Lorenzo Toscani

Sulfur and oxygen isotope compositions of Upper Triassic sulfates from Northerm Apennines (Italy): palaeogeographic and hidrogeochemical implications

Upper Triassic bedded evaporite sulfate of the Burano Formation outcropping at Cerreto Pass between Tuscany and Emilia-Romagna in the Northern Apennines were analyzed for sulfur and oxygen isotope compositions, yielding d34S and d18O values of 15.5±0.4‰ and 10.8±1.2‰, respectively (mean ±99% confidence intervals). Combining these values with those of other Burano Formation sulfate deposits along the Apennine chain, mean for d34S and d18O values are obtained (15.2±0.2‰ and 10.9±0.5‰, respectively). These isotopic signatures are interpreted as preserved primary features, despite the fact that the Burano Formation underwent anchizone to epizone metamorphism during the Apennine orogenesis. An overall d18O value of 10.9±1.5‰ (mean ± pooled standard deviation), obtained by combining consistent sets of data from Italy and Spain, closely approaches that of gypsum deposited from the Tethys ocean during the Late Triassic. In addition, reviewing the isotope data published on Late Triassic evaporite sulfates from the Mediterranean area and abroad, several d34S values appear to be lower than the inferred primary isotopic signature, and seemly decrease from East to West in the Mediterranean region, suggesting a similar trend for the Tethys ocean sulfate. Possibly, 34S-depleted sulfate entered the ocean through oxidation of volcanic SO2 emitted in the atmosphere and degassed from the seafloor during the development of Late Triassic rifting. On the other hand, positive shifts of d34S and d18O values also occur, defining a common trend that may be related to synsedimentary biological effects or post-depositional metasomatic-metamorphic effects, the latter affecting particularly the d18O signature. Therefore, the d34S and d18O signatures of evaporite sulfate may provide a like “slide-rule” diagram to distinguish between isotopic effects related to biological or abiological processes, thus contributing to the reconstruction of paleoenvironments and paleogeographic settings. Based on the d34S-d18O “slide-rule”, the isotopic composition of sulfate dissolved in spring and stream waters of northern Tuscany was interpreted in terms of origin of the sulfate and modifying processes in solution. It was concluded that sulfate in springs derives from Upper Triassic evaporite existing locally at depth (Burano Formation), whereas sulfate in streams is manifestly a mixture of Burano Formation sulfate with supergene sulfate from oxidation of sulfide in the rocks. In sulfurous springs, both sulfur and oxygen isotope fractionations with respect to the source sulfate signatures may be ascribed to bacterial effects. However, the oxygen isotope exchange of sulfate with water should have been a very minor process as supported by the nearsurface temperature values estimated by sulfate-water oxygen isotope thermometry.

Sulphide-bearing waters in Northern Apennines, Italy : general features and water rock interaction

Sulphide-bearing Ca-carbonate, Na-carbonate, Na-hydroxide, Na-chloride and Ca-sulphate waters from Northern Apennines were investigated in order to determine their main chemical and isotopic composition and draw inferences on water-rock interaction. δ2H and δ18O values suggest an origin mostly meteoric for the analysed waters but a well drilled in Miocenic sediments. The Na-carbonate and the Ca-sulphate waters are the most interesting geochemically. Na-carbonate type, which sometimes reaches extreme composition (Na/Ca up to 228, equivalent ratio), may have been derived through prolonged interaction of Ca-carbonate waters with rocks containing feldspar, montmorillonite and illite under calcite saturation/oversaturation; the high F and pH and the very low PCO2 agree with prograde dissolution of silicates and lasting water-rock interaction. However, Ca–Na ion exchange, involving clays of marine origin, cannot be excluded in addition. The Ca-sulphate waters, occurring in Messinian gypsum-bearing sediments, are saturated in gypsum and calcite and exhibit very high total H2S (up to 219 mg dm-3) and PCO2 (up to 0.32 bar). Mass balance of sulphate sulphur, sulphide sulphur and delta34S suggests sulphate – derived from gypsum – as source for H2S; CH4 and organic matter generate the reducing conditions and sulphate reduction is mediated by bacteria. One Na-chloride water from a well in Miocenic sediments has unusual composition, containing about 700 mgdm-3 of potential CaCl2 and having δ2H and δ18O (-47.5 and -4.9‰ respectively) which plot far from the meteoric water lines; probably it is derived by mixing of meteoric and formation waters. The Na-hydroxide water, with very high pH (11.2), is generated through protracted interaction of meteoric waters with ultramafites.

The groundwaters of Fontevivo (Parma Province, Italy): Redox processes and mixing with brine waters

This paper describes the chemical and isotopic characterization of H2S-bearing groundwaters of the Fontevivo area, northern Italy. Groundwaters from Fontevivo (Parma Province) contain dissolved H2S and minor hydrocarbons, which are released from the truncated front of a buried geological structure (Calabrian– Miocene terrains) and through abandoned unsealed oil wells. H2S concentration is up to 5.54 mg/l in groundwaters from the topographical high of the village and its distribution in the investigated area is inversely related with those of NH4+ and SO42−. Groundwaters are dominantly Ca-HCO3 type with lesser Ca-SO4 and Na-Cl types and display two compositional trends: group A, waters from Ca-HCO3 to Ca-SO4; group B, waters from Ca-HCO3 to Na-Cl. Group A water compositions are influenced by redox processes including the oxidation of H2S to SO42−. Primary sulphate from dissolution of Messinian evaporite is rare. Group B waters represent mixing of meteoric water with small amounts of brine. The most Cl (Br, I)-rich groundwaters are located in the NE of the investigated area, where a Cl–Br–I-rich brine was encountered by an exploration well in the Calabrian stratum. Berner has provided a classification of redox environments starting from the observation of the sequence of reduction/oxidation processes as shown by groundwater composition. At Fontevivo the Berner redox zones show an areal distribution where the anoxic zones occur in the topographical high. The δ2H and δ18O values of groundwaters plot close to the Global Meteoric Water Line. They indicate that local precipitation recharges the shallow aquifer (<30 m deep), whereas rainwater from the higher elevated Apennine ridge recharges the deeper aquifer (≧30 m deep) via the Taro river and its alluvial fan. Dissolved H2S is depleted in 34S consistent with biogenic sulphate reduction. Secondary origin from oxidation of H2S in shallow groundwater is invoked for depleted δ34S (SO42−). The studied saline sample (27.8 g/l TDS) show a δ34S (H2S) value of +24.9‰, suggesting a nearly complete reduction of Messinian sulphate within a system closed to H2S. A hydrogeological model is presented based on a chemical-thermodynamic, trace element statistical, and multi-isotope approach.

Magmatic evolution of the Gaussberg lamproite (Antarctica): volatile content and glass composition

Abstract The lamproite of Gaussberg is an ultrapotassic rock where leucite, olivine and clinopyroxene microphenocrysts occur in a glass-rich groundmass, containing microliths of leucite, clinopyroxene, apatite, phlogopite and rare K-richterite. Abundant silicate melt inclusions occur in olivine, leucite and, rarely, in clinopyroxene microphenocrysts. Raman investigations on melt inclusions showed the presence of pure CO2 in the shrinkage bubbles. On the other hand, the glass of the groundmass is CO2-poor and contains up to 0.70 wt.% of dissolved H2O, as estimated by infrared spectra. It is inferred that CO2 was released at every stage of evolution of the lamproite magma (CO2-rich shrinkage bubbles), whereas H2O was retained for longer in the liquid. At Gaussberg, CO2 seems to have a major role at relatively high pressure where it favoured the crystallization of H2O-poor microphenocrysts; the uprise of the magma to the surface decreased the solubility of CO2 and caused a relative increase in water activity. As a consequence, phlogopite and K-richterite appeared in the groundmass. The glass composition of both the groundmass and melt inclusions suggests different evolutions for the residual liquids of the investigated samples. Sample G886 shows the typical evolution of a lamproite magma, where the residual liquid evolves toward peralkaline and Na-rich composition and crystallizes K-richterite in the latest stage. Sample G895 derives from mixing/mingling of different batches of magma; effectively glasses from melt inclusions in leucite and clinopyroxene are more alkaline than those found in early crystallized olivine. Leucite and clinopyroxene crystallized early from a relatively more alkaline batch of lamproite magma and, successively, a less alkaline, olivine-bearing magma batch assimilated them during its rise to the surface.

Messinian Ca–Cl Brines from Mediterranean Basins: Tracing Diagenetic Effects by Ca/Mg Versus Ca/Sr Diagram

In natural resource exploration, Ca–Cl basinal brines are important for understanding the origin and spatial and temporal distribution of hydrocarbons and sedimentary ore deposits. Little attention has been paid to the possible connection between fossil basinal brines and paleo-seawaters and to the implications for reconstructing paleo-seawater compositions. Secular variations of Ca/Mg and Ca/Sr ratios in seawater have been documented mainly using fluid inclusions in halite, calcareous fossils and mineral analyses. However, brines and other sedimentary records connected to paleo-seawater or its evaporated residues may be chemically affected by burial diagenesis or the effects of continental waters of meteoric origin, thus complicating interpretations of the analytical results. To investigate these effects on fluids and minerals related to the Messinian salinity crisis of the Mediterranean basin, we re-evaluate published data from: (1) brackish-to-brine waters from onshore (Northern Apennine foredeep; Levantine basin) and offshore (porewaters from the Deep Sea Drilling Project); (2) Messinian parental seawater deduced from calcareous fossils, fluid inclusions and sulfate minerals; (3) meteoric waters dissolving evaporites. The compositional trends related to seawater evaporation, diagenesis and mixing that affect the Ca/Mg and Ca/Sr molar ratios of the basinal brines are effectively discriminated on a binary plot depicting the proper fields for seawater and meteoric-derived fluids. Brines showing stronger dolomitization start from Ca/Mg and Ca/Sr molar ratios of Messinian seawater deduced from the published analysis of fluid inclusions and open ocean fossils, that are therefore here validated ex post.

A conceptual hydrogeological model of ophiolitic aquifers (serpentinised peridotite): The test example of Mt. Prinzera (Northern Italy)

&NA; The main aim of this study is the experimental analysis of the hydrogeological behaviour of the Mt. Prinzera ultramafic massif in the northern Apennines, Italy. The analysed multidisciplinary database has been acquired through (a) geologic and structural survey; (b) geomorphologic survey; (c) hydrogeological monitoring; (d) physico‐chemical analyses; and (e) isotopic analyses. The ultramafic medium is made of several lithological units, tectonically overlapped. Between them, a low‐permeability, discontinuous unit has been identified. This unit behaves as an aquitard and causes a perched groundwater to temporary flow within the upper medium, close to the surface. This perched groundwater flows out along several structurally controlled depressions, and then several high‐altitude temporary springs can be observed during recharge, together with several perennial basal (i.e., low altitude) springs, caused by the compartmentalisation of the system because of high‐angle tectonic discontinuities.

Post-magmatic apatite + hematite + carbonate assemblage in the Jumilla lamproites. A fluid inclusion and isotope study

Abstract The lamproitic rocks of Jumilla (southeastern Spain) consist of magnesian olivine, phlogopite, clinopyroxene, F-apatite, sanidine and analcime in variable amounts, and of Cr-rich spinel (mostly included in olivine and clinopyroxene), K-rich amphibole, Ti-magnetite, ilmenite and late calcite. In a small area, a post-magmatic apatite + hematite + carbonate assemblage occurs in the form of thin veins. F-apatite, hematite and calcite are the dominant phases. Apatite is rich in several generations of fluid (sensu lato) inclusions. The prevalent primary inclusions are filled in part with a solidified saline melt and in part with a very low density gas; the solid/gas volume ratio in the inclusions is not constant suggesting that, at the time of entrapment in apatite, a vapour phase was coexisting with the saline melt. The final melting temperature of the solids contained in the inclusions is mostly in the range 630–700°C, which represents the minimum temperature of entrapment. Other inclusions are concentrated along healed fractures. Some of them are similar to the solid salt inclusions described above, but most of them contain liquid, vapour and, sometimes, abundant daughter minerals. The temperature of initial melting of frozen liquid-bearing inclusions is variable (ca. −54°C, −35/−39°C, ca. −11°C, ca. −2/−3°C) suggesting that aqueous fluids carrying different components were entrapped at different times. The strontium isotope ratios and the high content of fluorine and REE suggest that apatite crystallized from fluids prevalently segregated from the lamproitic magma. Strontium as well as oxygen and carbon isotopes of the carbonates associated with apatite suggest that the parent fluids were poligenic (magmatic and sedimentary components) or of prevalent sedimentary provenance.

Weathering of granodiorite and micaschists, and soil pollution at Mt. Mottarone (northern Italy)

Abstract At the top of Mt. Mottarone a thin level of micaschist, covered by soil, rests on granodioritic rocks. Both rock types underwent weathering with generation of new minerals and variation of the original chemical composition. The weathering produced phyllosilicates and Fe- and Al-hydroxides. Mass balance calculations on the basis of Zr immobility indicate that at least As, Bi, Cd, Mo and Sb were added to the micaschist, whereas the other elements were removed; the soil was also enriched in As, Bi, Cd, Mo and Sb during weathering. Dry and wet pollution was responsible for the addition of the elements listed above. On the other hand, Ca, Na, Mo and Sr were surely removed from the granodiorite during weathering, whereas Bi and Cu were added by percolation from the overlying micaschist. The chemical features of a spring issuing from granodiorite agree well with the element budget as deduced from the rock transformation. This is not the case, however, for a spring issuing from the micaschist.

Oxygen, Hydrogen, Boron and Lithium Isotope Data of a Natural Spring Water with an Extreme Composition: A Fluid from the Dehydrating Slab?

The chemical and isotope compositions of slab dehydration fluids from convergent margins have been theorized by many authors who have adopted several approaches. A direct collection of natural water is possible only in an oceanic environment, despite several difficulties in estimating the deepest component due to the mixing with seawater or hydrothermal fluids from the ridge. Accordingly, the study of melt inclusions is a valuable alternative. However, the latter mainly represents high temperature/pressure conditions in deep magmatic or metamorphic settings. Here, we present new H, O, Li and B isotope along with a revision of previously published chemical data from a potential natural example of slab dehydration water, sampled in a forearc region and affected by low-temperature metamorphism and serpentinization processes (Aqua de Ney, Northern California). Its extreme composition challenges the understanding of its origin and deep temperature, but this work is a further step on a topic of increasing interest for several scientists from different academic disciplines.