Numerical modelling of gas-water-rock interactions in volcanic-hydrothermal environment: the Ischia Island (Southern Italy) case study.

Hydrothermal systems hosted within active volcanic systems represent an excellent opportunity to investigate the interactions between aquifer rocks, infiltrating waters and deep-rising magmatic fluids, and thus allow deriving information on the activity state of dormant volcanoes. From a thermodynamic perspective, gas-water-rock interaction processes are normally far from equilibrium, but can be represented by an array of chemical reactions, in which irreversible mass transfer occurs from host rock minerals to leaching solutions, and then to secondary hydrothermal minerals. While initially developed to investigate interactions in near-surface groundwater environments, the reaction path modeling approach of Helgeson and co-workers can also be applied to quantitative investigation of reactions in high T-P environments. Ischia volcano, being the site of diffuse hydrothermal circulation, is an ideal place where to test the application of reaction-path modeling. Since its last eruption in 1302 AD, Ischia has shown a variety of hydrothermal features, including fumarolic emissions, diffuse soil degassing and hot waters discharges. These are the superficial manifestation of an intense hydrothermal circulation at depth. A recent work has shown the existence of several superposed aquifers; the shallowest (near to boiling) feeds the numerous surface thermal discharges, and is recharged by both superficial waters and deeper and hotter (150-260° C) hydrothermal reservoir fluids. Here, we use reaction path modelling (performed by using the code EQ3/6) to quantitatively constrain the compositional evolution of Ischia thermal fluids during their hydrothermal flow. Simulations suggest that compositions of Ischia groundwaters are buffered by interactions between reservoir rocks and recharge waters (meteoric fluids variably mixed - from 2 to 80% - with seawater) at shallow aquifer conditions. A CO2 rich gaseous phase is also involved in the interaction processes (fCO2 = 0.4-0.6 bar). Overall, our model calculations satisfactorily reproduce the main chemical features of Ischia groundwaters. In the model runs, attainment of partial to complete equilibrium with albite and K-feldspar fixes the Na/K ratios of the model solutions at values closely matching those of natural samples. Precipitation of secondary phases, mainly clay minerals (smectite and saponite) and zeolites (clinoptilolite), during the reaction path is able to well explain the large Mg-depletions which characterise Ischia thermal groundwaters; while pyrite and troilite are shown to control sulphur abundance in aqueous solutions. SiO2(aq) contents in model simulations fit those measured in groundwaters and are being buffered by the formation of quartz polymorphs and Si-bearing minerals. Finally, our simulations are able to reproduce redox conditions and Fe-depletion trends of natural samples. We conclude that reaction path modelling is an useful tool for quantitative exploration of chemical process within volcano-hosted hydrothermal systems

Quantitative models of hydrothermal fluid–mineral reaction:The Ischia case

The intricate pathways of fluid–mineral reactions occurring underneath active hydrothermal systems are explored in this study by applying reaction path modelling to the Ischia case study. Ischia Island, in Southern Italy, hosts a well-developed and structurally complex hydrothermal system which, because of its heterogeneity in chemical and physical properties, is an ideal test sites for evaluating potentialities/limitations of quantitative geochemical models of hydrothermal reactions. We used the EQ3/6 software package, version 7.2b, to model reaction of infiltrating waters (mixtures of meteoric water and seawater in variable proportions) with Ischia’s reservoir rocks (the Mount Epomeo Green Tuff units; MEGT). The mineral assemblage and composition of such MEGT units were initially characterised by ad hoc designed optical microscopy and electron microprobe analysis, showing that phenocrysts (dominantly alkali–feldspars and plagioclase) are set in a pervasively altered (with abundant clay minerals and zeolites) groundmass. Reaction of infiltrating waters with MEGT minerals was simulated over a range of realistic (for Ischia) temperatures (95–260° C) and CO2 fugacities (10 ^-0.2 to 10^0.5) bar. During the model runs, a set of secondary minerals (selected based on independent information from alteration minerals’ studies) was allowed to precipitate from model solutions, when saturation was achieved. The compositional evolution of model solutions obtained in the 95–260°C runs were finally compared with compositions of Ischia’s thermal groundwaters, demonstrating an overall agreement. Our simulations, in particular, well reproduce the Mg-depleting maturation path of hydrothermal solutions, and have end-of-run model solutions whose Na–K–Mg compositions well reflect attainment of full-equilibrium conditions at run temperature. High-temperature (180–260° C) model runs are those best matching the Na–K–Mg compositions of Ischia’s most chemically mature water samples, supporting quenching of deep-reservoir conditions for these surface manifestations; whilst Fe, SiO2 and, to a lesser extent, SO4 contents of natural samples are better reproduced in low-temperature (95°C) runs, suggesting that these species reflect conditions of water–rock interaction in the shallow hydrothermal environment. The ability of model runs to reproduce the compositional features of Ischia’s thermal manifestations, demonstrated here, adds supplementary confidence on reaction path modelling as a realistic and insightful representation of mineral–fluid hydrothermal reactions. Our results, in particular, demonstrate the significant impact of host rock minerals’ assemblage in governing the paths and trends of hydrothermal fluids’ maturation

Effect of equine chorionic gonadotropin treatment during a progesterone-based timed artificial insemination program on reproductive performance in seasonal-calving lactating dairy cows

peer-reviewedThe aim of this study was to investigate the effect of progesterone (P4)-based timed artificial insemination (TAI) programs on fertility in seasonal-calving, pasture-based dairy herds. A total of 1,421 lactating dairy cows on 4 spring-calving farms were stratified based on days in milk (DIM) and parity and randomly allocated to 1 of 3 treatments: (1) control: no hormonal treatment; cows inseminated at detected estrus; (2) P4-Ovsynch: cows received a 7-d P4-releasing intravaginal device (PRID Delta; CEVA Santé Animale, Libourne, France) with 100 μg of a gonadotropin-releasing hormone (GnRH) analog (Ovarelin; CEVA Santé Animale) at PRID insertion, a 25-mg injection of PGF2α (Enzaprost; CEVA Santé Animale) at PRID removal, GnRH at 56 h after device removal and TAI 16 h later; (3) P4-Ovsynch+eCG: the same as P4-Ovsynch, but cows received 500 IU of equine chorionic gonadotropin (eCG; Syncrostim; CEVA Santé Animale) at PRID removal. At 10 d before mating start date (MSD), all cows that were ≥35 DIM were examined by transrectal ultrasound to assess presence or absence of a corpus luteum; body condition score (BCS) was also recorded. Pregnancy diagnosis was performed by transrectal ultrasonography 30 to 35 d after insemination. Overall pregnancy/AI (P/AI) was not different between groups (50.9, 49.8, and 46.3% for control, P4-Ovsynch, and P4-Ovsynch+eCG, respectively) but the 21-d pregnancy rate was increased by the use of synchronization (35.0, 51.7, and 47.2%, respectively). Compared with the control group, synchronization significantly reduced the interval from MSD to conception (34.6, 23.0, and 26.5 d, respectively) and consequently reduced the average days open (98.0, 86.0, and 89.0 d). Across all treatment groups, DIM at the start of synchronization affected P/AI (42.3, 49.5, and 53.9% for 80 DIM, respectively), but neither parity (46.5, 50.4, and 48.4% for parity 1, 2, and ≥3, respectively) nor BCS (44.0, 49.4, and 58.6% for ≤2.50, 2.75–3.25, and ≥3.50, respectively) affected the likelihood of P/AI. Two-way interactions between treatment and DIM, parity, or BCS were not detected. In conclusion, the use of TAI accelerated pregnancy establishment in cows in a pasture-based system by reducing days open, but eCG administration at PRID removal did not affect P/AI

Editorial

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