Abstract: Carbon dioxide and CH(4), C(6)H(6) and C(7)H(8) fluxes from the soil cover of Case Passerini landfill site (Florence, Italy) were measured using the accumulation and static closed chamber methods, respectively. Results show that the CH(4)/CO(2), CH(4)/C(6)H(6) and CH(4)/C(7)H(8) ratios of the flux values are relatively low when compared with those of the 'pristine' biogas produced by degradation processes acting on the solid waste material disposed in the landfill. This suggests that when biogas transits through the cover soil, CH(4) is affected by degradation processes activated by oxidizing bacteria at higher extent than both CO(2) and mono-aromatics. Among the investigated hydrocarbons, C(6)H(6) has shown the highest stability in a wide range of redox conditions. Toluene behaviour only partially resembles that of C(6)H(6), possibly because de-methylation processes require less energy than that necessary for the degradation of C(6)H(6), the latter likely occurring via benzoate at anaerobic conditions and/or through various aerobic metabolic pathways at relatively shallow depth in the cover soil where free oxygen is present. According to these considerations, aromatics are likely to play an important role in the environmental impact of biogas released into the atmosphere from such anthropogenic emission sites, usually only ascribed to CO(2) and CH(4). In this regard, flux measurements using accumulation and static closed chamber methods coupled with gas chromatography and gas chromatography-mass spectrometry analysis may properly be used to obtain a dataset for the estimation of the amount of volatile organic compounds dispersed from landfills.
Abstract: The composition of non-methane organic volatile compounds (VOCs) determined in 139 thermal gas discharges from 18 different geothermal and volcanic systems in Italy and Latin America, consists of C(2)-C(20) species pertaining to the alkanes, alkenes, aromatics and O-, S- and N-bearing classes of compounds. Thiophenes and mono-aromatics, especially the methylated species, are strongly enriched in fluids emissions related to hydrothermal systems. Addition of hydrogen sulphide to dienes and electrophilic methylation involving halogenated radicals may be invoked for the formation of these species. On the contrary, the formation of furans, with the only exception of C(4)H(8)O, seems to be favoured at oxidizing conditions and relatively high temperatures, although mechanisms similar to those hypothesized for the production of thiophenes can be suggested. Such thermodynamic features are typical of fluid reservoirs feeding high-temperature thermal discharges of volcanoes characterised by strong degassing activity, which are likely affected by conspicuous contribution from a magmatic source. The composition of heteroaromatics in fluids naturally discharged from active volcanoes and geothermal areas can then be considered largely dependent on the interplay between hydrothermal vs. magmatic contributions. This implies that they can be used as useful geochemical tools to be successfully applied in both volcanic monitoring and geothermal prospection.
Abstract: Geological storage is presently one of the most promising options for reducing anthropogenic emissions of CO2. Among the several projects investigating the fate Of CO2 stored at depth, the EnCana's CO2 injection EOR (Enhancing Oil Recovery) project at Weyburn (Saskatchewan, Canada) is the most important oil production development that hosts an international monitoring project. In the Weyburn EOR Project CO2 is used to increase recovery of heavy oil from the Midale Beds, a Mississippian reservoir consisting of shallow marine carbonate, where about 3 billions standard m(3) of supercritical CO2 have been injected since 2000 with an injection rate of 5000 ton/day. In this work the available dataset (bulk mineralogy of the reservoir, gas-cap composition and selected pre- and post-CO2 injection water samples) provided by the International Energy Agency Weyburn CO2 Monitoring & Storage Project has been used in order to: i) reconstruct the pre-injection reservoir chemical composition (including pH and the boundary conditions at 62 degrees C and 15 MPa); ii) assess the evolution of the reservoir subjected to CO2 injection and predict dissolution/precipitation processes of the Weyburn brines over 100 years after injection; iii) validate the short-term (September 2000-2003) evolution of the in situ reservoir fluids due to the CO2 injection, by comparing the surface analytical data with the composition of the computed depressurized brines. To achieve these goals the PRHEEQC (V2.14) Software Package was used with both modified thermodynamic database and correction for supercritical CO2 fugacity. The oil-gas-water interaction and the non-ideality of the gas phase (with exception of CO2) were not considered in the numerical simulations. Despite intrinsic limitations and uncertainties of geochemical modeling, the main results can be summarized, as follows: 1) the calculated pre-injection chemical composition of the Midale Beds brine is consistent with the analytical data of the waters collected in 2000 (baseline survey), 2) the main reservoir reactions (CO2. and carbonate dissolution) take place within the first year of simulation, 3) the temporal evolution of the chemical features of the fluids in the Weyburn reservoir suggests that CO2 can safely be stored by solubility (as CO2(aq)) and mineral trapping (via dawsonite precipitation). The short-term validation performed by calculating chemical composition of the reservoir fluids (corrected for surface conditions) after the simulation of 3 years Of CO2 injection is consistent (error <= 5%) with the analytical data of the wellhead water samples collected in 2003, with the exception of Ca and Mg (error >90%), likely due to complexation effect of carboxilic acid. (C) 2009 Elsevier B.V. All rights reserved.
Abstract: A geochemical survey of thermal waters collected from submarine vents at Panarea Island (Aeolian islands, southern Italy) was carried out from December 2002 to March 2007, in order to investigate (i) the geochemical processes controlling the chemical composition of the hydrothermal fluids and (ii) the possible relations between the chemical features of the hydrothermal reservoir and the activity of the magmatic system. Compositional data of the thermal water samples were integrated in a hydrological conceptual model, which describes the formation of the vent fluid by mixing of seawater, seawater concentrated by boiling, and a deep, highly-saline end-member, whose composition is regulated by water-rock interactions at relatively high temperature and shows clear clues of magmatic-related inputs. The chemical composition of concentrated seawater was assumed to be represented by that of the water sample having the highest Mg content. The composition of the deep end-member was instead calculated by extrapolation assuming a zero-Mg end-member. The Na-K-Ca geothermometer, when applied to the thermal end-member composition, indicated an equilibrium temperature of approximately 300 degrees C, a temperature in agreement with the results obtained by gas-geothermometry. (c) 2008 Elsevier Ltd. All rights reserved.
Abstract: Waters and dissolved gases collected along vertical profiles in the five basins ( Main, Kabuno Bay, Kalehe, Ishungu, and Bukavu) forming the 485 m deep Lake Kivu ( Democratic Republic of the Congo) were analyzed to provide a geochemical conceptual model of the several processes controlling lake chemistry. The measured horizontal and vertical variations of water and gas compositions suggest that each basin has distinct chemical features produced by ( 1) different contribution from long circulating fluid system containing magmatic CO2, responsible of the huge CO2(CH4)-rich reservoir hosted within the deep lake water; ( 2) spatial variations of the biomass distribution and/or speciation; and ( 3) solutes from water-rock interactions. The Kabuno Bay basin is characterized by the highest rate of magmatic fluid input. Accordingly, this basin must be considered the most hazardous site for possible gas outburst that could be triggered by the activity of the Nyiragongo and Nyamulagira volcanoes, located a few kilometers north of the lake.
Abstract: The composition of non-methane volatile organic compounds (hereafter VOCs) in i) the cover soil, at depths of 30, 50 and 70 cm, and ii) gas recovery wells from Case Passerini landfill site, (Florence, Italy) was determined by GC-MS. The study, based on the analysis of interstitial gases sampled along vertical profiles within the cover soil, was aimed to investigate the VOC behaviour as biogas transits from a reducing to a relatively more oxidizing environment. A total of 48 and 63 different VOCs were identified in the soil and well gases, respectively. Aromatics represent the dominant group (71.5% of total VOC) in soil gases, followed by alkanes (6.8%), ketones (5.7%), organic acids (5.2%), aldehydes (3.0%), esters (2.6%), halogenated compounds (2.1%) and terpenes (1.3%). Cyclics, heterocyclics, S-bearing compounds and phenols are In the wells the VOC composition is characterized by higher concentrations of cyclic (7.6%) and S-bearing compounds (2%) and lower concentrations of C-bearing compounds. The vertical distribution of VOCs in the cover soil shows significant variations: alkanes, aromatics and cyclics decrease at decreasing depth, whereas an inverse trend is displayed by the O-bearing species. Total VOC and CH4 concentrations at a depth of 30 cm in the soil are comparable. inferring that microbial activity is likely affecting VOCs at a very minor extent with respect to CH4. According to these considerations, to assess the biogas emission impact, usually carried out on the sole basis of CO2 and CH4 emission rates, the physical-chemical behaviour of VOCs in the cover soil, regulating the discharge of these highly contaminant compounds in ambient air, has to be taken into account. The soil vertical distribution of these species can be used to better evaluate the efficiency of oxidative capability of intermediate and final covers. (C) 2009 Elsevier B.V. All rights reserved.
Abstract: The compositional features of fluids from both fumarolic discharges and productive geothermal wells of Ahuachapan-Chipilapa, Berlin-Chinameca, and San Vicente geothermal systems ( El Salvador) are described and discussed in order to investigate the complex geochemical interactions involving geothermal fluids within the shallowest part of the hydrothermal circulation pathways. Our results highlight that secondary processes are able to strongly affect and modify the chemical characteristics of geothermal gases once they discharge to the surface as natural manifestations, mainly in relation to the chemical-physical properties of each gas species. The effects of both gas dissolution in shallow aquifers and gas-water-rock chemical interactions on gas discharge composition make it difficult to get a correct evaluation of the thermodynamic conditions that characterize the geothermal reservoirs by applying the common geoindicators based on the chemical equilibria of the H2O-CO2-H-2-CH4-CO system. Differently, the composition of the C-1-C-2-C-3 alkanes and the C-3 and C-4 alkane-alkene pair, established within the geothermal reservoirs under the control of chemical reactions, remains stable in samples collected from discharging gas vents. These results suggest that the relative abundances of hydrocarbons characterized by similar structure and molecular size seem to be mainly regulated by the diffusion velocity of gases through the liquid-dominated system. Therefore the chemical features of the light organic gas fraction of naturally discharging fluids can be successfully utilized for the evaluation of geothermal reservoir temperatures and redox conditions, providing useful indications in terms of geothermal exploration and exploitation. On this basis, the distribution, speciation, and relative abundances of light hydrocarbons can also be considered highly promising in geochemical monitoring of active volcanic systems.
Abstract: A new analytical method for the determination of the sulfur species (SO2, H2S, S80) in volcanic gases is proposed by revising, updating, and improving previous methods. The most significant advantages of the proposed procedure can briefly be summarized, as follows: (i) the reaction among sulfur species stops during the gas sampling by using preevacuated thorion-tapped vials with purified 0.15M Cd(OH)2 in 4 M NaOH to favor the precipitation of H2S as CdS; (ii) all the sulfur species (SO2, H2S, S80) are analyzed by ion chromatography, after conversion to SO4, which allows the detection limit to be lowered significantly with respect to the previous studies; (iii) appropriate aliquots from intermediate steps may be used to determine other species commonly present in volcanic gases such as CO2, HCl, HF, HBr, HI, and so forth; (iv) determination of all the other gas species is not jeopardized by the proposed method, i.e., one single vial can be used for analyzing the full chemical composition of a volcanic gas with the exception of NH3. Statistical parameters calculated from gas sampling data at the F5 crater fumarole in Vulcano Island (Aeolian Islands, southern Italy), suggest that the standard error of mean (s/ ?n) is higher for S (0.10), followed by SO2, H2S, and CO2 (0.04, 0.038, and 0.028, respectively). SO2 shows the higher variation coefficient (12.1%) followed by H2S, S, and CO2 (5.7, 1.5, and 0.8%, respectively). Furthermore, if the time dependence of sampling is taken into account, the measured values, instead of fluctuating in a random manner, tend to follow systematic patterns, out of statistical control, possibly suggesting a sort of natural fluctuation of the volcanic system. Other crater fumaroles from volcanic systems located in different geodynamical areas (Hawaii, USA, El Chichon, Mexico, Poas, Costa Rica) have been analyzed as well.
Abstract: We report the results of a geochemical survey of fumaroles, thermal springs, and gas discharges from areas in and around the active crater lake of Poa?s volcano (Costa Rica) from February 1998 to February 2001. The springs are highly acidic-sulphate waters with temperatures approaching boiling point, whereas gas chemistry is characterized by typical magmatic species, such as SO2, HF, HCl, H2, and CO. From February 1998 new fumarolic fields formed inside the southern part of the crater. They moved anticlockwise from the S to the NE inner walls of the crater, while those located in the southern part of the crater and close to the pyroclastic cone south of the crater lake diminished or disappeared altogether, during 1999 and 2000. This shift was also characterized by chemical variation of the magmatic gas species. In spite of the chemical changes of fumaroles, the composition of the lake changed little during this time. This fact, together with the chemical profile with depth of the lake, suggests that the lake is a very efficient condenser of magmatic fluids. An apparent chemical stratification of the lake suggests that dilution with meteoric water is not complete, due to the presence of liquid sulphur at the lake bottom and/or due to the continuous influx of new magmatic components.
