Degradation mechanisms affecting non-methane volatile organic compounds (VOCs) during gas uprising from different hypogenic sources to the surface were investigated through extensive sampling surveys ...in areas encompassing a high enthalpy hydrothermal system associated with active volcanism, a CH4-rich sedimentary basin and a municipal waste landfill. For a comprehensive framework, published data from medium-to-high enthalpy hydrothermal systems were also included. The investigated systems were characterised by peculiar VOC suites that reflected the conditions of the genetic environments in which temperature, contents of organic matter, and gas fugacity had a major role. Differences in VOC patterns between source (gas vents and landfill gas) and soil gases indicated VOC transformations in soil. Processes acting in soil preferentially degraded high-molecular weight alkanes with respect to the low-molecular weight ones. Alkenes and cyclics roughly behaved like alkanes. Thiophenes were degraded to a larger extent with respect to alkylated benzenes, which were more reactive than benzene. Furan appeared less degraded than its alkylated homologues. Dimethylsulfoxide was generally favoured with respect to dimethylsulfide. Limonene and camphene were relatively unstable under aerobic conditions, while α-pinene was recalcitrant. O-bearing organic compounds (i.e., aldehydes, esters, ketones, alcohols, organic acids and phenol) acted as intermediate products of the ongoing VOC degradations in soil. No evidence for the degradation of halogenated compounds and benzothiazole was observed. This study pointed out how soil degradation processes reduce hypogenic VOC emissions and the important role played by physicochemical and biological parameters on the effective VOC attenuation capacity of the soil.
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•The composition of hypogenic gases depends on the genetic environment conditions.•Hypogenic light, non-alkylated and oxidised compounds are favoured in the soil.•Hypogenic heavy and alkylated species are preferentially degraded in the soil.•Soil processes are (co-)metabolic/hydrogenation/dealkylation/oxidation reactions.•They depend on local soil conditions and not on the CO2 and CH4 flux values.
We have addressed the origins of methane in fumarolic, thermal and cold emissions discharging from a diversity of geological settings spread all over the Italian Peninsula and at Panarea and ...Pantelleria islands. Fluid discharges from the main geothermal systems of the peri-Tyrrhenian area (including Mt. Amiata, Larderello, Latera and Manziana) show δ13C-CH4 and δD-CH4 values >−28‰ V-PDB and >−160‰ V-SMOW, respectively, and C1/C2+ concentration ratios >1000. These patterns suggest that CH4 discharged from these systems is primarily generated by abiogenic reduction of CO2 and/or CO. Methane seems to have, at least partially, a different origin than the higher hydrocarbons that might be entirely related to the thermal decomposition of organic matter or, alternatively, to methane polymerization. Fumaroles from the volcanic systems of Solfatara, Vesuvio, Panarea and Pantelleria have C1/C2+ concentration ratios in a wide range (from 17 to 4300), but δ13C-CH4 and δD-CH4 values >−21‰ V-PDB and >−120‰ V-SMOW, respectively. Such isotopic values are very similar to those reported for CH4 discharging from ultramafic hydrothermal systems. In agreement with recent evidence provided for Solfatara and Pantelleria we, therefore, infer that the CH4 in the volcanic fumaroles is mainly abiogenic, too. The δ13C-CH4 (from −21.6 to −36.9‰ V-PDB) and δD-CH4 (from −113 to −164‰ V-SMOW) values, as well as the C1/C2+ concentration ratios (from 19 to 2240), in the CO2-rich fluid discharges located between the geothermal-volcanic systems and the Apennine sedimentary chain tend to decrease eastwards as the temperatures of the fluid reservoirs progressively diminish, suggesting that the CH4 production is mainly related to thermogenic processes. According to this general trend, the CH4-dominated fluids from mud volcanoes located eastwards of the CO2-rich emissions are fed by an almost pure thermogenic source. The easternmost fluid discharges from the Po valley and the Adriatic coast, where organic matter evolves at relatively shallow depths in the presence of a low geothermal gradient, record the lowest δ13C-CH4 and δD-CH4 values, i.e. as low as −69‰ V-PDB and <−190‰ V-SMOW, respectively, and C1/C2+ concentration ratios up to 5500, suggesting that the CH4 production is mainly from microbially driven processes.
► We present original isotopic data (CH4 and CO2) in natural gas discharges of Italy. ► We investigate the origins and mechanisms of CH4 production in natural systems. ► Methane in fluids from volcanic/geothermal systems is mainly abiogenic. ► Hydrothermal fluids of medium enthalpy have thermogenic CH4. ► Biogenic CH4 dominates in fluids from the Po Plain and the Adriatic coast.
Landfills for solid waste disposal release to the atmosphere a large variety of volatile organic compounds (VOCs). Bacterial activity in landfill cover soils can play an important role in mitigating ...VOC emission. In order to evaluate the effects of degradation processes and characterize VOCs composition in landfill cover soil, gases from 60 sites and along 7 vertical profiles within the cover soil were collected for chemical and isotopic analysis at two undifferentiated urban solid waste disposal sites in Spain: (i) Pinto (Madrid) and (ii) Zurita (Fuerteventura, Canary Islands). The CO2/CH4 ratios and δ13C-CO2 and δ13C-CH4 values were controlled by either oxidation or reduction processes of landfill gas (LFG). VOCs were dominated by aromatics, alkanes and O-substituted compounds, with minor cyclics, terpenes, halogenated and S-substituted compounds. Degradation processes, depending on both (i) waste age and (ii) velocity of the uprising biogas through the soil cover, caused (i) an increase of degradation products (e.g., CO2, O-substituted compounds) and (ii) a decrease of degradable components (e.g., CH4, alkanes, alkylated aromatics, cyclic and S-substituted compounds). Terpenes, halogenated compounds, phenol and furans were unaffected by degradation processes and only depended on waste composition. These results highlight the fundamental role played by microbial activity in mitigating atmospheric emissions of VOCs from landfills. Nevertheless, the recalcitrant behaviour shown by compounds hazardous for health and environment remarks the importance of a correct landfill management that has to be carried out for years after the waste disposal activity is completed, since LFG emissions can persist for long time.
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•Greenhouse and toxic organic gases are produced from landfills.•Most organic gases are degraded passing through cover soils.•O-substituted compounds and benzene are secondarily produced within cover soils.•Most heteroatomic organic compounds are recalcitrant at oxidizing conditions.•Cover soils can effectively reduce organic gas emission from the landfills.
Volcanoes are currently to be regarded as natural sources of air pollutants. Climatic and environmental forcing of large volcanic eruptions are well known, although gases emitted through passive ...degassing during periods of quiescence or hydrothermal activity can also be highly dangerous for the environment and public health. Based on compositional and isotopic data, a survey on the spatial distribution in air of the main volatile compounds of carbon (CO2 and CH4) and sulfur (H2S and SO2) emitted from the fumarolic field of Pisciarelli (Campi Flegrei, Pozzuoli, Naples), a hydrothermal area where degassing activity has visibly increased since 2009, was carried out. The main goals of this study were (i) to evaluate the impact on air quality of these natural manifestations and (ii) inquire into the behavior of the selected chemical species once released in air, and their possible use as tracers to distinguish natural and anthropogenic sources. Keeling plot analysis of CO2 and CH4 isotopes revealed that the hydrothermal area acts as a net source of CO2 in air, whilst CH4 originated mainly from anthropogenic sources. Approaching the urban area, anthropogenic sources of CO2 increased and, at distances greater than 800 m from the Pisciarelli field, they prevailed over the hydrothermal signal. While hydrothermal CO2 simply mixed with that in the atmospheric background, H2S was possibly affected by oxidation processes. Therefore, SO2 measured in the air near the hydrothermal emissions had a secondary origin, i.e. generated by oxidation of hydrothermal H2S. Anthropogenic SO2 was recognized only in the furthest measurement site from Pisciarelli. Finally, in the proximity of a geothermal well, whose drilling was in progress during our field campaign, the H2S concentrations have reached values up to 3 orders of magnitude higher than the urban background, claiming the attention of the local authorities.
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•CO2, CH4, H2S, SO2 mole fractions in air, and δ13C isotopes, were measured in Pisciarelli.•CO2 and H2S concentrations in air were mainly related to the hydrothermal system emissions.•CO2 mixed with both the local background and anthropogenic sources.•CH4 emissions were likely governed by anthropogenic sources from the city.•SO2 concentrations were governed both from consumption of H2S and anthropogenic sources.
659 water samples from springs and wells in the Sabatini and Vicano-Cimino Volcanic Districts (central Italy) were analyzed for arsenic (As), fluoride (F−) and radon (222Rn) concentrations. Waters ...mostly sourced from a shallow and cold aquifer hosted within volcanic rocks, which represents the main public drinking water supply. Cold waters from perched aquifers within sedimentary formations and thermal waters related to a deep hydrothermal reservoir were also analyzed. The highest concentrations of As and F− were measured in the thermal waters and attributed to their enhanced mobility during water-rock interaction processes at hydrothermal temperatures. Relatively high concentrations of As and F− were also recorded in those springs and wells discharging from the volcanic aquifer, whereas waters hosted in the sedimentary units showed significantly lower contents. About 60% (As) and 25% (F−) of cold waters from the volcanic aquifer exceeded the maximum allowable concentrations for human consumption. Such anomalously high levels of geogenic pollutants were caused by mixing with fluids upwelling through faulted zones from the hydrothermal reservoir. Chemical weathering of volcanic rocks and groundwater flow path were also considered to contribute to the observed concentrations. Cold waters from the volcanic aquifer showed the highest 222Rn concentrations, resulting from the high contents of Rn-generating radionuclides in the volcanic units. Approximately 22% of these waters exceeded the recommended value for human consumption. A specific Quality Index (QI), comprised between 1 (very low) and 4 (very high), was computed for each water on the basis of As, F− and 222Rn concentrations and visualized through a spatial distribution map processed by means of geostatistical techniques. This map and the specific As, F− and 222Rn maps can be regarded as useful tools for water management by local authorities to both improve intervention plans in contaminated sectors and identify new water resources suitable for human consumption.
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•Volcanic-sedimentary aquifers from Central Italy were analyzed for As, F− and 222Rn.•Water-rock interaction and input of thermal fluids are sources of geogenic pollutants.•High contents of geogenic pollutants were pertaining to the volcanic aquifers.•Quality Indexes (QIs) were obtained by combining the As, F− and 222Rn concentrations.•QI distribution maps can be used for water management in geogenically polluted areas.
Spatial distribution maps of geogenic pollutants (As, F− and 222Rn) and quality indexes for water resources were determined in volcanic-sedimentary aquifers of central Italy for water management.
Arsenic concentrations were analysed for 328 water samples collected in the Vicano–Cimino Volcanic District (VCVD), an area where severe contamination of groundwater has become a serious problem ...following the recent application of the EU Directive on the maximum allowable concentration level for As in drinking waters. In addition, uranium and vanadium concentrations were also analysed in light of the enhanced interest on their environmental toxicity. Waters were collected from springs and wells fed by cold and shallow volcanic–sedimentary aquifers, which locally represent the main drinking water source. Thermal springs (≤63°C) related to an active hydrothermal reservoir and waters associated with a CO2-rich gas phase of deep provenance were also analysed. The collected data showed that the As concentrations in the shallow aquifers varied in a wide range (0.05–300μg/L) and were primarily controlled by water–rock interaction processes. High As concentrations (up to 300μg/L) were measured in springs and wells discharging from the volcanic products, and about 66% exceeded the limit of 10μg/L for drinking waters, whereas waters circulating within the sedimentary formations displayed much lower values (0.05–13μg/L; ~4% exceeding the threshold limit). Thermal waters showed the highest As concentrations (up to 610μg/L) as the result of the enhanced solubility of As-rich volcanic rocks during water–rock interaction processes at high temperatures. Where the local structural setting favoured the rise of fluids from the deep hydrothermal reservoir and their interaction with the shallow volcanic aquifer, relatively higher concentrations were found. Moreover, well overexploitation likely caused the lateral inflow of As-rich waters towards not contaminated areas.
Uranium and vanadium concentrations of waters circulating in the volcanic rocks ranged from 0.01 to 85μg/L and 0.05 to 62μg/L, respectively. Less than 2% of analysed samples exceeded the World Health Organization's provisional guidelines for U (30μg/L), while none of them was above the Italian limit value of V in drinking water (120μg/L). Lower U (0.07–22μg/L and 0.02–13μg/L, respectively) and V concentrations (0.05–24μg/L and 0.18–17μg/L, respectively) were measured in the water samples from the sedimentary aquifer and thermal waters. Local lithology appeared as the main factor affecting the U and V contents in the shallow aquifers, due to the high concentrations of these two elements in the volcanic formations when compared to the sedimentary units. In addition, high U concentrations were found in correspondence with U mineralization occurring within the VCVD, from which U is released in solution mainly through supergene oxidative alteration. Redox conditions seem to play a major role in controlling the concentrations of U and V in waters. Oxidizing conditions characterizing the cold waters favour the formation of soluble U- and V-species, whereas thermal waters under anoxic conditions are dominated by relatively insoluble species. Geostatistical techniques were used to draw contour maps by using variogram models and kriging estimation aimed to define the areas of potential health risk characterized by As, U and V-rich waters, thus providing a useful tool for water management in a naturally contaminated area to local Authorities.
•We analysed the As, U and V contents of waters emerging around Lake Vico (Italy).•Waters emerge both from cold shallow volcanic–sedimentary and deep geothermal aquifers.•Water–rock interactions mostly control the As, U and V contents in shallow aquifers.•Volcanic rocks and mineralized areas are the main sources of As, U and V in solution.•Geostatistical techniques were used for the elaboration of concentration maps.
Volcanic and hydrothermal areas largely contribute to the natural emission of greenhouse gases to the atmosphere, although large uncertainties in estimating their global output still remain. ...Nevertheless, CO2 and CH4 discharged from hydrothermal fluid reservoirs may support active soil microbial communities. Such secondary processes can control and reduce the flux of these gases to the atmosphere. In order to evaluate the effects deriving from the presence of microbial activity, chemical and carbon (in CO2 and CH4) isotopic composition of interstitial soil gases, as well as diffuse CO2 fluxes, of three hydrothermal systems from Italy were investigated, i.e. (i) Solfatara crater (Campi Flegrei), (ii) Monterotondo Marittimo (Larderello geothermal field) and (iii) Baia di Levante in Vulcano Island (Aeolian Archipelago), where soil CO2 fluxes up to 2400, 1920 and 346 g m−2 day−1 were measured, respectively. Despite the large supply of hydrothermal fluids, 13CO2 enrichments were observed in interstitial soil gases with respect to the fumarolic gas discharges, pointing to the occurrence of autotrophic CO2 fixation processes during the migration of deep-sourced fluids towards the soil-air interface. On the other hand, (i) the δ13C-CH4 values (up to ~48‰ vs. V-PDB higher than those measured at the fumarolic emissions) of the interstitial soil gases and (ii) the comparison of the CO2/CH4 ratios between soil gases and fumarolic emissions suggested that the deep-sourced CH4 was partly consumed by methanotrophic activity, as supported by isotope fractionation modeling. These findings confirmed the key role that methanotrophs play in mitigating the release of geogenic greenhouse gases from volcanic and hydrothermal environments.
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•Greenhouse gases are released from hydrothermal systems through diffuse degassing.•Carbon in CO2 from soil gases is isotopically heavier than that from fumaroles.•CO2/CH4 ratios in soil gases are higher than those measured in fumarolic emissions.•Autotrophs and methanotrophs mitigate the release of geogenic greenhouse gases.•Microbes contribute to regulate CH4 (and CO2) emissions from hydrothermal areas.
Saline-alkaline lakes of the East African Rift are known to have an extremely high primary production supporting a potent carbon cycle. To date, a full description of carbon pools in these lakes is ...still missing. More specifically, there is not detailed information on the quality of dissolved organic matter (DOM), the main carbon energy source for heterotrophs prokaryotes. We report the first exhaustive description of DOM molecular properties in the water column of a meromictic saline-alkaline lake of the East African Rift. DOM availability, fate and origin were studied either quantitatively, in terms of dissolved organic carbon (DOC) and nitrogen (DON) or qualitatively, in terms of optical properties (absorbance) and molecular characterization of solid-phase extracted DOM (SPE-DOM) through negative electrospray ionization Fourier-transform ion cyclotron resonance mass spectrometry (FT-ICR-MS). DOM availability was high (DOC ∼ 8.1 mM in surface waters) and meromixis imprinted a severe quantitative and qualitative change on DOM pool. At the surface, DOM was rich in aliphatic and moderately in aromatic molecules and thus mirroring autochthonous microbial production together with photodegradation. At the bottom changes were extreme: DOC increased up to 5 times (up to 50 mM) and, molecular signature drifted to saturated, reduced and non-aromatic DOM suggesting intense microbial activity within organic sediments. At the chemocline, DOC was retained indicating that this interface is a highly reactive layer in terms of DOM processing. These findings underline that saline-alkaline lakes of the East African Rift are carbon processing hot spots and their investigation may broaden our understanding of carbon cycling in inland waters at large.
•First detailed description of DOM in a tropical meromictic saline-alkaline lake.•High amount of autochthonous DOM was found in water column.•Solid-phase extracted DOM is microbially derived, photodegraded and aliphatic.•Changes in DOM quantity and quality were located at the chemocline.
Copahue volcano is part of the Caviahue–Copahue Volcanic Complex (CCVC), which is located in the southwestern sector of the Caviahue volcano-tectonic depression (Argentina–Chile). This depression is ...a pull-apart basin accommodating stresses between the southern Liquiñe–Ofqui strike slip and the northern Copahue–Antiñir compressive fault systems, in a back-arc setting with respect to the Southern Andean Volcanic Zone. In this study, we present chemical (inorganic and organic) and isotope compositions (δ13C-CO2, δ15N, 3He/4He, 40Ar/36Ar, δ13C-CH4, δD-CH4, and δD-H2O and δ18O-H2O) of fumaroles and bubbling gases of thermal springs located at the foot of Copahue volcano sampled in 2006, 2007 and 2012. Helium isotope ratios, the highest observed for a Southern American volcano (R/Ra up to 7.94), indicate a non-classic arc-like setting, but rather an extensional regime subdued to asthenospheric thinning. δ13C-CO2 values (from −8.8‰ to −6.8‰ vs. V-PDB), δ15N values (+5.3‰ to +5.5‰ vs. Air) and CO2/3He ratios (from 1.4 to 8.8×109) suggest that the magmatic source is significantly affected by contamination of subducted sediments. Gases discharged from the northern sector of the CCVC show contribution of 3He-poor fluids likely permeating through local fault systems. Despite the clear mantle isotope signature in the CCVC gases, the acidic gas species have suffered scrubbing processes by a hydrothermal system mainly recharged by meteoric water. Gas geothermometry in the H2O-CO2-CH4-CO-H2 system suggests that CO and H2 re-equilibrate in a separated vapor phase at 200°–220°C. On the contrary, rock–fluid interactions controlling CO2, CH4 production from Sabatier reaction and C3H8 dehydrogenation seem to occur within the hydrothermal reservoir at temperatures ranging from 250° to 300°C. Fumarole gases sampled in 2006–2007 show relatively low N2/He and N2/Ar ratios and high R/Ra values with respect to those measured in 2012. Such compositional and isotope variations were likely related to injection of mafic magma that likely triggered the 2000 eruption. Therefore, changes affecting the magmatic system had a delayed effect on the chemistry of the CCVC gases due to the presence of the hydrothermal reservoir. However, geochemical monitoring activities mainly focused on the behavior of inert gas compounds (N2 and He), should be increased to investigate the mechanism at the origin of the unrest started in 2011.
•We present the compositional data of gases from Copahue volcano (Argentina).•Helium and CO2 have a MORB isotopic signature.•Nitrogen mainly derived from subducted sediments.•A geochemical conceptual model is proposed.•Indications for the geochemical monitoring during the present unrest are provided.
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