Isotopic and fluid inclusion study of hydrothermal and metamorphic carbonates in the Larderello geothermal field and surrounding areas, Italy

Fluid inclusions have been studied on six calcite veins from the shallow part (480 to 1515 m below ground level) of the Larderello geothermal field and outcropping in peripheral zones of the geothermal area. Oxygen and carbon isotopic analyses have been carried out on these carbonate veins, as well as on the dolostone layers found inside the Paleozoic metamorphic units of the deep part of the field (from 1939 to 3177 m below ground level). Fluid inclusion observations suggest that boiling processes probably occurred during calcite precipitation in most of the veins. The fluids that formed or interacted with the calcite veins below the uppermost reservoir (made up of Mesozoic marine carbonates), and with the calcite hydrothermal veins of Sassa, were characterised by an apparent salinity from 1.3 to 5.3 wt.% NaCl eq. and a homogenisation temperature from 137 to 245°C. The fluid inclusions related to the calcite veins hosted above the uppermost reservoir show a wide range of apparent salinity (from 1.7 to 22.2 wt.% NaCl eq.) and homogenisation temperatures from 224 to 296°C. Apparent salinity/homogenisation temperature covariations of the latter veins are interpreted as being the result of a mixing process between a low-temperature, high-salinity fluid and a higher-temperature, moderate-salinity fluid. The oxygen isotopic compositions of the calcite veins (δ¹⁸O from 10.34 to 11.45‰) located below the Mesozoic carbonates and in the outcrops (δ¹⁸O from 9.42 to 17.07‰) indicate that the vapour in equilibrium with these veins was isotopically similar to the present-day discharge steam. The aqueous fluids in equilibrium with these veins could be meteoric water that interacted with the Mesozoic carbonates of the upper reservoir. The δ¹³C values of the CO₂ produced at Larderello and the constant concentration of this gas over time are, however, indicative of a deep source inside the reservoir that is probably related to the decarbonation reaction within the metamorphic units that form the present-day deep reservoir. Fluid inclusion salinities (up to 22.2 wt.% NaCl eq.) and isotopic results (δ¹⁸O from 13.43 to 21.99‰, δ¹³C between −1.26 and −0.18‰) on the calcite veins hosted above the uppermost reservoir suggest that the water circulating in these veins has strongly interacted with Mesozoic carbonates or Neogene sediments containing evaporite layers. The isotopic values (δ¹⁸O from 14.09 to 19.91‰, δ¹³C from −4.09 to 1.90‰) of dolomite samples present in the Paleozoic metamorphic rocks indicate a reaction with fluid of variable temperatures under different water/rock ratios. The isotopic composition of one sample reveals equilibrium with present-day discharge fluids. This fact aside, the remaining data indicate that the Paleozoic dolomitic layers do not seem to contribute significantly to the production of CO₂.     

An oxygen isotope study of silicates in the larderello geothermal field, Italy

Stable-isotope analyses were carried out on hydrothermal minerals sampled from the deep metamorphic units at Larderello, Italy. The ∂¹⁸O values obtained for the most retentive minerals, quartz and tourmaline, are from + 12.0‰ to + 14.7‰ and 9.9‰, respectively, and indicate deposition from an ¹⁸O-rich fluid. Calculated ∂¹⁸O values for these fluids range from + 5.3‰ to + 13.4‰. These values, combined with available fluid inclusion and petrographic data, are consistent with the proposed existence of an early thermal fluid of probable magmatic origin and a late meteoric water. Mixing between these two fluids occurred locally.     

Comparison of carbon dioxide emissions with fluid upflow, chemistry, and geologic structures at the Rotorua geothermal system, New Zealand

During 2002 and 2003, carbon dioxide fluxes were measured across the Rotorua geothermal system in the Taupo Volcanic Zone (TVZ), New Zealand. The results of a 956-measurement survey and of modeling studies show that CO₂ fluxes could be used to determine the main hot fluid upflow areas in Rotorua, and perhaps in undeveloped geothermal regions. Elevated degassing was observed along inferred fault traces and structures, lending confidence to their existence at depth. Degassing was also observed along lineaments that were consistent with the alignment of basement faulting in the TVZ. Areas where elevated degassing was spatially extensive typically overlapped with known regions of hot ground; however, elevated CO₂ fluxes were also observed in isolated patches of non-thermal ground. The total emission rate calculated from sequential Gaussian simulation modeling of CO₂ fluxes across the geothermal system was 620 t d⁻¹ from an 8.9-km² area. However, because approximately one-third of the geothermal system is known to extend beneath Lake Rotorua, we expect the emissions could be minimally on the order of 1000 t d⁻¹. Comparing the emission rate with geochemical analyses of geothermal fluids and estimated upflows suggests that the majority of deep carbon reaches the surface in the form of carbon dioxide gas, and that less than one tenth of the CO₂ emissions is dissolved in, or released from, the fluids at depth. Thus, the geothermal reservoir exerts very little control on deep degassing of CO₂. Carbon isotopic analyses of soil gases suggest a primarily magmatic source for the origin of the CO₂. The total Rotorua emission rate is comparable to those from active volcanoes such as at White Island, New Zealand, and, when normalized by geothermal area, is comparable to other volcanic and hydrothermal regions worldwide.     

Features of low-temperature oxidation of hydrogen in the medium of nitrogen,carbon dioxide,and water vapor at elevated pressures

The article discusses novel research results on combustion features of high-density Н₂/О₂ mixtures (ρ_H2 = 0.70–1.89 mol/dm³, ρ_O2 = 0.32–0.81 mol/dm³) diluted with nitrogen, carbon dioxide, or water vapor (from 46 to 76% mol.) at the uniform heating (1 K/min) of tubular reactor. Based on time dependencies of temperature increment in the reaction mixtures caused by the heat release during oxidation of H₂, it is found that the self-ignition temperature of Н₂/О₂/N₂ and Н₂/О₂/H₂O mixtures is by ≈ 30 K lower than that of the Н₂/О₂/СО₂ mixture. Unlike combustion of H₂ in the N₂ medium, in the CO₂ and H₂O media a chain-thermal explosion is observed at a certain concentration of reagents. The influencing mechanisms of diluents on the H₂ oxidation dynamics, as well as the contribution of homogeneous and heterogeneous reactions in the heat release are revealed. It is established that high heat capacity of H₂/O₂/CO₂ mixture, chemical interaction between its components, and presence of CO₂ molecules adsorbed on the reactor inner surface, are the factors determining the H₂ oxidation dynamics in CO₂ medium. At oxidation of H₂ in the H₂O medium, the process takes place against the background of water evaporation and, as a consequence, is characterized by increased heat capacity and thermal conductivity of the H₂/O₂/H₂O reaction mixture.     

The Tianjin geothermal field (north-eastern China): Water chemistry and possible reservoir permeability reduction phenomena

Injection of spent (cooled) thermal fluids began in the Tianjin geothermal district, north-eastern China, at the end of the 1990s. Well injectivities declined after 3–4 years because of self-sealing processes that reduced reservoir permeability. The study focuses on the factors that may have caused the observed decrease in permeability, using chemical and isotopic data on fluids (water and gas) and mineral phases collected from production and injection wells. The results of data processing and interpretation indicate that (1) it is very unlikely that calcite and silica precipitation is taking place in the reservoir; (2) the Fe- and Zn-rich mineral phases (e.g. sulfides, hydroxides and silicates) show positive saturation indexes; (3) SEM and XRD analyses of filtered material reveal that the latter mineral phases are common; (4) visual observation of casings and surface installations, and of corrosion products, suggests that a poor quality steel was used in their manufacture; (5) significant quantities of solids (e.g. quartz and feldspar crystals) are carried by the geothermal fluid; (6) seasonal changes in fluid composition lead to a reduction in casing corrosion during the summer.     

Assessing innovation in emerging energy technologies: Socio-technical dynamics of carbon capture and storage (CCS) and enhanced geothermal systems (EGS) in the USA

This study applies a socio-technical systems perspective to explore innovation dynamics of two emerging energy technologies with potential to reduce greenhouse gas emissions from electrical power generation in the United States: carbon capture and storage (CCS) and enhanced geothermal systems (EGS). The goal of the study is to inform sustainability science theory and energy policy deliberations by examining how social and political dynamics are shaping the struggle for resources by these two emerging, not-yet-widely commercializable socio-technical systems. This characterization of socio-technical dynamics of CCS and EGS innovation includes examining the perceived technical, environmental, and financial risks and benefits of each system, as well as the discourses and actor networks through which the competition for resources – particularly public resources – is being waged. CCS and EGS were selected for the study because they vary considerably with respect to their social, technical, and environmental implications and risks, are unproven at scale and uncertain with respect to cost, feasibility, and life-cycle environmental impacts. By assessing the two technologies in parallel, the study highlights important social and political dimensions of energy technology innovation in order to inform theory and suggest new approaches to policy analysis.     

A review of the effects of hydrogen,carbon dioxide,and water vapor addition on soot formation in hydrocarbon flames

Addition of reactive or inert substances is one of the most effective and practical ways to control soot formation in combustion of hydrocarbon fuels. In this paper, the research progress on the effects of hydrogen, carbon dioxide, and water vapor addition on soot formation in hydrocarbon flames in the last few decades is systematically summarized. The summary shows that the number of studies on the effects of these three common diluents has increased dramatically in the last five years. Although the overall effects of all these three common diluents suppress soot formation, there is inconsistency with regard to the role of their chemical effects. The chemical effect of hydrogen (CE-H₂) mainly acts on the soot nucleation process, followed by the soot surface growth and finally the soot oxidation process. CE-H₂ seems significantly affected by the fuel type, oxygen concentration, and the ambient pressure. The chemical effect of carbon dioxide (CE-CO₂) affects soot formation indirectly mainly through the reaction CO + OH ↔ CO₂ + H. Some studies believe that CE-CO₂ suppresses soot production by increasing the hydroxyl radical (OH) concentration, while other studies believe that it is primarily attributed to the decrease of the hydrogen radical (H) concentration. The reaction H₂O + H ↔ H₂ + OH plays a vital role in the chemical effect of water vapor (CE-H₂O) addition on inhibiting soot formation. Most studies support the view that the chemical effect of water vapor mainly increases the OH concentration and suppresses soot formation by weakening the soot nucleation process. Moreover, we believe that reaction H₂O + O ↔ OH + OH and phenylacetylene also play an essential effect on the CE-H₂O.     

Partitioning of rare earths and some major elements in the Kizildere geothermal field, Turkey

Rare earth elements and yttrium (REY), Na⁺, K⁺, Cl⁻, and Ca²⁺ were determined in water, steam, mineral scale and rock samples from the Kizildere geothermal field, Turkey. The CO₂-rich parent fluid originates from a sequence of mica schists with marble intercalations. The chemistry of the parent fluid varies with location and time. The average REY composition of the fluids is derived by extrapolation to the lowest Ca concentrations. The apparent vapor–liquid partitioning factors for REY at 145 °C and 5 bar total absolute pressure are about 0.2, whereas for Ca²⁺, Na⁺, K⁺ and Cl⁻ they are <0.05, about 0.0005, 0.0005 and about 0.02, respectively. Apparent scale-liquid distribution coefficients for REY at 145 and 190 °C are about 0.15 and 0.55, whereas at 100 °C they increase from 0.3 (La) to 1.5 (Lu).     

Vapour/liquid fractionation of rare earths,Y, Na,K, NH4, Cl,HCO3, SO4 and borate in fluids from the Piancastagnaio geothermal field,Italy

Vapour/liquid fractionation of rare earth elements and yttrium (REY), Na⁺, K⁺, NH₄⁺, HCO₃⁻, SO₄²⁻, Cl⁻ and borate in geothermal fluids from the Piancastagnaio geothermal field (Mt. Amiata geothermal area, Tuscany, central Italy) were evaluated based on the chemistry of collected liquids and condensed vapours. Apparent vapour–liquid partitioning factors (^appD^V/L) of REY vary from 0.3 to 0.01. These factors are much higher than those of Na (<0.001) and K (∼0.001). Volatile components are ion pairings such as NH₄HCO₃^o, NH₄Cl^o, NaHCO₃^o, CaSO₄^o and REYO(HCO)₃^o ⇔ REY(OH)CO₃^o. In vapour, REY and NH₄⁺ are negatively correlated. High and low ^appD^V/L(REY) indicate variations of NH₄⁺ concentrations in liquids. The results of this study are relevant to the understanding of element migration and deposition under hydrothermal boiling conditions.