ishiga, Kito and Imoto. This new stratigraphic evidence indicates that the Wupata‘erkan Group is possibly composed of rocks with different ages from Silurian to Permian, and therefore, it is probably an ophiolite mrlange. The discovery of Late Permian Albaillella sp. cf. A. excelsa provides more reliable evidence supporting the existence of a Permian relic ancient oceanic basin in the western part of Xinjiang South Tianshan.     

Theoretical Prediction of Gibbs Free Energies of Formation for Crystalline α-MOOH and α-M2O3 Based on a Linear Free-Energy Relationship

In the present study, the modified Sverjensky–Molling equation, derived from a linear-free energy relationship, is used to predict the Gibbs free energies of formation of crystalline phases of α-MOOH (with a goethite structure) and α-M2O3 (with a hematite structure) from the known thermodynamic properties of the corresponding aqueous trivalent cations (M3+). The modified equation is expressed as ΔG0f,MVX=aMVXΔG0n,M3++bMVX+βMVXγM3+, where the coefficients aMVX, bMVX, and βMVX characterize a particular structural family of MvX (M is a trivalent cation [M3+] and X represents the remainder of the composition of solid); γ3+ is the ionic radius of trivalent cations (M3+); ΔG0f,MVX is the standard Gibbs free energy of formation of MvX; and ΔG0n,M3+ is the non-solvation energy of trivalent cations (M3+). By fitting the equation to the known experimental thermodynamic data, the coefficients for the goethite family (α-MOOH) are aMVX=0.8838, bMVX=?424.4431 (kcal/mol), and βMVX=115 (kcal/mol.?), while the coefficients for the hematite family (α-M2O3) are aMVX=1.7468, bMVX=?814.9573 (kcal/mol), and βMVX=278 (kcal/mol.?). The constrained relationship can be used to predict the standard Gibbs free energies of formation of crystalline phases and fictive phases (i.e. phases that are thermodynamically unstable and do not occur at standard conditions) within the isostructural families of goethite (α-MOOH) and hematite (α-M2O3) if the standard Gibbs free energies of formation of the trivalent cations are known.