Determining Seasonal Natural Effects over Isotopic Baselines for CO2 Storage Monitoring

AbstractDissolved carbon stable isotopes in surface waters can be utilized as a monitoring tool of CO2 geological storage and as a good indicator of potential CO2 leakages, since each source of carbon has a specific isotopic signature. The isotopic carbon baseline value and its range will determine whether the situation responds to a leak or a natural modification as part of the system's annual cycle and its seasonal effects. We measured water temperature, pH, dissolved inorganic carbon (DIC) concentration and other geochemical variables, during the different annual stages, in order to characterize the contribution of different sources of carbon to the natural isotopic evolution of DIC in the area of Hontomin. This area is the selected site for the Spanish research facility for CO2 geological storage operated by CIUDEN. The average value for δ13C-DIC at the study site is -10.7 ‰ (V-PDB), which is very different of the CO2 generated during the oxycombustion process (about -28 ‰ vs V-PDB). After statistical analysis of the sampling efforts, we observed light differences on their average isotopic values which imply certain seasonal effects, although we could not find effects over the DIC concentration

Hunting long-lived gluinos at the Pierre Auger Observatory

A ps version of the paper with high resolution figures is available at: http://www.hep.physics.neu.edu/staff/doqui/rhadron_highres.psEventual signals of split sypersymmetry in cosmic ray physics are analyzed in detail. The study focusses particularly on quasi-stable colorless R-hadrons originating through confinement of long-lived gluinos (with quarks, anti-quarks, and gluons) produced in pp collisions at astrophysical sources. Because of parton density requirements, the gluino has a momentum which is considerable smaller than the energy of the primary proton, and so production of heavy (mass ~ 500 GeV) R-hadrons requires powerful cosmic ray engines able to accelerate particles up to extreme energies, somewhat above 10^{13.6} GeV. Using a realistic Monte Carlo simulation with the AIRES engine, we study the main characteristics of the air showers triggered when one of these exotic hadrons impinges on a stationary nucleon of the Earth atmosphere. We show that R-hadron air showers present clear differences with respect to those initiated by standard particles. We use this shower characteristics to construct observables which may be used to distinguish long-lived gluinos at the Pierre Auger Observatory.Peer reviewe

Revisiting the Hubble sequence in the SDSS DR7 spectroscopic sample: a publicly available bayesian automated classification

We present an automated morphological classification in 4 types (E,S0,Sab,Scd) of ~700.000 galaxies from the SDSS DR7 spectroscopic sample based on support vector machines. The main new property of the classification is that we associate to each galaxy a probability of being in the four morphological classes instead of assigning a single class. The classification is therefore better adapted to nature where we expect a continuos transition between different morphological types. The algorithm is trained with a visual classification and then compared to several independent visual classifications including the Galaxy Zoo first release catalog. We find a very good correlation between the automated classification and classical visual ones. The compiled catalog is intended for use in different applications and can be downloaded at http://gepicom04.obspm.fr/sdss_morphology/Morphology_2010.html and soon from the CasJobs database.Comment: A&A in press, english corrections from language editor adde

Tracking the oxygen isotopic signature from the rainfall to the speleothems in Ortigosa de Cameros caves (La Rioja, Spain)

A one-year monitoring survey has been carried out in La Paz and La Vin~a Caves in the Ortigosa de Cameros Cave System (NE Iberian Peninsula), in order to track the oxygen isotope signal from rainfall to speleothem calcite, assessing the ability of this signal to retain environmental information. Oxygen isotope signals of rainfall events, drip water —sampled every three months—, and speleothem calcite, precipitated over three-months, are com- pared. Water dripping follows precipitation events in winter, spring and summer, more closely in the near-surface drip points than in the deeper ones. In autumn, dripping is delayed with respect to rainfall, suggesting that water stays in the epikarst before dripping resumes after summer. This delay causes a deviation of the total drip water sig- nal (average d18O=-8.39‰ V-SMOW) from the rainfall signal (average d18O=-7.41‰ V-SMOW). On the contrary, in winter the isotopic signal of drip water keeps the rainfall signal. Calcite isotopic signal (total average d18O=-6.83‰ V-PDB) shows a small offset (0.62–0.75%) with respect to the signal predicted by drip water oxygen composition; this points to a limited kinetic effect in calcite precipitation, therefore calcite retains the signal of rainfall, especially in winter

Morphological and geochemical features of crater lakes in Costa Rica: an overview.

This paper describes the compositional and morphological features of the crater lakes found in the volcanoes of Rincón de La Vieja, Poás, Irazú, Congo and Tenorio volcanoes (Costa Rica). As evidenced by the distribution of the water and dissolved gas chemistry along vertical profiles, the different fluid sources feeding the lakes reflect the present status of each of the volcanic systems. The chemical features of the Caliente (Poás volcano) and Rincón crater (Rincón de la Vieja volcano) lakes are mainly dependent on i) inputs of magmatic fluids from sub-lacustrine fumaroles and ii) water-rock interaction processes. Conversely, the Irazú lake is mainly affected by the presence of CO2(H2S)-rich fluids discharged from a hydrothermal system, which masked possible magmatic fluid contributions. Rainfall and organic activity are the main factors responsible for the chemical composition of Hule, Botos, Congo and Tenorio lakes. The chemical and isotopic water composition of Botos, Irazú and Hule lakes have displayed no significant variations along the vertical profiles. In contrast, Caliente lake shows a distinctive chemical stratification, mainly involving F-, Cl- and SO4 2-. The behaviour of these compounds seems to be governed by both dissolution of highly acidic species, i.e. HF, HCl and SO2 released from the magmatic environment, and microbial activity. Despite the significant increases with depth of dissolved CO2 at Caliente and Irazú lakes, the hazard for Nyos-type gas eruptions can be considered negligible, since i) the water volumes are too small and ii) the convective heat transfer limits the CO2 recharge rate. The relatively high concentrations of dissolved CO2 measured at the maximum depth of the Hule lake are likely produced by both degradation of organic material and degassing from a deep source. The sporadic episodes of fish deaths recently observed in this lake can be associated with lake overturn processes that have favoured the rise up to the lake surface of deep, oxygen-depleted waters.Journal of limnolog

Fine-scale metabolic discontinuity in a stratified prokaryote microbiome of a Red Sea deep halocline

Deep-sea hypersaline anoxic basins are polyextreme environments in the ocean’s interior characterized by the high density of brines that prevents mixing with the overlaying seawater, generating sharp chemoclines and redoxclines up to tens of meters thick that host a high concentration of microbial communities. Yet, a fundamental understanding of how such pycnoclines shape microbial life and the associated biogeochemical processes at a fine scale, remains elusive. Here, we applied high-precision sampling of the brine–seawater transition interface in the Suakin Deep, located at 2770 m in the central Red Sea, to reveal previously undocumented fine-scale community structuring and succession of metabolic groups along a salinity gradient only 1 m thick. Metagenomic profiling at a 10-cm-scale resolution highlighted spatial organization of key metabolic pathways and corresponding microbial functional units, emphasizing the prominent role and significance of salinity and oxygen in shaping their ecology. Nitrogen cycling processes are especially affected by the redoxcline with ammonia oxidation processes being taxa and layers specific, highlighting also the presence of novel microorganisms, such as novel Thaumarchaeota and anammox, adapted to the changing conditions of the chemocline. The findings render the transition zone as a critical niche for nitrogen cycling, with complementary metabolic networks, in turn underscoring the biogeochemical complexity of deep-sea brines.Versión del edito

Effects of nitrate contamination and seasonal variation on the denitrification and greenhouse gas production in La Rocina stream (Doñana National Park, SW Spain)

Climatic influence (global warming and decreased rainfall) could lead to an increase in the ecological and toxicological effects of the pollution in aquatic ecosystems, especially contamination from agricultural nitrate (NO3 −) fertilizers. Physicochemical properties of the surface waters and sediments of four selected sites varying in NO3 − concentration along La Rocina Stream, which feeds Marisma del Rocio in Do˜nana National Park (South West, Spain), were studied. Electrical conductivity, pH, content in macro and microelements, total organic carbon and nitrogen, and dissolved carbon and nitrogen were affected by each sampling site and sampling time. Contaminant NO3 − in surface water at the site with the highest NO3 − concentration (ranged in 61.6–106.6mgL−1) was of inorganic origin, most probably from chemical fertilizers, as determined chemically (90% of the total dissolved nitrogen from NO3 −) and by isotopic analysis of ı15N-NO3 −. Changes in seasonal weather conditions and hydrological effects at the sampling sites were also responsible for variations in some biological activities (dehydrogenase, -glucosidase, arylsulphatase, acid phosphatase and urease) in sediments, as well as in the production of the greenhouse gases CO2, CH4 and N2O. Both organic matter and NO3 − contents influenced rates of gas production. Increased NO3 − concentration also resulted in enhanced levels of potential denitrification measured as N2O production. The denitrification process was affected by NO3 − contamination and the rainfall regimen, increasing the greenhouse gases emissions (CO2, CH4 and especially N2O) during the driest season in all sampling sites studied.This work was supported by grants CGL2006-06870 and CTM2009-1473-C02-02 from Ministerio de Ciencia e Innovación (Spain) and RNM-4746 from Consejería de Innovación, Ciencia y Empresa de la Junta de Andalucía (Spain), all of them co-financed by the European Regional Development Fund (ERDF). Support of Junta de Andalucía to Research Group BIO-275 is also acknowledged. D. David Correa thanks Ministerio de Educación for predoctoral grant AP2007-03967.Peer reviewe

New speleothem data from Molinos and Ejulve caves reveal Holocene hydrological variability in northeast Iberia

New speleothem records from northeastern Iberian caves provide data to explore the climatic patterns during the Holocene. We present delta C-13 and Mg/Ca from three speleothems from two different caves located in the Iberian Range allowing replication of the climatic signal for several millennia. Through the integration of those stalagmites covering since the Holocene onset to 2 ka, the early Holocene (11.7-8.5 ka) appears as the wettest interval. A marked change towards aridity is observed during the middle Holocene (8.5-4.8 ka) and an increase of humidity afterwards (4.8-2 ka). This three-part pattern, contrasting with other Iberian sequences, seems to be associated with the different role that seasonality has played in the response of different proxies (or records) to changes in water availability. Interpreting our speleothem records as changes in winter-spring precipitation along the Holocene allows reconciling previous data on hydrological variability from the western Mediterranean borderlands

The Campo de Calatrava Volcanic Field (central Spain): Fluid geochemistry in a CO2-rich area.

The Campo de Calatrava Volcanic Field (CCVF) located in central-southern Spain (along with Selva-Emporda in Catalonia, NE Spain) is regarded as one of the most important CO emitting zones in Peninsular Spain. Here, we report and evaluate new molecular and isotopic geochemistry of thermal waters and COrich gas discharges from the CCVF. Locally, these CO-rich fluid emissions represent the remnants of the past volcanic activity that affected this area from the late Miocene through the Quaternary, with the most recent events occurring in the Holocene. The locations of discharging fluids and previous volcanic centers appear to be aligned along well-defined NW-SE and NNW-SSE lineaments, with subordinate trends in the ENE-WSW direction. The chemical and isotopic composition of the thermal waters suggests a meteoric origin, dominated by three distinct geochemical facies: 1) HCO-Mg(Ca) type waters, associated with a relatively shallow aquifer and related to the interaction of meteoric waters with CO-rich gases, alkaline volcanic products, and sedimentary formations, 2) SO(Cl)-Ca(Mg) type waters, which stems from the two rivers (Guadiana and Jabalón) that drain Triassic evaporitic rocks before entering the study area, and 3) HCO-Na type waters, hosted in deep geopressurized CO-rich reservoirs within the Ordovician basement rocks. The Sr/Sr isotopic compositions (ranging between 0.70415 and 0.71623) and δS-SO values (+10.7 to +18.3‰ vs. CDT) of CO-rich fluids are consistent with interactions between water and either the Paleozoic basement, Triassic evaporites, Quaternary volcanic rocks, or a combination thereof. Dissolution of a CO-rich gas phase into the aquifer produces low pH values (down to 5.4) and enhances water-rock interactions causing relatively high salinity (Total Ionic Salinity: up to ∼185 meq/L). Carbon dioxide is by far the most abundant gas constituent (up to 992 mmol/mol) and is dominated by mantle-derived sources as indicated by the combination of relatively high helium isotopic ratios (up to 2.7 R/Ra), high isotopic ratios of carbon in CO (ranging between −6.8 and −3.2‰ V-PDB), and the carbon isotopic signature of TDIC (from −6.8 to +2.2‰ vs. VPDB). In the last two decades, numerous (CO-rich) gas blowouts have occurred in the area during well drillings, suggesting the presence of a geopressurized gas reservoir at relatively shallow depth.The Municipality of Almagro is gratefully acknowledged for the help provided during the sampling activities. We would like to thank Dr. Luis Perez del Villar for his help during the first sampling fieldwork at CCVF. We wish to thank D. Melero Cabañas who accompanied us in the field to collect the water samples during the first survey. Many thanks are also due to the personnel of Amphos21 (J. Bruno, A. Cedez, F. Grandia) and Ciudad de la Energia (D. Angel) and F. Capecchiacci (Dept. Earth Science of Florence) for their help during the second survey. We would like to acknowledge the comments and suggestions provided by two reviewers, who greatly improved an early version of the manuscript. This work was partially funded by Ciudad de la Energia (Resp. OV; Grant contract: ALM-08-006) and the Laboratory of Stable Isotopes and Fluid Geochemistry of the Department of Earth Sciences (University of Florence)

Geochemistry of hydrothermal fluids from the eastern sector of the Sabatini Volcanic District (central Italy).

This study reports a complete geochemical dataset of 215 water and 9 gas samples collected in 2015 from thermal and cold discharges located in the eastern sector of the Sabatini Volcanic District (SVD), Italy. Based on these data, two main aquifers were recognized, as follows: 1) a cold Ca-HCO3 to Ca(Na)-HCO3 aquifer related to a shallow circuit within Pliocene-Pleistocene volcanic and sedimentary formations and 2) a deep CO2-pressurized aquifer hosted in Mesozoic carbonate-evaporitic rocks characterized by a Ca- HCO3(SO4) to Na(Ca)-HCO3(Cl) composition. A thick sequence of low-permeability formations represents a physical barrier between the two reservoirs. Interaction of the CO2-rich gas phase with the shallow aquifer, locally producing high-TDS and low-pH cold waters, is controlled by fractures and faults related to buried horst-graben structures. The d18O-H2O and dD-H2O values indicate meteoric water as the main source for both the shallow and deep reservoirs. Carbon dioxide, which is characterized by d13C-CO2 values ranging from 4.7 to þ1.0‰ V-PDB, is mostly produced by thermo-metamorphic decarbonation involving Mesozoic rock formations, masking possible CO2 contribution from mantle degassing. The relatively low R/Ra values (0.07e1.04) indicate dominant crustal He, with a minor mantle He contribution. The CO2/3He ratios, up to 6 1012, support a dominant crustal source for these two gases. The d34SH2S values (from þ9.3 to þ11.3‰ V-CDT) suggests that H2S is mainly related to thermogenic reduction of Triassic anhydrites. The d13C-CH4 and dD-CH4 values (from 33.4 to 24.9‰ V-PDB and from 168 to 140‰ V-SMOW, respectively) and the relatively low C1/C2þ ratios (<100) are indicative of a prevailing CH4 production through thermogenic degradation of organic matter. The low N2/Ar and high N2/ He ratios, as well as the 40Ar/36Ar ratios (<305) close to atmospheric ratio, suggest that both N2 and Ar mostly derive from air. Notwithstanding, the positive d15N-N2 values (from þ0.91 to þ3.7‰ NBS air) point to a significant extra-atmospheric N2 contribution. Gas geothermometry in the CH4-CO2-H2 and H2S-CO2-H2 systems indicate equilibrium temperatures <200 C, i.e. lower than those measured in deep geothermal wells (~300 C), due to either an incomplete attainment of the chemical equilibria or secondary processes (dilution and/or scrubbing) affecting the chemistry of the uprising fluids. Although the highly saline Na-Cl fluids discharged from the explorative geothermal wells in the study area support the occurrence of a well-developed hydrothermal reservoir suitable for direct exploitation, the chemistry of the fluid discharges highlights that the uprising hydrothermal fluids are efficiently cooled and diluted by the meteoric water recharge from the nearby Apennine sedimentary belt. This explains the different chemical and isotopic features shown by the fluids from the eastern and western sectors of SVD, respectively, the latter being influenced by this process at a lesser extent. Direct uses may be considered a valid alternative for the exploitation of this resource.Published187-2016A. Geochimica per l'ambiente2IT. Laboratori sperimentali e analitici1VV. AltroJCR Journa