molecular and isotopic composition of free hydrocarbon gases from sicily italy 1 chemical and isotopic data have been used as geochemical tracers for a genetic characterization of hydrocarbon gases from a total of eleven manifestations located in eastern and central southern sicily italy the molecular analysis shows that almost all the samples are enriched in methane up to 93 2 vol with the exception of four gas samples collected around mt etna showing high mantle derived co2 content methane isotope signatures suggest that these are thermogenic gases or a mixture between thermogenic gases and microbial gases although samples from some mud volcanoes in southern sicily macalube di aragona show isotope signatures consistent with a mixing model between thermogenic and microbial by combining the molecular compositions c1 c2 c3 and the methane isotope ratios 13c1 such a process seems to be excluded therefore the occurrence of secondary post genetic processes should be invoked two main hypotheses have been considered the first hypothesis includes that the gas is produced by microbial activity and altered post genetically by microbial oxidation of methane while according to the second hypothesis thermogenic gas have modified their molecular ratios due to vertical migration

chemical and isotopical characterisation of fluid manifestations of ischia island italy abstract between 1994 and 1995 gas samples from fumaroles and thermal waters were collected on ischia island the chemical composition of the shallow and deep natural hydrothermal fluids discharged is related to the main hydrological and lithological characteristics of the rock formations present in the reservoir a biphase reservoir liquid gas is identified where the dominant liquid has a temperature of about 280 c on the basis of 13ctdc values it was possible to hypothesize a deep source characterised by carbon isotopic values varying from 0 to 3 these values are noticeably more positive with respect to those attributed to magmatic co2 13 c co 2 ranging from 5 to 8 thus suggesting a magmatic source modified by crustal contamination this hypothesis is supported by the carbon isotopic composition of co2 in sampled gases which varied from 0 to 5 the inferred isotopic value of carbon of magmatic co2 would then be about 2 the observed differences in c isotopic composition between fumarolic and magmatic gases would be caused by kinetic and or equilibrium fractionation processes these processes would cause a fractionation of 13c of deep co2 towards more negative values down to 5 actually co2 removal or addition processes caused by the interaction between deep gases and shallow hydrothermal waters are likely to be responsible for the different chemical and isotopic compositions of gaseous emissions for these reasons and on the basis of the homogeneity of geothermometric values the existence of a single large reservoir that feeds all of the fluids discharged at ischia island can be hypothesised based on acquired data a new geochemical model of the geothermal system of ischia island is proposed

physical speciation of trace metals in fe mn concretions from a rendzic lithosol developed on sinemurian limestones france abstract because of their high content in heavy metals fe mn concretions present in soils can be a source of release of trace metals in the environment metal rich concretions were isolated from a top horizon of a rendzic lithosol developed on limestones in france the distribution of metallic elements cr co ni cu zn pb was studied at different scales field sampling isolated concretions and individual particles methods of investigation combined bulk chemical analysis optical microscopy x ray diffraction xrd and microanalysis using scanning and transmission electron microscopes the concretions are constituted by concentric rings and contain quartz feldspars kaolinite mica goethite and ti oxide as crystalline phases a strong heterogeneity in the chemical composition is evidenced at all different scales the total composition of different populations of fe mn concretions depends on field sampling metals are detected at the micrometer and nanometer scales with variable frequencies occurrences reflecting the abundance of metal bearing components and the size of metal clusters statistical treatments of microanalytical data show marked trends a strong positive correlation of mn and to a lesser extent of ca with ni zn and to a lesser extent with co and cu indicates trace metals to be associated with poorly crystallized mn ca rich areas the correlation of pb with fe and p suggests its incorporation in an fe rich phosphate component no correlation of metals with well crystallized silicates fe sesquioxides or sulfate minerals is established cr was diffusely distributed

hydrothermal hydrocarbon gases in the sediments of the king george basin bransfield strait antarctica thermogenic hydrocarbons formed by the thermal alteration of organic matter are encountered in several piston core stations in the king george basin anatarctica these hemipelagic sediments are being deposited in an area of active hydrothermalism associated with the back arc spreading in the bransfield strait the lateral extent of sediments infiltrated by the hydrothermally influenced interstitial fluids is characterized by basalt diapirix intrusions and is delineated by an acoustically turbid zone in the sediments of the eastern part of the basin iron sulphide bearing veins and fractures cut across the sediment in several cores they appear to be conduits for flow of hydrothermally altered fluids these zones have the highest c2 and ethene contents the thermogenic hydrocarbons have molecular c1 c2 c3 ratios typically 50 and 13ch4 values between 38 and 48 indicating an organic source which has undergone strong thermal stress several sediment cores also have mixed gas signatures which indicate the presence of substantial amounts of bacterial gas predominantly methane hydrocarbon generation in the king george basin is thought to be a local phenomenon resulting from submarine volcanism with temperatures in the range 70 150 c there are no apparent seepages of hydrocarbons into the water column and it is not believed that significant accumulation of thermogenic hydrocarbons reside in the basin

segmentation and configuration of subducted lithosphere in italy an important control on thrust belt and foredeep basin evolution the apennine foredeep basin system located on continental crust consists of four roughly parallel basin segments each containing a flexural outer rise and an inner trough that deepens continuously toward the thrust belt flexural modeling of subsidence data across the basin indicates that this foredeep basin results mainly from deep subsurface loads acting on the subducted slab from within the subduction zone rather than from the topographic load of the apennine mountains the geometry of the four basin segments observed within the apennine foredeep is thus inferred to reflect subduction of segmented lithosphere where each lithospheric segment corresponds to a segment of the foredeep basin beneath the basin and in the foreland the lithosphere is continuous segmentation occurs only at depth beneath the thrust belt this pattern olf segmentation of the subducted lithosphere at depth is reflected in the large scale geometry of the outer part of the apennine thrust belt and appears to control it similarly the pattern of segmentation also appears to control the position of the eastern limit of back arc type extension in western italy these relations strongly suggest a genetic relation between subduction zone processes foredeep basin geometry and thrust belt evolution in which the configuration of the subducted lithosphere largely controls the large scale surface deformation observed in the apennine system

geochemistry of some gases in hydrothermal fluids from the southern juan de fuca ridge five samples of hydrothermal fluids from two vent areas on the southern juan de fuca ridge were analyzed for dissolved gases concentrations in the end member hydrothermal fluid of h2 270 527 mol kg ch4 82 118 mol kg and co2 3920 4460 mol kg are well above values in ambient seawater and are similar to concentrations reported for other ridge crest hydrothermal systems the carbon isotopic ratios of the ch4 13c 17 8 to 20 8 and co2 13c 3 6 to 4 7 suggest that at least some of the ch4 and co2 in the fluids is basalt derived the range of 13c values for the basalt derived co2 is 6 8 to 9 7 calculated by assuming conservation of recharge co2 during hydrothermal circulation apparent temperatures of equilibration between the ch4 and the basalt derived co2 range from 640 c to 750 c small amounts of ethane c2h6 ch4 0 9 10 3 2 2 10 3 propane and butane detected in the samples may also have formed in the basalt one sample of almost pure 95 5 hydrothermal fluid contained a significant fraction up to 63 and 74 respectively of the recharge ar and n2 this suggests that the fluid has not undergone extensive vapor liquid phase separation

carbon isotope geochemistry of hydrocarbons in the cerro prieto geothermal field baja california norte mexico hydrocarbon abundances and stable isotopic compositions were measured in wells m5 m26 m35 and m102 which represent a range of depths 1270 2000 m and temperatures 275 330 degrees c in the field in order to simulate the production of the geothermal hydrocarbons gases were collected from the pyrolysis of lignite in the laboratory this lignite was obtained from a well which sampled rock strata which are identical to those occurring in the field but which have experienced much lower subsurface temperatures in both the well and the laboratory observations high temperature environments favored higher relative concentrations of methane ethane and benzene and generally higher delta 13c values in the individual hydrocarbons the best correlation between the laboratory and well data is obtained when laboratory produced gases from experiments conducted at lower 400 degrees c and higher 600 degrees c temperatures are mixed this improved correlation suggests that the wells are sampling hydrocarbons produced from a spectrum of depths and temperatures in the sediments

composition and origin of hydrothermal petroleum and associated lipids in the sulfide deposits of the rainbow field mid atlantic ridge at 36 n the lipid components in hydrothermal sulfide deposits from the rainbow vent field mid atlantic ridge at 36 n were studied by gas chromatography mass spectrometry the rainbow vent field is one of two known active hydrothermal systems related to abyssal circulation where high temperature fluids are formed during serpentinization of ultrabasic crustal rocks the major amount of the extractable organic matter from the sulfides consists of normal and branched alkanes ucm pahs terpenoids and fatty acids the branched alkanes are comprised of unique gem diethylalkane series possibly from sulfide oxidizing bacteria and biphytanes from archaea the characteristic lipid and biomarker compounds found in the hydrothermal samples support a predominantly biological origin of the bitumens from the thermal transformation of the biomass of microorganisms bacteria and archea and minor macrofauna of this vent field a search for molecular evidence for abiogenic thermocatalytic synthesis of organic compounds was negative however methane in the hydrothermal fluids and possibly a minor amount of the alkanes in the sulfides may be of an abiogenic origin in the rainbow vent field

fluid migration and origin of a mud volcano in the northern apennines italy the role of deeply rooted normal faults introductionsurface seeps of gas oil and salinewaters areconsideredtobeindicatorsof deep seated hydrocarbon accumu lationandhavebeenused forover60years as a guide to hydrocarbonprospectivity a wide spectrum ofseepages belongs to di erent geologi cal settings e g camerlenghi etal 1992 1995 thrasher etal 1996 schulz etal 1997 kopf etal 1998 graue 2000 spectacular seepagescan be found in basins with highsedimentation rates that generateoverpressureandmuddiapirism gu liev and feyzullayev 1996 up dipcarrier beds and active tectonic fea tures act as channels for subsurface uidandlocalizesurfaceemissionsuptotens orevenahundred kilometresfrom the reservoir thrasher etal 1996 during migration the domi nant mechanism that changeshydrocarbon composition is phasepartitioning migration of hydrocar bons is then largely the result ofbuoyancy of the free phase formedduringthisprocess matthews 1996 eventually thegeologyofthebasinisthe key to interpreting complicated uidmigrationpathways manystud ies simply focus on the oil and gascomponents of the migrating uidrather than on the characteristics ofthewaterandmudthatareassociatedwithhydrocarbonmigrationandalsoextruded by spontaneous seeps eventhough water is invoked as beingresponsibleforatleastlighthydrocar bon removal klusman and saaed 1996 watersofdi erentprovenancecontributetotheascending uidsandtheir geochemical characteristics canhelp in understanding their evolutionduring diagenesis and migration e g white 1965 hanor 1987 holyshandto th 1996 thispaperpresentssomeanalytical data from a spontaneoussurface seep bearing saline water mud gas and oil at the foothills ofthe northern apennines the aimsare i to provide some insight intothedepthandoriginofthe uidsandthe nature of the seepage pathway and ii tode nethelossofsubsurface uids accumulation related to thegeologicalpattern geological setting and structuralcontrol of the regnano mudvolcanoin the external portion of the nor thern apennines spontaneous uidemissions are distributed along twobelts borgia etal 1986 nanni andvivalda 1999 minissaleetal 2000 the rst belt stretches along the poplainfoothills whilethesecondoneisinternal and runs nearly parallel tothe main apenninic divide fig 1 theregnanomudvolcanoconsistsofmud breccias and mud ows spread ing over an area of 0 5km

recognising biodegradation in gas oil accumulations through the δ13c compositions of gas components a large suite of natural gases 93 from the north west shelf and gippsland and otway basins in australia have been characterised chemically and isotopically resulting in the elucidation of two types of gases about 26 of these gases have anomalous stable carbon isotope compositions in the c1 c4 hydrocarbons and co2 components and are interpreted to have a secondary biogenic history the characteristics include unusually large isotopic separations between successive n alkane homologues up to 29 pdb and isotopically heavy co2 up to 19 5 pdb irrespective of geographic location these anomalous gases are from the shallower accumulations 600 1700 m where temperatures are lower than 75 c the secondary biogenic gases are readily distinguishable from thermogenic gases 74 of this sample suite which should assist in the appraisal of hydrocarbons during exploration where hydrocarbon accumulations are under 2000 m while dissolution effects may have contributed to the high 13c enrichment of the co2 component in the secondary biogenic gases the primary signature of this co2 is attributed to biochemical fractionation associated with anaerobic degradation and methanogenesis correlation between biodegraded oils and biodegraded dry gas supports the concept that gas is formed from the bacterial destruction of oil resulting in secondary biogenic gas furthermore the prominence of methanogenic co2 in these types of accumulations along with some isotopically depleted methane provides evidence that the processes of methanogenesis and oil biodegradation are linked it is further proposed that biodegradation of oil proceeds via a complex anaerobic coupling that is integral to and supports methanogenesis

origin of the fumarolic fluids of vulcano island italy and implications for volcanic surveillance variations in d and 18o values with h2o contents and outlet temperatures indicate that the fumaroles of la fossa crater have discharged mixtures of magmatic water and marine hydrothermal water since 1979 the contribution of meteoric water was low in the period 1979 1982 and very low afterwards the 18o values of the marine hydrothermal component of 5 to 7 2 are due to isotopic exchange with the 18o rich silicates of the rocks under high temperature and low permeability conditions the 18o value of the magmatic end member is generally 3 5 to 4 3 although values as high as 5 5 to 6 5 were reached in the summer of 1988 when magma degassing appears to have extended into the core of the magma body the d values of the end member were close to 20 typical of andesitic waters both the isotopic values and chemical data strongly support a dry model consisting of a central magmatic gas column and a surrounding hydrothermal envelope in which marine hydrothermal brines move along limited fracture zones to undergo total evaporation on approaching the conduits of magmatic fluids the vents at the eastern and western boundaries of the fumarolic field are fed by fluids whose pressure is governed by the coexistence of vapor liquid and halite giving rise to a high risk of phreato magmatic explosions should magma penetrate into these wet environments most la fossa eruptions were triggered by an initial hydrothermal blast and continued with a series of phreatomagmatic explosions the fluids discharged by the forgia vecchia fumaroles are mixed with meteoric water which is largely evaporated although subordinate loss of condensed steam may be responsible for scrubbing most of the acidic gas species the temperatures and pressures and the risk of a sudden pressure increase are low a boiling hydrothermal aquifer at 230 c is present underneath the baia di levante beach this area has a minor risk of hydrothermal explosions

the geochemistry of potassic lavas from vulsini central italy and implications for mantle enrichment processes beneath the roman region major and trace element and 143nd 144nd 0 51209 0 51216 and 87sr 86sr 0 70879 0 71105 isotope analyses are presented on a representative group of lavas from the vulsini district of the roman magmatic province three distinct series are identified the high k and low k series are similar to those described from other italian volcanoes while the third is represented by a group of relative ly undifferentiated leucite basanites which are thought to be near primary mantle melts major and trace element variations within the high k series are consistent with fractional crystallisation from a parental magma similar to the most magnesian leucitites crustal contamination resulted in an increase in 87sr 86sr with increasing fractionation but it was superimposed on magmas which had already inherited a range of incompatible element and isotope ratios from enrichment processes in the sub continental mantle these are reviewed using the available results from vulsini roccamonfina and ernici transition element abundances and ta yb ratios indicate that the pre enrichment mantle was similar to that of e type morb and that these elements were not mobilised by the enrichment process mixing calculations suggest that three components were involved in the enrichment process mantle comparable with the source of morb and two other components rich in trace elements one the low k component had high sr nd th ta and ba nb and no europium anomaly while the second had lower sr nd a negative europium anomaly and very high th ta it was also characterised by low nb ba and high rb ba ratios similar to those reported from phlogopite rich peridotite xenoliths the trace element enrichment processes are therefore thought to have occurred in the mantle wedge above a subduction zone with the trace element characteristics of the high k end member reflecting the subduction of sediments and the stabilisation of mantle phlogopite

chemical and isotopic equilibrium between co2 and ch4 in fumarolic gas discharges generation of ch4 in arc magmatic hydrothermal systems the chemical and isotopic composition of fumarolic gases emitted from nisyros volcano greece and of a single gas sample from vesuvio italy was investigated in order to determine the origin of methane ch4 within two subduction related magmatic hydrothermal environments apparent temperatures derived from carbon isotope partitioning between ch4 and co2 of around 340 c for nisyros and 470 c for vesuvio correlate well with aquifer temperatures as measured directly and or inferred from compositional data using the h2o h2 co2 co ch4 geothermometer thermodynamic modeling reveals chemical equilibrium between ch4 co2 and h2o implying that carbon isotope partitioning between co2 and ch4 in both systems is controlled by aquifer temperature n2 3he and ch4 3he ratios of nisyros fumarolic gases are unusually low for subduction zone gases and correspond to those of midoceanic ridge environments accordingly ch4 may have been primarily generated through the reduction of co2 by h2 in the absence of any organic matter following a fischer tropsch type reaction however primary occurrence of minor amounts of thermogenic ch4 and subsequent re equilibration with co existing co2 cannot be ruled out entirely co2 3he ratios and 13cco2 values imply that the evolved co2 either derives from a metasomatized mantle or is a mixture between two components one outgassing from an unaltered mantle and the other released by thermal breakdown of marine carbonates the latter may contain traces of organic matter possibly decomposing to ch4 during thermometamorphism

geochemistry and habitat of natural gases in italy abstract systematic chemical and isotopic analyses were carried out on natural gases from 92 fields which represent more than 90 of the original gas reserves of italy a quantitative assessment of the various genetic gas types indicates that most of the gaseous hydrocarbons 80 were generated through bacterial activity and or diagenetic processes while only a minor amount 20 was produced by thermal degradation of organic matter the formation of the gas accumulations was geologically controlled by the neogene tectonic phases and by the sedimentary events associated with the growth of the apennines and southern alps in fact about 80 of italian natural gas reserves have been found in the apennine foredeep while the remaining part is equally distributed in the folded belt and in the foreland furthermore the influence exerted by tectono sedimentary characteristics is emphasized by the fact that thermal degradation of organic matter was the only process responsible for most of the gas generated in the apennine folded belt 97 thermogenic gases on the other hand the high rates of subsidence turbiditic sedimentation and very early compressional tectonics in the foredeep favored processes leading to the accumulation of very large quantities of biogenic gas 82 moreover geochemical and geological data as well as mathematical modelling demonstrate that migration and accumulation of italian natural gases mainly occurred later than 5 my ago and in some cases these phenomena are still active in fact in the multipay zone gas fields of the northern adriatic a kind of steady equilibrium is reached between loss of gas through the thin cap rocks often less than 1 m and continous replenishment from the bacterial fermentation and or low temperature thermochemical reactions

hydrothermal methane fluxes from the soil at pantelleria island italy abstract chemical and isotopic analyses of the main gas manifestations of the island of pantelleria italy were used to gain insight on the origin of the released methane results indicate that the most probable origin is through abiogenic reactions within the hydrothermal system methane and co 2 flux measurements from the soils were made with the accumulation chamber method in an area of about 0 015 km 2 within the main fumarolic area of the island favara grande the 23 measurements range from 34 to 3550 mg m 2 d 1 for ch 4 and from 0 6 to 379 g m 2 d 1 for co 2 the relationships between ch 4 and co 2 fluxes and the ch 4 co 2 ratios in the gases collected between the depths of 25 and 100 cm provide evidence for methanotrophic processes within the soils methane output for the surveyed area was calculated to be 2 5 t a 1 and extrapolated to about 5 10 t a 1 for the entire volcanic hydrothermal system of the island previous higher estimates of the ch 4 output at pantelleria etiope et al 2007 j volcanol geotherm res 165 76 86 were based on soil co 2 output and ch 4 co 2 ratios in fumarolic gases the present work provides the first direct ch 4 flux data and it suggests that methanotrophic activity in the soil could be substantial in reducing the ch 4 emission to the atmosphere

excess methane in continental hydrothermal emissions is abiogenic thermogenic hydrocarbons entirely deriving from the thermal degradation of organic matter usually exhibit methane to ethane plus propane ratios smaller than 100 we present hydrocarbon distribution data of continental hydrothermal gases whose methane has been independently identified to derive from the abiogenic reduction of co2 we find that excess amounts of methane with respect to thermogenic hydrocarbon distributions are characteristic for the investigated gases a similar pattern is observed for well discharges whose temperatures are too high to support any microbially mediated methanogenesis these findings strongly suggest that abiogenic methane production in continental hydrothermal systems is a more widespread process than previously assumed the maximum contribution of such emissions to the modern atmospheric ch4 budget is estimated at 1

pedogenic manganese oxide coatings calcium buserite on fracture surfaces in tortonian upper miocene red mudstones southern turkey abstract fracture surfaces of red mudstones overbank deposits within the kuzgun formation of late miocene tortonian age are coated by thin black colored manganese oxide beneath a thin soil cover in the mersin area of southern turkey these manganese oxide coatings have been investigated by a range of analytical techniques including x ray diffraction xrd infrared spectral ir differential thermal analysis thermal gravimetric dta tg scanning electron microscopy and energy dispersive x ray sem edx analyses the basal reflections at 10 00 7 22 5 00 3 35 2 50 2 29 and 2 10 a sharp infrared spectral lines at 469 and 519 cm 1 and typical dehydration of interlayer water

geochemistry of water and gas discharges from the mt amiata silicic complex and surrounding areas central italy abstract the mt amiata volcano in central italy is intimately related to the post orogenic magmatic activity which started in pliocene times major trace elements and isotopic composition of thermal and cold spring waters and gas manifestations indicate the occurrence of three main reservoir of the thermal and cold waters in the mt amiata region the deepest one is located in an extensive carbonate reservoir buried by thick sequences of low permeability allochthonous and neo autochthonous formations thermal spring waters discharging from this aquifer have a neutral ca so4 composition due to the presence of anhydrite layers at the base of the carbonate series and possibly to absorption of deep derived h2s with subsequent oxidation to so42 in a system where ph is buffered by the calcite anhydrite pair marini and chiodini 1994 isotopic signature of these springs and n2 rich composition of associated gas phases suggest a clear local meteoric origin of the feeding waters and atmospheric o2 may be responsible for the oxidation of h2s the two shallower aquifers have different chemical features one is ca hco3 in composition and located in several sedimentary formations above the mesozoic carbonates the other one has a na cl composition and is hosted in marine sediments filling many post orogenic nw se trending basins strontium ba f and br contents have been used to group waters associated with each aquifer although circulating to some extent in the same carbonate reservoir the deep geothermal fluids at latera and mt amiata and thermal springs discharging from their outcropping areas have different composition na cl and ca so4 type respectively considering the high permeability of the reservoir rock the meteoric origin of thermal springs and the two different composition of the thermal waters self sealed barriers must be present at the boundaries of the geothermal systems the complex hydrology of the reservoir rocks greatly affects the reliability of geothermometers in liquid phase which understimate the real temperatures of the discovered geothermal fields more reliable temperatures are envisaged by using gas composition based geothermometers bulk composition of the 67 gas samples studied seems to be the result of a continuous mixing between a n2 rich component of meteoric origin related to the ca so4 aquifer and a deep co2 rich component rising largely along the boundaries of the geothermal systems nitrogen rich gas samples have nearly atmospheric n2 ar 83 and 15 n 14 n 0 ratios whereas co2 rich samples show anomalously high 15n values up to 6 13 likely related to n2 from metamorphic schists lying below the carbonate formations on the basis of average 13 c 12 c isotopic ratio 13c around 0 co2 seems to originate mainly from thermometamorphic reactions in the carbonate reservoir and or in carbonate layers embedded in the underlying metamorphic basement distribution of 3 he 4 he isotopic ratios indicates a radiogenic origin of helium in a tectonic environment that in spite of the presence of many post orogenic basins and mantle derived magmatics can presently be considered in a compressive phase

the larderello geothermal field a review abstract this paper reviews published geological geophysical petrological and geochemical data together with reservoir engineering parameters of the larderello geothermal reservoir of southern tuscany italy some theories are proposed on the deep origin evolution in time and natural state of this geothermal field prior to its exploitation the interaction between the vapor dominated reservoir and surrounding aquifers is discussed analysis of hydrogeochemical data suggests that meteoric waters from shallow external aquifers contribute little to the production of steam the vapor dominated system and the cold external aquifers are separated by areas of very low permeability where physical conditions change greatly over short distances the presence and significance of liquid phases in the peripheral areas of the vapor dominated reservoir are interpreted as being due to steam condensation the latter is a consequence of a low permeability conditions in the deep buried parts of the carbonate reservoir formations in the north northwestern sector of the field and b by the mixing of ascending superheated steam from depth with cold caso4 meteoric waters circulating in unconfined shallow aquifers within the outcrops of the carbonate reservoir formations in the south southeastern parts of the field the presence of steam below these liquid dominated sectors of the reservoir seems possible the limited natural recharge of the system the constant steam production rate for geothermal power generation 3000 t h 1 since 1951 the persistence of natural thermal features and the fact that reinjection has had little effect on the characteristics of the fluid discharged seem to indicate a steady state for the larderello field the main contribution to production seems to be from superheated steam ascending from depth and the in situ evaporation of water stored in the small pores of the rocks present in larderello in a system that is much larger than the one known at present

mineralogy and composition of concentric layers within a manganese nodule from the north pacific ocean abstract the minor element composition of concentric layers within a single ferromanganese nodule from the eastern north pacific exhibits strong correlations with fe and mn contents but appears to be independent of pronounced mineralogic variations on the basis of these correlations the elemental composition of individual layers apparently is controlled by the relative contribution of two sources seawater and interstitial water of associated sediment in contrast the mineralogy of the nodule consisting of birnessite in the outer few layers and todorokite in the inner layers is considered to be a function of nodule diagenesis

principles of engineering geomorphology for managing channel erosion and bedload transport examples from french rivers abstract french rivers have been transformed by centuries of development to satisfy various social demands such as navigation hydro electric power production flood control or checking erosion these modifications have led to impacts that are detrimental to ecology to resources and to human interests in recent years increased public and management awareness of these problems has given way to new conceptions and objectives in the field of river engineering among which the goal of establishing sustainable long term management strategies is of the highest importance because many of these problems are directly or indirectly related to changes in the geomorphological functioning of fluvial systems there is a need to integrate a geomorphological approach into river engineering practices the principles of engineering geomorphology are developed here and are illustrated by examples taken from rivers that drain the french alps and their piedmont

fluid geochemical transect in the northern apennines central northern italy fluid genesis and migration and tectonic implications chemical and isotopic characteristics of natural gas and thermal water discharges from the western back arc tyrrhenian sea across the apennine thrust belt to the po valley and adriatic coast foredeep basins in the northern apennines central northern italy reveal a large scale fluid motion in the upper crust both vertically and horizontally on the basis of gas compositions two different domains of rising fluids have been distinguished 1 co2 rich he poor 3he 4he high domain in the western peri tyrrhenian extensional sector 2 ch4 rich he rich 3he 4he low domain in the eastern adriatic compressional sector such gases rising from various depths are crossed by a huge lateral n2 rich water flow in the peri tyrrhenian sector of ca so4 hco3 meteoric derived waters that move in a regional wide aquifer hosted in a quite thick mesozoic carbonate series morphologically the co2 vents consist of mud basins with high gas rate emission where the rising fluids move upwards through diatremes on the other hand ch4 emissions seep out from typical mud volcanoes with a reduced gas flow rate where the fluid motion is likely related to saline diapir extrusions and the methane is mostly carried to the surface by the associated mud the two rising mechanisms described locate southwest and northeast of the apennine watershed respectively from a seismic point of view the ch4 domain in the thrust belt and foredeep areas is characterized by a large number of earthquakes indirectly pointing to a different rheological behavior of the terrains with respect to the more internal peri tyrrhenian area owing to the quite high thermal gradient of the latter the boundary of the brittle ductile crust in the peri tyrrhenian sector can be located at a 10 km shallow depth although the presence of several post orogenic basins would suggest widespread extensional tectonics in all areas west of the apennine watershed those located in the easternmost part display gas vents with typical crustal 3he 4he ratios as this ratio is very sensitive to deep fluids rising from the mantle we hypothesize that such basins at the foot of the apennines are not due to tensive stress as suggested by their morphological shape they are piggy back thrust top basins developed and evolved in a still acting compressive tectonic regime

sources and mechanisms of formation of gaseous hydrocarbons in sedimentary rocks abstract accepted concepts of principal stages of hydrocarbon formation fail to satisfactorily explain the accumulation of supergiant gasfields in west siberia u s s r such as for example urengoy which comprise 30 of the proven gas reserves of the world a new mathematical model has been developed which applies the concept of activation energy distribution to the formation of gases characteristic differences in the molecular structure of humic and sapropelic source organic matter are expressed in different activation energy distributions the model allows the calculation of isotope values for different types of organic matter and their dependence on maturity application of the model to west siberia suggests that the supergiant gas accumulations in urengoy are more likely formed from terrestrial organic matter through thermochemical reactions at moderate depths and are not the result of either deep overmature or bacteriogenic processes the new mathematical model suggests that humic organic matter in general has a high methane generating capacity at comparably low maturities of organic matter equivalent to 0 5 0 7 on the vitrinite reflectance scale

submarine gas burst at panarea island southern italy on 3 november 2002 a magmatic versus hydrothermal episode 1 on 3 november 2002 fishermen observed the sudden appearance at the sea surface of three large whitish plumes 3 km offshore of panarea island aeolian islands southern italy caused by the uprising from the seafloor of huge columns of gas bubbles mixed with sediments and colloidal sulfur the degassing event partly superimposed an already existing gentle degassing fumarolic field since 12 november 2002 a discontinuous geochemical monitoring program of these new discharging fluids have been carried out the submarine emissions collected on november 2002 were an emulsion made by a co2 dominated continuous gas phase with suspended sediments colloidal sulfur and water condensate microdroplets acidified by dissolution of compounds such as so2 hcl and hf in the gas phase light unsaturated hydrocarbons also occurred possibly related to relatively high temperature and oxidizing conditions due to local input of magmatic fluids at depth whose occurrence was also supported by the relative high values of 3he 4he isotopic ratio r rair 4 62 with respect to previously measured values r rair 4 2 the flux of the submarine emissions significantly decreased in a couple of months together with the almost complete disappearance of the magmatic chemical markers and the decrease of the helium isotopic ratio thus the most striking feature of the temporal and spatial evolution in the chemical and isotopic compositions of the submarine fumaroles was the relatively rapid restoration since january 2003 of the precrisis conditions i e typical of a stationary hydrothermal system

monitoring and modelling morphological change in a braided gravel bed river using high resolution gps based survey recent research in fluvial geomorphology has emphasized the direct monitoring of channel topography as a useful tool to better understand the interrelationship between river form and process and in particular to estimate bedload transport rates and reach scale sediment budgets until recently however this morphometric approach has been limited to comparison of repeatedly surveyed cross sections with the associated problems of low frequency sampling and an emphasis on cross stream as opposed to downstream morphological dynamics recent advances in analytical photogrammetry have however permitted the acquisition of data at sufficient resolutions to represent macroform 101 m and microform 10 m channel geometry in fully three dimensions while inherently spatially distributed the photogrammetric approach to land surveying is however restricted to observable areas of the channel and is thus of limited use in the subaqueous zone especially if flows are turbid or highly coloured this paper presents an alternative approach to the study of three dimensional morphological dynamics of a divided reach of the gravelly river feshie scotland in which topographic survey of both exposed and submerged areas of the reach was undertaken using the global positioning system gps survey results from two field programmes in 1998 and 1999 are presented in which a geotronics geotracer 2000 real time kinematic gps receiving unit was used to survey a 200 80 m reach rapid radial survey methods were employed permitting the collection of 2000 survey points per day giving a mean density over the 13 ha reach of 1 1 points per square metre a detailed assessment of survey errors and dem quality is presented and a limit of detection of c 10 cm proposed as an upper threshold for the identification of significant change between dems preliminary interpretation of channel dynamics in 1998 99 reveals relatively little change to the overall macroscale reach structure dem differencing techniques however highlight important local changes including the progradation of submerged bar fronts bar head aggradation and scour along major channel thalwegs and the erosion of fines from sloughs copyright 2000 john wiley sons ltd

mineralogy of fe mn nodules in albeluvisols in the carpathian foothills poland fe mn nodules are common components occurring in various soils and especially in soils exhibiting imperfect drainage the formation distribution chemical composition size and shape of fe mn nodules are the subject of many studies and the research literature contains a lot of information concerning these issues on the other hand data regarding the mineral composition of fe mn nodules in the soil environment are limited to only a few studies the main aim of the present study was to determine the mineral composition of the fe mn nodules found in albeluvisols in the carpathian foothills in poland using quantitative x ray diffraction qxrd fourier transform infrared spectroscopy ftir and mossbauer spectroscopy ms the obtained results show that fe mn nodules from albeluvisols in the carpathian foothills in poland are composed mainly of silicates quartz k feldspars plagioclases and phyllosilicates dioctahedral mica smectite chlorite and kaolinite which are impregnated with iron and manganese oxides iron minerals are represented by goethite and probably lepidocrocite both iron minerals are characterized by very small particles and poor crystallinity goethite occurring in all of the studied fe mn nodules clearly prevails over lepidocrocite which exhibits a higher concentration only in nodules from the lower part fragipan of the soil profile located on a footslope and showing the strongest stagnic color pattern manganite and todorokite represent manganese minerals however todorokite was observed only in nodules obtained from illuvial horizons btx btg of the studied albeluvisols the fe mn nodules obtained from eluvial horizons eg show higher amounts of silicates quartz k feldspars plagioclases than the nodules obtained from illuvial horizons on the other hand fe mn nodules obtained from illuvial horizons fragipan and argillic exhibit higher amounts of phyllosilicates i e clay minerals in comparison with the eluvial horizon the differences in the quantitative mineral composition of the fe mn nodules between eluvial and illuvial horizons are related to the translocation of clay minerals from upper soil horizons into the lower part of the soil profiles this indicates that the nodules from e horizons were formed after translocation of major portion of clay fraction down the soil profile the similar mineral composition of the fe mn nodules and bulk soil material indicates that the nodules were formed in situ because of cyclic reduction and oxidation of fe and mn oxides

evolution of the latera geothermal system ii metamorphic hydrothermal mineral assemblages and fluid chemistry abstract the latera field vulsini volcanic complex latium italy is one of the geothermal areas of the peri tyrrhenian belt along which a regional high thermal anomaly has been detected so far nine deep wells have been drilled within the latera caldera and four of them have been productive the geothermal reservoir is located within the fractured carbonatic rocks of the tuscan nappe the overlying volcanic units sealed by hydrothermal minerals mainly calcite and anhydrite act as an impervious cover the fluid produced by the wells comes from a deep aquifer about 1000 1500 m depth which at present is not connected with the shallow aquifer in the volcanoclastic units fluid temperatures range between 200 and 230 c in hole temperatures as high as 343 c at 2775 m depth have been measured in dry wells the study of the newly formed mineral assemblages from both volcanic and sedimentary units as sampled from the geothermal wells can be used to reconstruct the thermal evolution of the geothermal field the intrusion of a syenitic melt up to a depth of about 2000 m dated 0 86 ma represents the major thermal event for the units in the area and is assumed to represent the first step in the geothermal evolution of the latera system the above mentioned newly formed mineral assemblages can be divided into three groups a contact metasomatic calcite anhydrite diopsidic pyroxene grossularitic garnet phlogopite wollastonite or monticellite b high temperature hydrothermal calcite anhydrite k feldspar vesuvianite melanitic garnet tourmaline amphibole epidote sulphides c low temperature hydrothermal calcite anhydrite k feldspar clay minerals sulphides group a minerals are now relics part of b and all of c group are still in equilibrium with the existing conditions in different parts of the geothermal system thermodynamic calculations on the observed mineral assemblages permitted estimates of the p t conditions and gas fugacities

medium and short term channel planform changes on the rivers tay and tummel scotland abstract channel planform change was analysed using a variety of data sources for the medium term 25 years and

isotope geochemistry of pantelleria volcanic fluids sicily channel rift a mantle volatile end member for volcanism in southern europe chemical and isotopic ratio he c h and o analysis of hydrothermal manifestations on pantelleria island the southernmost active volcano in italy provides us with the first data upon mantle degassing through the sicily channel rift zone south of the african european collision plate boundary we find that pantelleria fluids contain a co2 he rich gas component of mantle magmatic derivation which at shallow depth variably interacts with a main thermal 100 c aquifer of mixed marine meteoric water the measured 3he 4he ratios and 13c of both the free gases 4 5 7 3 ra and 5 8 to 4 2 respectively and dissolved helium and carbon in waters 1 0 6 3 ra and 7 1 to 0 9 together with their covariation with the he co2 ratio constrain a 3he 4he ratio of 7 3 0 1 ra and a 13c of ca 4 for the magmatic end member these latter are best preserved in fluids emanating inside the active caldera of pantelleria in agreement with a higher heat flow across this structure and other indications of an underlying crustal magma reservoir outside the caldera the magmatic component is more affected by air dilution and at a few sites by mixing with either organic carbon and or radiogenic 4he leached from the u th rich trachytic host rocks of the aquifer pantelleria magmatic end member is richer in 3he and has a lower closer to morb 13c than all fluids yet analyzed in volcanic regions of italy and southern europe including mt etna in sicily 6 9 0 2 ra 13c 3 1 this observation is consistent with a south to north increasing imprint of subducted crustal material in the products of italian volcanoes whose he and c but also o and sr isotopic ratios gradually evolve towards crustal values northward of the african eurasian plate collision boundary our results for pantelleria extend this regional isotopic pattern further south and suggest the presence of a slightly most pristine or less contaminated 3he richer mantle source beneath the sicily channel rift zone the lower than morb 3he 4he ratio but higher than morb co2 3he ratio of pantelleria volatile end member are compatible with petro geochemical evidence that this mantle source includes an upwelling himu em1 type asthenospheric plume component whose origin according to recent seismic data may be in the lower mantle

mechanisms of anabranch avulsion within gravel bed braided rivers observations from a scaled physical model the physical modelling of gravel bed braided rivers using a 1 20 froude scale model permits analysis of the types and relative occurrence of different avulsion mechanisms anabranch avulsion within braided rivers involves three main mechanisms choking avulsion caused by blockage of one channel by a sediment lobe constriction avulsion produced by deflection confinement and subsequent diversion of the flow by a barform and apex avulsion following erosion at the outside of sinuous thalwegs and confined meander bends each avulsion mechanism is described and analysis of the abundance of each type illustrates choking avulsion to be predominant without braided rivers three factors are found to control anabranch avulsions namely flow discharge sediment flux and floodplain topography these are briefly discussed together with the implications of avulsion type for the alluvial architecture of gravelly braided alluvium

multiple origins of methane in the earth methane occurrences in the earth s crust are predominantly of biogenic origin i e their ultimate source is biologically formed organic matter methane can also form through inorganic reactions and is consequently termed abiogenic biogenic methanes can either form through bacterial or thermogenic processes bacterial processes follow a co2 reduction and or fermentation pathway the fermentation processes are quantitatively more important in recent fresh sediments and swamps methane formed by co2 reduction however is most common in older sediments and commercial gasfields temperature organic substrate and age may be the major factors controlling the relative importance of the two pathways stable isotope concentrations in thermogenic methanes seem to be controlled by the extent of conversion of organic matter the timing of gas expulsion and trapping the different character of methane in individual sedimentary basins may be a result of the geologic history geothermal methanes are most likely derived from pyrolysis of organic matter abiogenic methane occurs in hydrothermal vents and ophiolite complexes inorganic reactions either surficial or deep seated are the likely source of such methanes a uniform mantle origin of methane is not supported by the observed isotope variations in naturally occurring methanes

origin of carbon in fumarolic gas from island arcs abstract we have measured 3 he 4 he ratios 13c values and co 2 3 he ratios of fumaroles and hot spring gases in three volcanic areas in japan the 3 he 4 he ratios 13c values and co 2 3 he ratios vary from 02 05 ratm 9 7 to 2 7 and from 7 74 109 to 1 18 1011 respectively based on these data and those in the literature we present the first quantitative estimates of the upper mantle sediment and limestone including slab components in co2 of volcanic and hydrothermal fluids from subduction zones taking compiled c isotopic data of limestone and organic sediment assuming that the co 2 3 he ratio and 13c value of mid ocean ridge basalt morb are representative of the upper mantle component and that later isotopic and elemental fractionations are minimal it is possible to deconvole each fraction of c on the basis of simple mixing equations up to 20 of the carbon in high temperature volcanic gases in subduction zones is derived from a morb type source while the major fraction of the gases is attributable to co2 produced by decarbonation of subducted marine limestone and slab carbonate

fluid geochemistry and geothermometry in the western sector of the sabatini volcanic district and the tolfa mountains central italy abstract a geochemical survey of 197 fluid discharges cold and thermal waters and bubbling pools and 15 gas emissions from the western sector of the sabatini volcanic district and the tolfa mountains latium central italy was carried out in 2007 2008 the chemical and isotopic compositions of the fluid discharges indicate the occurrence of two main sources 1 relatively shallow aquifers with ca na k hco 3 and ca mg hco 3 compositions when trapped in volcanic and sedimentary formations respectively and 2 a deep reservoir which is hosted in the mesozoic carbonate sequence rich in co 2 and having a ca so 4 hco 3 composition dissolution of a co 2 rich gas phase into the shallow aquifers produces high tds and high pco 2 cold waters while oxidation of deep derived h 2 s to so 4 2 generates low ph the 13 c co 2 values for gas emissions from 2 8 to 2 7 vs vpdb suggest that the origin of co 2 associated with the deep fluids is mainly related to thermo metamorphic reactions within the carbonate reservoir although significant mantle contribution may also occur however r r a values 0 37 0 62 indicate that he is mainly produced by a crustal source with a minor component from a crust contaminated mantle on the basis of the 13 c ch 4 and d ch 4 values from 25 7 to 19 5 vs vpdb and from 152 to 93 4 vs vsmow respectively ch 4 production is associated with thermogenic processes possibly related to abiogenic co 2 reduction within the carbonate reservoir the 34 s h 2 s values from 9 3 to 10 4 vs vcdt are consistent with the hypothesis of a sedimentary source of sulfur from thermogenic reduction of triassic sulfates geothermometric evaluations based on chemical equilibria co 2 ch 4 and separately h 2 s suggest that the reservoir equilibrium temperature is up to 300 c the d and 18 o data indicate that water recharging both the shallow and deep aquifers has a meteoric origin fluid geochemistry coupled with gravimetric data and tectonic lineaments supports the idea that significant contributions from a deep seated geothermal brine are present in the stigliano thermal fluid discharges exploration surveys investigated this area during 70 s 90 s for geothermal purposes nevertheless presently the area is still under exploited the presence of thermal waters and anomalous heat flow together with the demographic growth of the last years makes this site a suitable location for direct applications of the geothermal resource

unravelling abiogenic and biogenic sources of methane in the earth s deep subsurface at four underground sites in precambrian shield rocks in canada and south africa hydrocarbon and hydrogen gases exsolving from saline fracture waters are analyzed for compositional and isotopic signatures dominated by reduced gases such as ch4 h 2 and higher hydrocarbons ethane propane butane the most 13 c enriched methane end members at all four sites show a pattern of carbon and hydrogen isotopic values similar to abiogenic gases produced by water rock interaction that have been identified previously at one site on the precambrian shield in canada the abiogenic nature of these gases was not previously recognized due to mixing with a second methane component produced by microbial processes the microbial methane end member is identified based on carbon and hydrogen isotopic signatures and dna gene amplification pcr data that indicate the presence of methanogens a framework is presented to estimate the relative contribution of abiogenic versus microbial hydrocarbon gases at these sites this approach has important implications for evaluation of potential abiogenic hydrocarbon reservoirs in a wide range of geologic settings including the longstanding controversy concerning the possible contribution of abiogenic gases to economic petroleum hydrocarbon reservoirs the association of high concentrations of h2 with 13 c enriched ch4 end members and h2 depletion in the 13 c depleted methanogenic end members further suggests the possibility that abiogenic gases may support h2 autotrophy linked to methanogenesis in the deep subsurface d 2005 elsevier b v all rights reserved

carbon isotope composition of organic compounds produced by abiotic synthesis under hydrothermal conditions although it is widely believed that production of organic compounds by fischer tropsch synthesis and related processes occurs in many geologic environments unambiguous identification of compounds with an abiotic origin in natural samples has been hampered by a lack of means to discriminate between abiotic compounds and organic matter from biological sources while isotopic compositions might provide a means to discriminate between biologic and non biologic sources of organic matter there are few data presently available to constrain the isotopic composition of compounds produced by abiotic processes in geologic systems here we report results of laboratory experiments conducted to evaluate the isotopic composition of organic compounds synthesized abiotically under hydrothermal conditions we find the organic products are depleted in 13c to a degree typically ascribed to biological processes indicating that carbon isotopic composition may not be a particularly effective diagnostic means to differentiate between biologic and non biologic sources furthermore our results suggest that the isotopic compositions of reduced carbon compounds found in many ancient rocks that have heretofore been attributed to biological sources could be consistent with an abiotic origin in a hydrothermal setting

comment on mantle hydrocarbons abiotic or biotic by r sugisaki and k mimura this article is a comment on the research reported on by r sugisaki and k mimura concerning the origin of hydrocarbons in mantle xenoliths and other mantle derived rocks such as basalt several lines of research suggest that the source of the hydrocarbons is abiogeneic this research may have important implications for petroleum exploration and production

dating constituent formation in soils to determine rates of soil processes a review abstract rates of soil processes are poorly known one approach to determine them could be through the radiogenic isotopic dating of soil constituents such methods have been recently used to date minerals in soils and weathering profiles thanks to the development of high resolution techniques such as 40ar 39ar u series of micro drilled samples u series by laser ablation and u th he and to the development of suitable methodology expanding application of the techniques to a variety of supergene minerals e g fe and mn oxihydroxides carbonates etc in this paper we identify i the main soil constituents that can be dated through these isotopic methods that are mainly fe oxides mn oxides pedogenic carbonates and organic matter ii the main pedogenic processes that leads to their formation in soils and iii the different soil settings that allow transforming soil constituent ages into rates of soil processes namely growth bands transformation fronts and chronosequences

organic synthesis during fluid mixing in hydrothermal systems hydrothermal circulation can lead to fluid mixing on any planet with liquid water and a source of heat aqueous fluids with differing compositions especially different oxidation states are likely to be far from thermodynamic equilibrium when they mix and provide a source of free energy that can drive organic synthesis from co 2 and h 2 and or supply a source of geochemical energy to chemolithoautotrophic organisms results are presented that quantify the potential for organic synthesis during unbuffered fluid mixing in present submarine hydrothermal svstems as well as hypothetical systems that may have existed on the early earth and mars dissolved hydrogen present in submarine hydrothermal fluids owing to the high temperature reduction of h 2 o as seawater reacts with oceanic crustal rocks provides the reduction potential and the thermodynamic drive for organic synthesis from co 2 or bicarbonate as hydrothermal fluids mix with seawater the potential for organic synthesis is a strong function of the h 2 content of the hydrothermal fluid which is in turn a function of the prevailing oxidation state controlled by the composition of the rock that hosts the hydrothermal system hydrothermal fluids with initial oxidation states at or below those set by the fayalite magnetite quartz mineral assemblage show the greatest potential for driving organic synthesis these calculations show that it is thermodynamically possible for 100 of the carbon in the mixed fluid to be reduced to a mixture of carboxylic acids alcohols and ketones in the range 250 50 c as cold seawater mixes with the hydrothermal fluid as the temperature drops larger organic molecules are favored which implies that fluid mixing could drive the geochemical equivalent of a metaholic system this enormous reduction potential probably drives a large portion of the primary productivity around present seafloor hydrothermal vents and would have been present in hydrothermal systems on the early earth or mars the single largest control on the potential for organic synthesis is the composition of the rock that hosts the hydrothermal system

channel change and the significance of floodplain stratigraphy 1990 flood event lower river tay scotland during february 1990 a flood event on the river tay with an estimated recurrence interval of 70 years in its lower reaches caused extensive flooding and geomorphological change the most extensive area of flooding and dramatic geomorphological change the erosion of two new channels across the floodplain was in the vicinity of the village of caputh perthshire the location of the eroded channels relates to the position of former river courses identifiable by depressions in the floodplain surface and floodplain stratigraphy the lower floodplain surface elevation and occurrence of gravel and sand deposits along the line of the former river courses caused the area to be more vulnerable to erosion and controlled the morphology of the eroded channels

origin of light hydrocarbons in gases from mud volcanoes and ch4 rich emissions abstract this paper presents new chemical data of hydrocarbon rich gases discharged from mud volcanoes and ch4 rich emissions located in different areas of italy northern apennines and sicily the determination of c5 c10 alkanes cyclics and aromatics was carried out by gc ms while the main gas species and c1 c4 hydrocarbons were analyzed by gc tdc and gc fid respectively methane is by far the most abundant component of all the investigated gas emissions with the exception of part of those discharging close to mt etna volcano which are co2 rich the gas samples collected from the emilia apennine and sicily show d ch4 and 13c ch4 values typical of thermogenic gases most gases from the romagna apennine discharge methane with a biogenic isotopic signature non methane hydrocarbons of biogenic gases are almost exclusively c2 c4 alkanes with minor amounts fraction of mol mol of c4 compounds including few aromatics and cyclics likely deriving from minor thermogenic contribution not evidenced by the 13c ch4 and d ch4 values the etnean gases whose r ra and 13c co2 values indicate a strong contribution from a hydrothermal fluid source related to the nearby volcanic system show a significant enrichment of aromatics compounds up to 36 of the non methane organic gas fraction which is likely produced by catalytic reforming processes such as dehydrocyclization of alkanes the thermogenic gases from the apennines and southwestern sicily are characterized by the presence of more than 20 different cyclic compounds with concentrations up to several mol mol cyclic compounds are likely formed by i thermal cracking and ii uncompleted aromatization of alkanes occurring at depth 3 km and temperatures not exceeding 120 150 c

a thermodynamic assessment of the potential synthesis of condensed hydrocarbons during cooling and dilution of volcanic gases the possibility for abiotic synthesis of condensed hydrocarbons in cooling diluting terrestrial volcanic gases has been evaluated on the basis of the consideration of metastable chemical equilibria involving gaseous co co2 h2 and h2o the stabilities of n alkanes and polycyclic aromatic hydrocarbons pahs have been evaluated for several typical volcanic gas compositions under various conditions for cooling diluting of quenched volcanic gas the modeling shows that n alkanes and pahs have a thermodynamic potential to form metastably from h2 and co below 250 c within the stability field of graphite despite the predominance of co2 in volcanic gases synthesis of hydrocarbons from co2 and h2 is less favored energetically than from co and h2 both low temperature and a high h c atomic ratio in volcanic gas generally favor stability of hydrocarbons with higher h c ratios pahs are thermodynamically stable at temperatures 10 50 c higher than large n alkanes however at lower temperatures pahs and n alkanes have similar stabilities and are likely to form metastable mixtures both the energetic drive to form hydrocarbons and possible temperatures of formation increase as the oxidation state o2 of the volcanic gases decreases and as the cooling dilution ratios of volcanic gases increase synthesis of hydrocarbons is energetically more likely in cooling trapped gases than in ashcloud eruptive columns mechanisms for hydrocarbon formation may include fischer tropsch type synthesis catalyzed by magnetite from solid volcanic products on the early earth mars and jupiter s satellite europa several factors would have provided more favorable conditions for hydrocarbon synthesis in volcanic gases than under current terrestrial conditions and might have contributed to the production of organic compounds required for the emergence of life

the determination of deep temperatures by means of the co co2 h2 h2o geothermometer an example using fumaroles in the campi flegrei italy chromatographic analyses of fumarolic gases collected in sampling bottles containing an alkaline solution have been carried out using a thermal conductivity detector and a flame ionization detector after catalytic conversion of co and ch4 the latter method enables the concentration of carbon monoxide to be measured with sufficient accuracy for use in a co co2 h2 h2o geothermometer application of this geothermometer to fumaroles in the crater of solfatara in the campi flegrei italy indicates that they are fed from a steam reservoir at 250 15 c and at 10 36 2atm of oxygen on the other hand the ch4 co2 h2 h2o geothermobarometer seems to re equilibrate at superficial temperatures and cannot be used for infering thermodynamic conditions at depth regular sampling of these fumaroles together with a geothermometric interpretation of the gas analyses provides a means of monitoring with comparative accuracy the chemical and thermal evolution of the hydrothermal reservoir below the solfatara crater such monitoring would probably detect an increase in temperature at depth and the injection of magmatic gas into the reservoir

volatile lines of descent in submarine plutonic environments insights from stable isotope and fluid inclusion analyses microthermometric and isotopic analyses of fluid inclusions in primitive olivine gabbros oxide gabbros and evolved granitic material recovered from ocean drilling program hole 735b at the southwest indian ridge provide new insights into the evolution of c o h nacl fluids in the plutonic foundation of the oceanic crust the variably altered and deformed plutonic rocks span a crustal section of over 1500 m and record a remarkably complex magma hydrothermal history magmatic fluids within this suite followed two chemically distinct paths during cooling through the subsolidus regime the first path included formation of co21ch41h2o1c fluids with up to 43 mole ch 4 the second path produced hypersaline brines that contain up to 50 nacl equivalent salinities subsequent to devolatilization respeciation of magmatic co2 attendant graphite precipitation and cooling from 800 c to 500 c promoted formation of ch 4 enriched fluids these fluids are characterized by average d 13 c ch4 values of 227 1 6 4 3 n5 45 with associated d 13 c co2 compositions ranging from 224 9 to 21 9 n539 and average dd values of exsolved vapor of 241 6 12 n523 in pods veins and lenses of highly fractionated residual material hypersaline brines formed during condensation and by direct exsolution in the absence of a conjugate vapor phase entrapped co21ch41h2o rich fluids within many oxide bearing rocks and felsic zones are significantly depleted in 13 c with d 13 c co2 values down to about 225 and contain co 2 concentrations higher than those predicted by equilibrium devolatilization models we hypothesize that lower effective pressures in high temperature shear zones promoted infiltration of highly fractionated melts and compositionally evolved volatiles into focused zones of deformation significantly weakening the rock strength in felsic rich zones volatile build up may have driven hydraulic fracturing of gabbroic wall rocks resulting in the formation of magmatic breccias comparison of isotopic compositions of fluids in plutonic rocks from 735b the mark area of the mid atlantic ridge and the mid cayman rise indicate 1 that the carbon isotope composition of the lower oceanic crust may be far more heterogeneous than previously believed and 2 that carbon bearing species in the oceanic crust and their distribution at depth are highly variable copyright 2001 elsevier science ltd

evidence of subsurface anaerobic biodegradation of hydrocarbons and potential secondary methanogenesis in terrestrial mud volcanoes abstract the assessment of gas origin in mud volcanoes and related petroleum systems must consider post genetic processes which may alter the original molecular and isotopic composition of reservoir gas beyond eventual molecular and isotopic fractionation due to gas migration and microbial oxidation investigated in previous studies we now demonstrate that mud volcanoes can show signals of anaerobic biodegradation of natural gas and oil in the subsurface a large set of gas geochemical data from more than 150 terrestrial mud volcanoes worldwide has been examined due to the very low amount of c 2 in mud volcanoes isotopic ratios of ethane propane and butane generally the best tracers of anaerobic biodegradation are only available in a few cases however it is observed that 13 c enriched propane is always associated with positive 13 c co2 values which are known indicators of secondary methanogenesis following anaerobic biodegradation of petroleum data from carbon isotopic ratio of co 2 are available for 134 onshore mud volcanoes from 9 countries azerbaijan georgia ukraine russia turkmenistan trinidad italy japan and taiwan exactly 50 of mud volcanoes all releasing thermogenic or mixed methane show at least one sample with 13 c co2 5 pdb thermogenic ch 4 associated with positive carbon isotopic ratio of co 2 generally maintains its 13 c enriched signature which is therefore not perturbed by the lighter secondary microbial gas there is however high variability in the 13 c co2 values within the same mud volcanoes so that positive 13 c co2 values can be found in some vents and not in others or not continuously in the same vent this can be due to high sensitivity of 13 c co2 to gas water rock interactions or to the presence of differently biodegraded seepage systems in the same mud volcano however finding a positive 13 c co2 value should be considered highly indicative of anaerobic biodegradation and further analyses should be made especially if mud volcanoes are to be used as pathfinders of the conditions indicative of subsurface hydrocarbon accumulations in unexplored areas

orogens and slabs vs their direction of subduction abstract subduction zones appear primarily controlled by the polarity of their direction i e w directed or e to nne directed probably due to the westward drift of the lithosphere relative to the asthenosphere the decollement planes behave differently in the two end members in the w directed subduction zone the decollement of the plate to the east is warped and subducted whereas in the e to nne directed it is ramping upward at the surface there are w directed subduction zones that work also in absence of active convergence like the carpathians or the apennines w directed subduction zones have shorter life 30 40 ma than e or ne directed subduction zones even longer than 100 ma the different decollements in the two end members of subduction should control different ptt paths and therefore generate variable metamorphic assemblages in the associated accretionary wedges and orogens these asymmetries also determine different topographic and structural evolutions that are marked by low topography and a fast eastward migrating structural wave along w directed subduction zones whereas the topography and the structure are rapidly growing upward and expanding laterally along the opposite subduction zones the magmatic pair calc alkaline and alkaline tholeiitic volcanic products of the island arc and the back arc basin characterise the w directed subduction zones magmatic rocks associated with e or ne directed subduction zones have higher abundances of incompatible elements and mainly consist of calc alkaline shoshonitic suites with large volumes of batholithic intrusions and porphyry copper ore deposits the subduction zones surrounding the adriatic plate in the central mediterranean confirm the differences among subduction zones as primarily controlled by the geographic polarity of the main direction of the slab the western margin of the adriatic plate contemporaneously overridden and underthrust europe toward the west to generate respectively the alps and the apennines while the eastern margin subducted under the dinarides hellenides these belts confirm the characters of the end members of subduction zones as a function of their geographic polarity similarly to the pacific subduction zones

geophysical and petrological modelling of the structure and composition of the crust and upper mantle in complex geodynamic settings the tyrrhenian sea and surroundings abstract information on the physical and chemical properties of the lithosphere asthenosphere system las can be obtained by geophysical investigation and by studies of petrology geochemistry of magmatic rocks and entrained xenoliths integration of petrological and geophysical studies is particularly useful in geodynamically complex areas characterised by abundant and compositionally variable young magmatism such as in the tyrrhenian sea and surroundings a thin crust less than 10 km overlying a soft mantle where partial melting can reach about 10 is observed for magnaghi vavilov and marsili which belong to the central tyrrhenian sea backarc volcanism where subalkaline rocks dominate similar characteristics are seen for the uppermost crust of ischia a crust about 20 km thick is observed for the majority of the continental volcanoes including amiata vulsini roccamonfina phlegraean fields vesuvius vulture stromboli vulcano lipari etna and ustica a thicker crust is present at albani about 25 km and at cimino vico sabatini about 30 km the structure of the upper mantle in contrast shows striking differences among various volcanic provinces volcanoes of the roman region vulsini sabatini alban hills sit over an upper mantle characterised by vs mostly ranging from about 4 2 to 4 4 km s at the alban hills however slightly lower vs values of about 4 1 km s are detected between 60 and 120 km of depth this parallels the similar and rather homogeneous compositional features of the roman volcanoes whereas the lower vs values detected at the alban hills may reflect the occurrence of small amounts of melts within the mantle in agreement with the younger age of this volcano the axial zone of the apennines where ultrapotassic kamafugitic volcanoes are present has a mantle structure with high velocity lid vs 4 5 km s occurring at the base of a 40 km thick crust beneath the campanian volcanoes of vesuvius and phlegraean fields the mantle structure shows a rigid body dipping westward a feature that continues southward up to the eastern aeolian arc in contrast at ischia the upper mantle contains a shallow low velocity layer vs 3 5 4 0 km s just beneath a thin but complex crust the western aeolian arc and ustica sit over an upper mantle with vs 4 2 4 4 km s although a rigid layer vs 4 55 km s from about 80 to 150 km occurs beneath the western aeolian arc in sardinia no significant differences in the las structure are detected from north to south the petrological geochemical signatures of italian volcanoes show strong variations that allow us to distinguish several magmatic provinces these often coincide with mantle sectors identified by vs tomography for instance the roman volcanoes show remarkable similar petrological and geochemical characteristics mirroring similar structure of the las the structure and geochemical isotopic composition of the upper mantle change significantly when we move to the stromboli campanian volcanoes the geochemical signatures of ischia and procida volcanoes are similar to other campanian centres but sr pb isotopic ratios are lower marking a transition to the backarc mantle of the central tyrrhenian sea the structural variations from stromboli to the central vulcano and lipari and western aeolian arc are accompanied by strong variations of geochemical signatures such as a decrease of sr isotope ratios and an increase of nd pb isotope and lile hfse ratios the dominance of mafic subalkaline magmatism in the tyrrhenian sea basin denotes large degrees of partial melting well in agreement with the soft characteristics of the uppermost mantle in this area in contrast striking isotopic differences of plio quaternary volcanic rocks from southern to northern sardinia does not find a match in the las geophysical characteristics the combination of petrological and geophysical constraints allows us to propose a 3d schematic geodynamic model of the tyrrhenian basin and bordering volcanic areas including the subduction of the ionian adria lithosphere in the southern tyrrhenian sea and to place constraints on the geodynamic evolution of the whole region

trace element accumulation in mn fe oxide nodules of a planosolic horizon the aim of this work was to determine the importance of nodule formation on the dynamics of major and trace elements tes along a planosol toposequence developed in metamorphic parent material at la ch tre massif central france the different horizons were sampled within three pits and analysed for major and trace element contents the nodule rich horizon was studied more closely a simplified sequential extraction scheme x ray diffraction xrd and microscopic approaches were used in order to determine the individual phases containing te in nodules along the slope the nodule rich horizon varies in thickness is composed of different oxide fractions and has different scavenging efficiencies according to the te considered iron was found to accumulate in the middle of the slope while mn accumulated at the base the scavenging effect is only evident for ni in profile 1 for fe and cu it is maximal in profile 2 where the nodule rich horizon is the thickest for pb and mn maximal scavenging effect is recorded for both profiles 2 and 3 in the lowest part of the slope cr is not accumulated at all this was related to the water dynamic and the hydromorphic conditions prevailing along the slope results obtained by sequential extractions and associated x ray diffraction on the different nodule size fractions and those obtained by electron microprobe allow inference of the te distribution in nodules nodules were mainly composed of three to four types of cements surrounding grains of quartz feldspars micas and accessory minerals iron rich cements si and al rich cements mn rich cements and ti rich cements in places the iron rich cements consist of poorly crystalline goethite and possibly some ferrihydrite ferrihydrite is associated with cr as demonstrated by extractions goethite contained mn and most of the te extracted except for ni and pb fine grained si and al rich cements were also observed they contain variable amounts of ti and mn mn rich cements were not present in all the nodules and were mainly linked to the dark zones of the nodules the nature of these mn oxides could not be determined they were found to contain co ni cu and probably pb

multiple origins of methane at the lost city hydrothermal field abstract the high concentrations of methane in the vent fluids of the lost city hydrothermal field represent the sum of abiotic and biological sources and sinks stable isotopes of carbon are of limited value in discriminating between the various sources of methane because the isotope effects associated with the multiple processes forming and consuming methane are each poorly constrained and the products of these processes are pooled furthermore reservoir effects complicate interpretation the near quantitative reduction of inorganic carbon to methane under highly reducing conditions limits the isotope effects associated with methanogenesis however the carbon isotope compositions of lipids derived from anaerobic methanotrophs suggest that more than one isotopically distinct pool of methane exists at lost city in this analysis we integrate multiple lines of evidence to constrain the relative contribution of various processes at lost city the processes that we consider here include i fischer tropsch type ftt abiotic synthesis of methane and other hydrocarbons ii the sabatier process for the abiotic synthesis of methane alone iii biological methane production by methanosarcinales and iv biological methane consumption by anaerobic and aerobic methanotrophs this analysis suggests that abiotic processes particularly the sabatier reaction are likely to be the dominant source of methane at lost city biological methane is present in the vent fluids but does not compose a high fraction of the total methane pool these observations imply that ultramafic systems could have supplied abundant reduced carbon to the early earth even without biological catalysis

the main characteristics of the lithosphere asthenosphere system in italy and surrounding regions we present a summary of the available information on rayleigh wave dispersion data for the italian area the dispersion curves can be grouped into two main families according to their shape one with an almost linear trend in the period range from 40 to 150 sec the other with a relatively flat portion in the period range from 40 to 80 sec the inversion of these data shows that there are strong lateral variation in the lithosphere system a very rapid transition in the lithospheric thickness from about 130 km to about 30 km as well as in the s wave velocity of the lithosphere and asthenosphere

origins of methane discharging from volcanic hydrothermal geothermal and cold emissions in italy abstract 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 13c ch4 and d 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 13c ch4 and d 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 13c ch4 from 21 6 to 36 9 v pdb and d 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 13c ch4 and d ch4 values i e as low as 69 v pdb and

a model for ischia hydrothermal system evidences from the chemistry of thermal groundwaters abstract ischia volcano in central italy has long been known for its copious surface hydrothermal manifestations signs of a pervasive circulation of hot fluids in the subsurface because of the significant chemical heterogeneity of fumarolic gas discharges and hot spring discharges evidences of a complex hydrothermal setting a definite model of fluid circulation at depth is currently unavailable in spite of the several previous efforts here we report on the chemical and isotopic composition of 120 groundwater samples collected during several sampling surveys from 2002 to 2007 the acquired data suggest that the composition of surface manifestations reflect contributions from meteoric water sea water and thermal fluids rising from two distinct hydrothermal reservoir with equilibrium temperatures of respectively 150 c and 270 c and depths of 150 300 m and 300 m but possibly 1000 m we also make use of an isotopic characterization of the dissolved gas phase in thermal waters to demonstrate that the ischia hydrothermal system is currently supplied by a deep rising gas component dgc characterized by co2 97 7 1 2 vol on a water free basis 13cco2 3 51 0 9 and helium isotopic ratio of about 3 5 ra 3he 4he ratio normalized to the air ratio ra likely magmatic in origin an assessment of the thermal budget for ischia hydrothermal system is also presented in the attempt to derive a first estimate of the size and rate of degassing of the magmatic reservoir feeding the gas emissions we calculate that a heat flow of about 153 222 mw presently drives hydrothermal circulation on the island which we suggest is supplied in convective form e g by the ascent of a high t magmatic vapour phase by complete degassing of 2 2 3 3 107 m3 yr 1 of trachytic magma with 2 1 wt dissolved h2o content if extrapolated to entire period of quiescence lasting since the arso eruption in 1302 a d this volume corresponds to 1 6 2 3 1010 m3 of magma degassed in about 700 years of quiescent activity

geochemistry of high h2 and ch4 vent fluids issuing from ultramafic rocks at the rainbow hydrothermal field 36 14 n mar the flores diving cruise was part of the mast iii amores 1995 1998 program funded by the european union one of the major achievements of the flores cruise was the discovery of the rainbow hydrothermal field hosted in ultramafic rocks south of the amar segment on the mid atlantic ridge mar the rainbow hydrothermal fluids exhibit temperatures of 365 c ph of 2 8 high chlorinity 750 mmol kg and low silica 6 9 mmol kg the uniformity in endmember major minor trace element concentrations and gas contents suggests that all rainbow fluids originate from the same deep source although h2s content is relatively low 1 20 mmol kg all vent fluids show extraordinary high h2 16 mmol kg ch4 2 5 mmol kg and co 5 mol kg endmember concentrations compared to fluids collected from other vent sites along the mar hydrogen represents more than 40 of the total gas volume extracted from the fluids at rainbow h2 production is likely associated with alteration of olivine and orthopyroxene minerals during serpentinization given that exposures of ultramafic rock may be common particularly along slow spreading ridges the production of h2 may have important implications for microbial activity at and beneath the seafloor

temperature pressure and redox conditions governing the composition of the cold co2 gases discharged in north latium central italy abstract gases rich in co2 are produced over the northern latium area by metamorphic reactions involving carbonate formations or by magma degassing the gas migrates towards the surface and accumulates in sedimentary permeable structures which act as gas traps in that environment the pco2 is a variable externally fixed and the redox conditions at which the gases equilibrate are governed by the c co2 buffer temperature in the interval 100 180 c and pco2 from few bar to tens of bar have been estimated by means of the ratios between the redox sensitive gas species and co2 the composition of gases from two geothermal wells located in the study area and of other hydrothermal fluids suggest that the redox potential of low medium temperature carbonate hosted hydrothermal systems may be fixed by the c co2 buffer

the origin of the fumaroles of la solfatara campi flegrei south italy abstract the analysis of gaseous compositions from solfatara campi flegrei south italy fumaroles since the early 1980s clearly reveals a double thermobarometric signature a first signature at temperatures of about 360 c was inferred by methane based chemical isotopic geoindicators and by the h2 ar geothermometer these high temperatures close to the critical point of water are representative of a deep zone where magmatic gases flash the hydrothermal liquid forming a gas plume a second signature was found to be at around 200 240 c at these temperatures the kinetically fast reactive species h2 and co re equilibrate in a pure vapor phase during the rise of the plume a combination of these observations with an original interpretation of the oxygen isotopic composition of the two dominant species i e h2o and co2 shed light on the origin of fumarolic fluids by showing that effluents are mixture between fluids degassed from a magma body and the vapor generated at about 360 c by the vaporization of hydrothermal liquids a typical andesitic water type d 20 18o 10 and a co2 rich composition x co 2 0 4 has been inferred for the magmatic fluids while for the hydrothermal component a meteoric origin and a co2 fugacity fixed by fluid rock reaction at high temperatures have been estimated in the time the fraction of magmatic fluids in the fumaroles increased up to 0 5 at each seismic and ground uplift crisis bradyseism which occurred at campi flegrei suggesting that bradyseismic crises are triggered by periodic injections of co2 rich magmatic fluids at the bottom of the hydrothermal system

geochemistry of hydrothermal fluids from an intraplate ocean island everman volcano socorro island mexico abstract socorro island mexico still volcanically active is an alkaline and peralkaline volcanic island in the eastern pacific ocean located on a mid ocean ridge spreading center that was abandoned at 3 5 ma gas and water samples collected on the island in 1999 from the dome fumaroles and hot springs of everman volcano have been analyzed for major components h o c s he and ar isotopic composition and noble gas abundances the boiling point temperature steam vents and low salinity thermal springs discharge cl free meteoric water and are typical surface manifestations of a high temperature hydrothermal system high h 2 and ch 4 contents up to 14 and 3 5 vol in dry gas respectively and an enrichment of ch 4 in 13 c 13 c ch 4 18 may suggest that these reduced gases were at least partially produced by the interaction of ultramafic rocks with water inside volcanic edifice due to serpentinization of olivine the 3 he 4 he ratios 6 0 6 6 r a which are lower than the morb values and the high he ne ratios 4000 and he ar ratios up to 4 indicate a contribution of radiogenic he from the oceanic crust or shallow magma chamber like at a low 3 he hot spot the maximum of the 40 ar 36 ar values 311 is close to the maximum value found in the socorro volcanic rocks noble gas abundances are close to values for the partially degassed air saturated water however with some excess ne concentrations an enrichment in 132 xe or depletion in 84 kr of the least air contaminated gas sample he ne 4000 relative to air saturated water can be related to the contribution of noble gases from a non atmospheric source probably oceanic crustal component assimilated in a shallow magma reservoir

origin of nitrogen rich natural gases in the california great valley evidence from helium carbon and nitrogen isotope ratios abstract dry natural gases produced from the sacramento and northern san joaquin basins contain up to 87 nitrogen 15n measurements for gases with n2 8 vary from 0 9 to 3 5 methane 13c values vary from 61 to 15 3 he 4 he ratios indicate the presence of mantle derived helium in addition to radiogenic crustal helium and suggest that the gases may originate from mixing between three principal components a hydrocarbon rich gas with 3 he 4 he 0 1r a derived from the microbial and thermogenic alteration of sedimentary organic matter a hydrocarbonrich gas with 3 he 4 he 2 75r a derived from the localized pyrolysis of sediments by magmatic volatiles and a nitrogenrich gas with 3 he 4 he 1r a the nitrogen rich component is characterized by methane 13c less negative than 25 and n 2 ar ratios as high as 22 000 nitrogen concentrations tend to increase towards the basement along the shallow eastern margin of the valley suggesting that the nitrogen rich component is derived from metasedimentary rocks deep within the crust the coast ranges fraciscan complex which was thrust well beneath the great valley during late mesozoic and early cenozoic subduction appears to be the most likely source

geochemical investigations of submarine volcanic exhalations to the east of panarea aeolian islands italy abstract results are presented on scubadiving investigations carried out on thermal manifestations in the area of panarea aeolian islands the area investigated falls inside a caldera which extends from the main island to the group of islets located to the northeast the distribution of the gaseous manifestations is regulated by the ne sw nw se and n s regional tectonic directrices through which the more recent basic magma intruded giving rise to dikes and pillow lavas f o 2 temperature relation of the gases sampled in the investigated area was calculated to be log f o 2 11 24 593 t which indicates that a buffering mechanism acted on the gases as they cooled down during their ascent the high 3 he 4 he ratio 6 10 6 and the 13 c 3 2 pdb suggest the presence of a magmatic component in the gas feeding the investigated manifestations the above relations and the almost constant high he n 2 ratio suggest that all the fumaroles are fed by the same deep hot fluids on the basis of both the chemical characters of the fluids and the geothermo barometric data a deep geothermal body having a temperature of about 240 c is recognized two other shallower thermal aquifers with a temperature of 170 210 c are identified a circulation pattern of the geothermal fluids is also proposed on the basis of calculations regarding the convective energy released by the geothermal system of panarea and the magmatic mass responsible for the positive gravimetric anomaly of the area it was estimated that the last volcanic activity took place less then 10 000 years ago

thermal springs in italy their relation to recent tectonics the large scale circulation of thermal waters in italy is reviewed from both a chemical and an isotopic point of view two main areas are recognized one in the alpine region and the other in the central southern apennine region the alps are an area of very high hydraulic heads and low thermal gradients where hot deep seated waters of meteoric origin rapidly reach the surface along active boundary fault systems the apennines in contrast are characterized by lower hydraulic heads and higher thermal gradients all thermal springs in italy including those in active volcanic areas originate essentially from meteoric waters and most follow long pathways in mesozoic carbonate anhydritic aquifers before emerging as indicated by relations among present hydrothermal activity in central southern italy deep crustal structures and pco2 content in thermal waters

the contribution of fluid geochemistry to the volcano monitoring of stromboli abstract the persistent open vent mild explosive activity of stromboli volcano is episodically interrupted by more violent and dangerous explosive events major explosions and paroxysms according to the nature of erupted products paroxysms can be related either to the explosion of overpressured gas pockets located in the proximity of the magma column or to the sudden uprise of hot gas rich magma from a deep part of the plumbing system in both cases these more energetic explosive events should be preceded by an escape or a preferential uprise of the highly mobile volatiles which in turn should produce gas leakage anomalies at the surface in sites of high vertical permeability such as deep reaching faults in order to identify such gas leaking sites a systematic co2 soil flux survey has been carried out on the island using an accumulation chamber four hundred sixty one points have been measured with a high density in the summit crater area where high flux values have been found 10 3 10 2 cm s anomalous points are concentrated along the main ne sw axial feeding system of the volcano co2 soil flux decreases from the crater zone to the base of the volcanic cone where however an interesting gas leakage anomaly occurs pizzillo mofette in the pizzillo area thermal water wells also occur whose chemistry indicates an origin by sea water heated by hot gas soil gases have been sampled in the sites with the highest co2 flux in the crater area and at the base of the cone chemical and isotopic analyses indicate the presence of a deep gas component especially in the crater zone samples high co2 appreciable contents of he and h2 3he 4he values up to 3 55 13c of co2 2 the sc5 low flux fumarole on the crater rim has shown during six years a remarkable persistence of temperature 93 95 c with only minor fluctuations of chemistry appearance of anomalous peaks of h2 in correspondence with strombolian explosions was observed during a 2 h 30 min experiment of continuous recording of hydrogen content of the fumarole together with previous data on h2o co2 and he this experiment confirms that strombolian blasts produce rapid fluctuations in the fumarolic gas composition in the light of this study sc5 fumarole and pizzillo mofette look promising sites for the testing of a continuous geochemical monitoring system of stromboli volcano

abiogenic fischer tropsch synthesis of hydrocarbons in alkaline igneous rocks fluid inclusion textural and isotopic evidence from the lovozero complex n w russia a detailed fluid inclusion study has been carried out on the hydrocarbon bearing fluids found in the peralkaline complex lovozero petrographic microthermometric laser raman and bulk gas data are presented and discussed in context with previously published data from lovozero and similar hydrocarbon bearing alkaline complexes in order to further understand the processes which have generated these hydrocarbons ch4 dominated inclusions have been identified in all lovozero samples they occur predominantly as secondary inclusions trapped along cleavage planes and healed fractures together with rare h2o dominant inclusions they are consistently observed in close association with either arfvedsonite crystals partially replaced by aegirine aegirine crystals or areas of zeolitization the majority of inclusions consist of a low density fluid with ch4 homogenisation temperatures between 25 and 120 c those in near surface hand specimens contain ch4 h2 up to 40 mol higher hydrocarbons however inclusions in borehole samples contain ch4 higher hydrocarbons h2 indicating that at depth higher hydrocarbons are more likely to form estimated entrapment temperatures and pressures for these inclusions are 350 c and 0 2 0 7 kbar a population of high density liquid ch4 dominant inclusions have also been recorded mainly in the borehole samples homogenising between 78 and 99 c these consist of pure ch4 trapped between 1 2 and 2 1 kbar and may represent an early ch4 bearing fluid overprinted by the low density population the microthermometric and laser raman data are in agreement with bulk gas data which have recorded significant concentrations of h2 and higher hydrocarbons up to c6h12 in these samples these data combined with published isotopic data for the gases ch4 c2h6 h2 he and ar indicate that these hydrocarbons have an abiogenic crustal origin and were generated during postmagmatic low temperature alteration reactions of the mineral assemblage this would suggest that these data favour a model for formation of hydrocarbons through fischer tropsch type reactions involving an early co2 rich fluid and h2 derived from alteration reactions this is in contrast to the late magmatic model suggested for the formation of hydrocarbons in the similar peralkaline intrusion ilimaussaq at temperatures between 400 and 500 c

dissolution of kaolinites and accumulation of iron oxides in lateritic ferruginous nodules mineralogical and microstructural transformations abstract in situ geochemical and structural microanalysis of non disturbed samples of laterite and mineralogical identifications of microsamples demonstrate an orderly succession of mineralogical and structural transformations these transformations result in the formation of fe nodules they start from a micaceous phase whose micropores are occupied by hematite because the source of iron is external to micas this hematite corresponds to an absolute accumulation in the meaning of brewer 1964 the following transformations constitute a succession of three mineral phases corresponding to relative accumulations with the removal of some components and in situ reutilization of residual materials 1 phase of fe kaolinite accumulation during which the structures inherited from micas are preserved 2 phase of al hematite accumulation resulting from a dissolution of fe kaolinite with development of pedoplasma and vesicular porosity 3 phase of accumulation of more or less aluminous goethite which ultimately results in the crystallization of geodes at the borders of voids

chemistry of thermal springs in the larderello travale geothermal region southern tuscany italy abstract thirty two thermal spring eleven cold spring and six steam condensates in the larderello travale geothermal region have been studied from a geochemical point of view the aim of this work was to delineate the relation between the chemical composition of the natural thermal manifestations and the thermal anomaly which is among the best known in the world the larderello spring both hot and cold are characterized by low salinity total dissolved solids generally lower than 1000 mg kg and alkaline earth bicarbonate composition in contrast an alkaline earth sulfate composition characterizes the thermal springs of the travale area this difference is due to the fact that the underground pathways of the larderello hot springs are only in shallow flyschoid caprock formations whereas at travale the paths are longer and in carbonate anhydritic mesozoic rocks which constitute the main reservoir formations in both the larderello and travale areas the thermal character of larderello springs is therefore mainly due to rock conduction whereas in travale it is mostly due to inflows of hot fluid phases from the geothermal reservoir comparison between ammonia li and b in fluid phases both steam condensates and hot springs in the larderello area suggests that in some of them their temperatures might be partly due to direct vapor inflows