silicon isotope fractionation during silica precipitation from hot spring waters evidence from the geysir geothermal field iceland this study aims to explore the extent and controls of silicon isotope fractionation in hot spring systems of the geysir geothermal area iceland a setting where sinter deposits are actively formed the 30si values of dissolved silica measured in the spring water and sampling sites along outflowing streams covering a temperature range between 20 and 100 c were relatively constant around 0 2 whereas the 30si signatures of associated opaline sinters from the streambeds were between 0 1 and 4 0 becoming progressively more negative in the downstream parts of the aprons here the deposited sinters represent some of the most 30si depleted abiotically produced terrestrial materials documented to date compared to the data reported for icelandic basalts considered to be the source of the silicon the 30si values of the fluids and sinter deposits are higher and lower respectively the resulting values for apparent solid water isotope fractionation 30sisolid water decreased with decreasing temperature from ca 0 7 at 80 c to 3 7 at 20 c locally down to 4 4 this temperature relationship was reproducible in each of the investigated hot spring systems and is qualitatively consistent with recent findings in laboratory experiments on kinetic fractionation for a flowing fluid however the apparent fractionation magnitudes observed in the field are ca 2 more negative and thus significantly larger we infer that solid water silicon isotope fractionation during deposition of amorphous silica from a flowing fluid correlates inversely with temperature but is essentially a function of the precipitation rate such that the fractionation factor decreases with increasing rate as an important corollary the effective fractionation behavior during precipitation of silica from saturated solutions is a system dependent feature which should be taken into account when using silicon isotopes for paleo environmental reconstructions

carbonates in cm2 chondrites constraints on alteration conditions from oxygen isotopic compositions and petrographic observations high precision measurements of the oxygen isotopic compositions of carbonates calcite and dolomite from five cm2 chondrites are presented and put into context of the previously determined mineralogic alteration index mai which places these meteorites into an alteration sequence the carbonate oxygen isotopic compositions range from 20 0 to 35 7 for 18o 8 0 to 17 7 for 17o and 0 7 to 2 7 for 17o carbonate 17o values are inversely correlated with mai and track the evolution of fluid composition from higher to lower 17o values with increasing alteration on the cm parent body similar 17o values for calcite and dolomite fractions from the same splits of the same meteorites indicate that calcite and dolomite in each split precipitated from a single fluid reservoir however reversed calcite dolomite fractionations 18odol 18occ indicate that the fluid was subject to processes such as freeze thaw or evaporation that fractionated isotopes in a mass dependent way consideration of the carbonate isotopic data in the context of previously proposed models for aqueous alteration of carbonaceous chondrites has provided important insights into both the evolving alteration conditions and the utility of the models themselves the data as a whole indicate that the isotopic evolution of the fluid was similar to that predicted by the closed system two reservoir models but that a slightly larger matrix water fractionation factor may apply in the context of this model more altered samples largely reflect greater reaction progress and thus probably indicate more extended times of fluid exposure petrographic observations of carbonates reveal a trend of variable carbonate morphology correlated with alteration that is also consistent with changes in the duration of fluid rock interaction the data can also be reconciled with fluid flow models in a restricted region of the parent body which is consistent with assertions that the different types of carbonaceous chondrites derive from different regions of their parent bodies in this case the model results for a 9 km radius body and our data place the location of the cm chondrite formation in a 100 m thick zone 1 km from the surface the size of this zone could be increased if the model parameters were adjusted

cross hole fracture connectivity assessed using hydraulic responses during liner installations in crystalline bedrock boreholes abstract in order to continually improve the current understanding of flow and transport in crystalline bedrock environments developing and improving fracture system characterization techniques is an important area of study the presented research examines the installation of flexible impermeable flute liners as a means for assessing cross hole fracture connectivity flute liners are used to generate a new style of hydraulic pulse with pressure response monitored in a nearby network of open boreholes drilled in gneissic rock of the canadian shield in eastern ontario canada borehole liners were installed in six existing 10 15 cm diameter boreholes located 10 35 m apart and drilled to depths ranging between 25 45 m liner installation tests were completed consecutively with the number of observation wells available for each test ranging between one and six the collected pressure response data have been analyzed to identify significant groundwater flow paths between source and observation boreholes as well as to estimate inter well transmissivity and storativity using a conventional type curve analysis while the applied solution relies on a number of general assumptions it has been found that reasonable comparison can be made to previously completed pulse interference and pumping tests results of this research indicate areas where method refinement is necessary but nonetheless highlight the potential for use in crystalline bedrock environments this method may provide value to future site characterization efforts given that it is complementary to and can be used in conjunction with other currently employed borehole liner applications such as the removal of cross connection at contaminated sites and the assessment of discrete fracture distributions when boreholes are sealed recreating natural hydraulic gradient conditions

a combined in situ oxygen silicon isotopic and fluid inclusion study of a chert sample from onverwacht group 3 35ga south africa new constraints on fluid circulation abstract cherts have been extensively used as a proxy of precambrian environmental conditions of the earth cherts from the onverwacht group 3 5 3 3 ga south africa are considered as well preserved and have been used as a paleo oceanic thermometer especially by using the oxygen isotope composition of the chert nevertheless there are several lines of evidence size and number of the quartz veins that fluids circulated through these cherts after their deposition these cherts are composed mainly of microquartz with large quartz veins 100 m and iron carbonates as ankerites a combined study of oxygen silicon and fluid inclusions study have been performed on one chert sample from the onverwacht group in order to assess the effect of these fluid circulations on the chert oxygen and silicon isotopic compositions in situ oxygen and silicon isotopic compositions on microquartz and vein quartz were measured at high spatial resolution using a multicollector cameca 1270 ion probe crpg cnrs nancy moreover fluid inclusions present in the quartz veins are considered to determine the origin and conditions of the fluid circulation three types of primary fluid inclusions carbonic lc aqueous carbonic fluids lc w and aqueous fluid lw have been observed the temperatures of this fluid circulation were determined by microthermometry and using quartz carbonate pair thermometry at between 200 c and 300 c fluid pressures range from 100 mpa to 30 mpa which correspond to depths ranging from 4 to 1 km this evolution could be related to an exhumation associated with a dilution and cooling process this fluid circulation could be associated to the gold bearing fluid responsible of the sheba fairview ore system dated at 3074 6 ma the results of the isotopic study show that these fluid circulations homogenised the oxygen isotope composition but not the entire silicon isotope composition of the microquartz the 18 o value calculated for the fluid show that it equilibrated with carbonate rocks and is similar to the composition of the gold bearing fluid the silicon isotope composition of the microquartz allows determination of the initial 30 si of the microquartz precursor this precursor has been precipitated from a hydrothermal fluid hence a combined 18 o 30 si and fluid inclusion study allows the conditions of the fluid circulation to be constrained and the origins of chert to be determined

interpretation of field tracer tests of a single fracture using a transient solute storage model the results and interpretation of five induced gradient tracer tests performed at five different average interborehole fluid velocities in a single fracture in monzonitic gneiss are described the experiments were conducted using radioactive 82br and a fluorescent dye as conservative tracers where the tracers were pulse injected into radial convergent and injection withdrawal flow fields the flow fields were established between straddle packers isolating the fracture in three boreholes over distances of 12 7 29 8 m the tracer breakthrough curves were determined from samples of the withdrawn groundwater and were interpreted using residence time distribution rtd theory and two deterministic simulation models the rtd curves of the tracer experiments were interpreted by fitting to the field data a simple advection dispersion model and an advection dispersion model with transient solute storage in immobile fluid zones both models consider the different flow field geometries associated with injection withdrawal and radial convergent tests comparison of the fits obtained by the simulation models suggest that the initial period of solute transport in single fractures is advection dominated and with increasing tracer residence time or decreasing fluid velocity transport progresses toward more fickian like behavior during the advective dominated period the transient solute storage model is shown to adequately describe the asymmetries and long tails characteristic of the fracture rtds interpretation of the tracer experiments using both simulation models further suggests that induced gradient tracer experiments are likely to underestimate the dispersive characteristics of single fractures under natural flow conditions

oxygen isotope studies of carbonaceous chondrites abstract the carbonaceous chondrites display the widest range of oxygen isotopic composition of any meteorite group as a consequence of the interaction of primordial isotopic reservoirs in the solar nebula these isotopic variations can be used to identify the reservoirs and to determine conditions and loci of their interactions we present a comprehensive set of whole rock analyses of cv co ck cm cr ch and ci chondrites as well as selected components of some of these meteorites a simple model is developed which describes the isotopic behavior during parent body aqueous alteration processes the process of thermal dehydration also produces a recognizable effect in the oxygen isotopic composition

the oxygen isotope record in murchison and other carbonaceous chondrites the ranges of 18o and 17o in components of the murchison c2 chondrite exceed those in all other meteorites analyzed previous authors have proposed that c2 chondrites are the products of aqueous alteration of anhydrous silicates a model is presented to determine whether the isotopic variations can be understood in terms of such alteration processes the minimum number two of initial isotopic reservoirs is assumed two major stages of reservoir interaction are required one at high temperature to produce the16o mixing line observed for the anhydrous minerals and another at low temperature to produce the matrix minerals the isotopic compositions severely constrain the conditions of the low temperature process requiring temperatures 44 extension of the model to the data on c1 chondrites requires aqueous alteration in a warmer wetter environment

hydraulic tests in highly permeable aquifers 1 a semianalytical solution is presented for a mathematical model describing the flow of groundwater in response to a slug or pumping test in a highly permeable confined aquifer this solution which is appropriate for wells of any degree of penetration and incorporates inertial mechanisms at both the test and observation wells can be used to gain new insights into hydraulic tests in highly permeable settings the oscillatory character of slug and pumping induced responses will vary considerably across a site even in an essentially homogeneous formation when wells of different radii depths and screen lengths are used thus variations in the oscillatory character of responses do not necessarily indicate variations in hydraulic conductivity k existing models for slug tests in partially penetrating wells in high k aquifers neglect the storage properties of the media that assumption however appears reasonable for a wide range of common conditions unlike in less permeable formations drawdown at an observation well in a high k aquifer will be affected by head losses in the pumping well those losses which affect the form of the pumping induced oscillations can be difficult to characterize thus analyses of observation well drawdown should utilize data from the period after the oscillations have dissipated whenever possible although inertial mechanisms can have a large impact on early time drawdown that impact decreases rapidly with duration of pumping and distance to the observation well conventional methods that do not consider inertial mechanisms should therefore be viable options for the analysis of drawdown data at moderate to large times

ci chondrite like clasts in the nilpena polymict ureilite implications for aqueous alteration processes in ci chondrites abstract we have carried out a detailed petrographic and mineralogical study of carbonaceous chondrite matrix clasts in the nilpena polymict ureilite the bulk compositions of a number of clasts determined by electron microprobe show that they have close affinities to ci chondrite matrix and differ substantially from cm matrix material transmission electron microscopy studies show that the mineralogy of the clasts is also consistent with ci chondrite matrix indicated by the presence of saponitic smectite clays serpentine magnetite pentlandite pyrrhotite and ferrihydrite phases such as tochilinite and cronstedtite diagnostic of cm matrix are absent based on the oxygen isotopic composition of the matrix the phase chemistry and the bulk clast chemistry we suggest that the matrix clasts in nilpena represent material which is less altered than orgueil the difference in oxygen isotopic composition of the nilpena matrix clasts from ci chondrites may be because the clasts underwent alteration at a lower water rock ratio increased alteration of nilpena type material should result in the oxidation of fe bearing saponite and sulfides to produce ferrihydrite and more mg rich saponite such as that in orgueil matrix although the presence of ci like matrix clasts in the polymict ureilites suggests that ci matrix may have been a precursor to the ureilites in detail this seems highly unlikely the trace element and carbon isotopic compositions of ureilites are incompatible with a significant ci chondrite precursor we suggest that the ci like matrix clasts in nilpena represent a component of a late accreting veneer on the ureilite parent body

collisional facilitation of aqueous alteration of cm and cv carbonaceous chondrites abstract cm chondrites exhibit a strong correlation between the degree of alteration and the extent of particle alignment i e the strength of the petrofabric it seems likely that the s1 shock stage of essentially every cm and the high matrix abundance 70 vol of these samples ensured that the shock waves that produced cm petrofabrics by collapsing matrix pores and squeezing chondrules into pore spaces were significantly attenuated and were too weak to damage olivine crystal lattices random collisions on the cm body produced petrofabrics and created fractures in the target rocks subsequent impact mobilization of water caused hydrated phases to form preferentially in the more fractured regions those with the strongest petrofabrics the less deformed less fractured cm regions experienced lower degrees of aqueous alteration many cv3 chondrites also have petrofabrics roughly half are from the oxidized bali like subgroup cv3 oxb roughly half are from the reduced subgroup cv3 r and none is from the oxidized allende like subgroup cv3 oxa which is less altered than cv3 oxb nearly all cvs with petrofabrics are s3 s4 and nearly all cvs that lack petrofabrics are s1 oxidized cvs have much higher porosities typically 20 28 than reduced cvs 0 6 8 facilitating more extensive aqueous alteration the cv3 r chondrites formed from low porosity material that inhibited oxidation during alteration the oxidized cv subgroups formed from higher porosity materials the cv3 oxb samples were shocked became extensively fractured and developed petrofabrics the cv3 oxa samples were not shocked and never developed petrofabrics when water was mobilized both sets of porous cv chondrites became oxidized the more fractured cv3 oxb subgroup was more severely altered

modeling aqueous alteration of cm carbonaceous chondrites results from an inorganic geochemical modeling study support a scenario in which low temperature aqueous alteration of an anhydrous cm asteroidal parent body and melt water from h20 and co ices produces the altered assemblage observed in cm carbonaceous chondrites chrysotile greenalite tochilinite cronstedtite and minor calcite and magnetite we consider a range of possible precursor mineral assemblages varying with respect to the fe oxidation state of the initial anhydrous phases the aqueous solutions produced by this alteration are generally strongly basic and reducing and a large quantity of h2 and possible ch4 gas can be released during aqueous alteration

geophysical geological and hydrogeological characterization of a tributary buried bedrock valley in southern ontario buried bedrock valleys infilled with quaternary aged sediment have the potential to become productive aquifers owing to prevalent sand and gravel deposits often associated with these topographic lo

sulfur isotopic composition of fe ni sulfide grains in ci and cm carbonaceous chondrites in situ secondary ion mass spectrometry analyses of 32 s 33 s and 34 s in iron nickel sulfide grains in two ci1 chondrites and six cm chondrites were performed the results show a wider range of both enrichment and depletion in 34 s relative to troilite from the canyon diablo meteorite cdt than has been observed in previous studies all data points lie within error of a single mass dependent fractionation line sulfides from ci1 chondrites show 34 scdt from 0 7 to 6 8 while sulfide grains in the cm1 chondrite are generally depleted in heavy sulfur relative to cdt 34 s from 2 9 to 1 8 cm2 chondrites contain sulfide grains that show enrichment and depletion in 34 s 34 scdt from 7 0 to 6 8 sulfates forming from sulfide grains during aqueous alteration on the chondrite parent body are suggested to concentrate light sulfur leaving the remaining sulfide grains enriched in the heavy isotopes of sulfur the average degree of enrichment in 34 s in cm chondrite sulfides is broadly consistent with previously suggested alteration sequences

flow bearing structures of fractured rocks insights from hydraulic property scalings revealed by a pumping test abstract a long duration pumping test conducted over 151 days in a fractured sandstone and shale formation displays a nonstandard drawdown response and anomalous pressure diffusion which cannot be properly interpreted using existing frameworks e g homogeneous double porosity boundary conditions and fractal models an alternative framework with simple geometry and more complex hydraulic properties is thus proposed to interpret such kind of drawdown responses the analytical development allows first to demonstrate all scaling relations in this interpretation framework then and most importantly the multi scale hydraulic test provides consistent scalings of transmissivity t to storativity s over distances ranging from 83 to 383 m in a faulted area drawdown analysis in several monitoring wells shows persistent decrease of transmissivity in highly channelized fracture flow structures in one structure the cubic dependency of transmissivity to storativity identifies a well defined fault and also demonstrates the validity of poiseuille flow at a scale rarely investigated in the other structure the linear dependency of transmissivity to storativity indicates that the flow bearing structure is the surrounding fracture network well designed pumping tests combined with scaling analysis driven by geological evidence thus provide essential information on flow bearing structures for site characterization and modeling tasks at least for moderate to low permeable fractured rocks the scaling of transmissivity to storativity appears to be more informative than any separate interpretation of hydraulic property scaling exponents

minor and trace element concentrations in carbonates of carbonaceous chondrites and implications for the compositions of coexisting fluids abstract abundances of fe mg mn sr na b and ba in meteoritic calcites and dolomites have been determined using the ion microprobe the compositions of these carbonates are consistent with their precipitation from or recrystallization in equilibrium with aqueous solutions at low temperatures coexisting calcites and dolomites in cm chondrites are not in equilibrium and presumably formed in distinct events calculated molar element ca ratios for fluids in equilibrium with these carbonates suggest that dolomites in cm and cl chondrites formed from compositionally similar brines calcite solutions were also saline but lower in mg fe and mn calculations suggest that these solutions became more like dolomite solutions with increasing alteration of the host cm meteorite reflecting progressive evolution of solution compositions asteroid brines may have formed by membrane nitration after the formation of compacted phyllosilicates lowered permeability by addition of components to fluids during phyllosilicate forming reactions or through low pressure boiling occurrences of vein filling calcite followed by dolomite and later by sulfates in carbonaceous chondrites represent the final stages of a protracted aqueous alteration sequence

oxygen isotopes of chondritic components we review the oxygen isotopic compositions of chondrite components refractory inclusions chondrules and matrix and their inter and intra crystalline oxygen isotopic distributions primary oxygen isotopic compositions acquired before planetesimal accretion are easily disturbed by parent body processes such as aqueous alternation and thermal metamorphism primary or original oxygen isotopic compositions of refractory inclusions ca al rich inclusions and amoeboid olivine aggregates distribute along a slope 1 line on the three oxygen isotope diagram over the range of 60 17 o 18 o 16 o rich and 17 o 18 o rich during refractory inclusion formation on the other hand primary minerals of most chondrules have small isotopic variations and are enriched in 17 o and 18 o relative to refractory inclusions suggesting that chondrule formation occurred in 17 o 18 o rich nebular gas however rare 16 o rich chondrules have been found suggesting some overlap in the timing of formation of chondrules and refractory inclusions in the solar nebula oxygen isotopic compositions of matrix grains distribute along the slope 1 line over the same range as refractory inclusions and chondrules the similarity in oxygen isotopic distributions suggests that matrix was originally a mechanical mixture of nebular dusts co generated with chondrules and refractory inclusions presolar grains with oxygen isotopic compositions that are clearly distinct from those of solar nebular materials are a trace component of chondrite matrices based on these oxygen isotopic characteristics more than 99 5 of the solid materials in the nebula formed locally in the solar nebula and the remainder formed in interstellar space the astrophysical setting of chondrite component formation in the early solar system is also discussed refractory inclusions and 16 o rich matrix dusts formed around the inner edge of the solar nebula on the other hand most chondrules and 17 o 18 o rich matrix dusts seem to have formed elsewhere in the solar nebula efficient large scale radial mixing of the solar nebular materials may have been an essential process in the formation of chondritic planetesimals

natural variations of δ30si ratios during progressive basalt weathering hawaiian islands abstract silicon stable isotopes can be used to trace the biogeochemical pathways of si as it moves from its continental sources to its sink in ocean sediments along the way si is incorporated into clay minerals taken up by plants where it forms plant opal and leached into rivers the major land to ocean conduit compared to igneous rocks the waters that drain continents are enriched in heavy si isotopes but the mechanisms that control fractionation have not been elucidated we studied si isotope fractionation along a 4 million yr basaltic soil chronosequence on the hawaiian islands using the natural context of these samples in combination with laboratory experiments we demonstrate that the isotopic composition of dissolved si in weathering systems is determined by the combined effects of rock disintegration clay mineral neosynthesis and si biocycling weathering preferentially releases 28si into solution whereas secondary mineral formation preferentially removes 28si from solution in humid environments leached soils have lost large amounts of this soluble si thus creating a net loss of 30si from the entire soil system as soils develop and greater fractions of si reside in neoformed clay minerals 30sibulk soil values change progressively toward more negative values basalt 30si values are about 0 5 but older soils have 30si values up to 2 5 the difference between the solid and solution 30si values remains more or less constant with progressive weathering and therefore soil water from older soils has a more negative 30si composition in the upper horizons of the hawaiian soils this weathering driven 30si shift is modified by the addition of unweathered primary minerals via dust carrying 30si values of about 0 5 and by biocycling of si via plants producing negative 30si values in phytoliths and positive 30si values in soil solutions derived from upper horizons due to the high concentrations of dissolved si in these near surface layers rivers have more positive 30si values than predicted based on the weathering status of the lower horizons when combined with published 30si values from large rivers worldwide we find that the results from hawaii point to weathering control of si isotopes delivered to the oceans and thus to an important continent ocean linkage that warrants further investigation

diatom silicon isotopes as a proxy for silicic acid utilisation a southern ocean core top calibration despite a growing body of work that uses diatom 30si to reconstruct past changes in silicic acid utilisation few studies have focused on calibrating core top data with modern oceanographic conditions in this study a microfiltration technique is used to divide southern ocean core top silica into narrow size ranges separating components such as radiolaria sponge spicules and clay minerals from diatoms silicon isotope analysis of these components demonstrates that inclusion of small amounts of non diatom material can significantly offset the measured from the true diatom 30si once the correct size fraction is selected generally 2 20 m diatom 30si shows a strong negative correlation with surface water silicic acid concentration r2 0 92 highly supportive of the qualitative use of diatom 30si as a proxy for silicic acid utilisation the core top diatom 30si matches well with mixed layer filtered diatom 30si from published in situ studies suggesting little to no effect of either dissolution on export through the water column or early diagenesis on diatom 30si in sediments from the southern ocean however the core top diatom 30si shows a poor fit to simple rayleigh or steady state models of the southern ocean when a single source term is used the data can instead be described by these models only when variations in the initial conditions of upwelled silicic acid concentration and 30si are taken into account a caveat which may introduce some error into quantitative reconstructions of past silicic acid utilisation from diatom 30si

structural and statistical characterization of joints and multi scale faults in an alternating sandstone and shale turbidite sequence at the santa susana field laboratory implications for their effects on groundwater flow and contaminant transport abstract this paper describes the properties of faults and fractures in the upper cretaceous chatsworth formation exposed at santa susana field laboratory and its surroundings simi hills california where groundwater flow and contamination have been studied for over three decades the complex depositional architecture of this turbidite consisting of alternating sandstones and shales interacting with formative stress conditions are responsible for multi scale fault hierarchies and permeable fractures in which nearly all groundwater flow occurs intensity and distribution of background fractures and their relation to bedding thickness are established for sandstones the dominant lithology the architecture of faults with increasing displacement is described and relationships among fault dimensional parameters captured data from 400 boreholes and piezometers reveal the effect of faults and fractures on groundwater flow large hydraulic head differences observed across fault zones with shale rich cores indicate these structures as cross flow barriers moreover hydraulic head profiles under ambient conditions and pumping tests suggest strong hydraulic connectivity in all directions to depth of hundreds of meters this outcrop based structural characterization relates the horizontal hydraulic conductivity to the observed well connected fracture network and explains the strong vertical connectivity across low hydraulic conductivity shales as faults and sheared fractures provide flow pathways

mineralogy and composition of matrix and chondrule rims in carbonaceous chondrites abstract the degree of compositional variation of fine grained minerals displayed by the members within any carbonaceous chondrite group i e ci cm cv cr is a direct reflection of the range of aqueous alteration assemblages present matrix and fine grained chondrule rims within any particular carbonaceous chondrite are mineralogically nearly identical to one another but not necessarily similar in bulk elemental composition even though they have subsequently experienced post accretional secondary processing aqueous alteration under identical conditions this may indicate preferential alteration of one component brecciation exchange of components between rims and matrix and or accretion of matrix and rims from mineralogically or compositionally distinct materials we propose that co chondrites experienced parent body conditions of low f o2 low water rock ratios and temperatures below 50 c cr chondrites experienced higher water rock ratios potentially higher temperatures 150 c and a wide range of f o2 the alteration mineralogy of cv chondrites indicates water rock ratios at the high end at least of the range for cr chondrites essebi and mac 87300 cm chondrites experienced temperatures below 50 c low f o2 and low water rock ratios except eet 83334 which probably experienced relatively higher f o2 and b 7904 and y 86720 which experienced postalteration temperatures in the range 500 700 c most ci chondrites experienced temperatures between 50 and 150 c relatively high water rock ratios and variable f o2 with a late stage increase in the latter due possibly to brecciation and consequent release of methane y 82162 witnessed post alteration heating possibly as high as 400 c

ca carbonate in the orgueil ci carbonaceous chondrite mineralogy microstructure and implications for parent body history the orgueil ci carbonaceous chondrite is a breccia and some of its constituent clasts contain ca carbonate grains whose mineralogy is undetermined but may yield new information on the history of its asteroidal or cometary parent body characterisation of one such clast shows that in addition to ca carbonate it contains magnetite olivine and orthopyroxene grains that are supported within a finely crystalline saponite serpentine ferrihydrite groundmass the ca carbonate grains are typically rounded less than 10 m in diameter and backscatter kikuchi patterns identify all those analysed as calcite electron backscatter diffraction orientation contrast maps show that most calcites have sub m sized e twins some of which are cut by corroded grain margins these microstructures demonstrate that the clast experienced very mild shock during aqueous alteration and probably accompanying impact gardening of the parent body regolith the sample studied hosts several other millimeter sized clasts and a fine grained clastic matrix that are free of ca carbonate olivine and orthopyroxene although can contain apatite dolomite and pyrrhotite within one of these clasts is a network of phyllosilicate magnetite veins that are inferred to have acted as fluid flow conduits during parent body aqueous alteration sulphur rich reaction rims within the same clast are likely to have formed during post fall remobilization and crystallization of pre terrestrial sulphates this study provides good evidence for alteration of the ci carbonaceous chondrites in a dynamic parent body regolith

another continental pool in the terrestrial silicon cycle silicon is the second most abundant element on earth and is involved in important terrestrial and marine biogeochemical processes however its terrestrial cycle is not well quantified and there is a missing reservoir in the budget of silicon isotopes water in seas and rivers is enriched in silicon 30 compared with igneous rocks suggesting that there is an unknown continental reservoir that is depleted in silicon 30 now with the help of a new generation mass spectrometer basile doelsch et al have obtained in situ measurements of silicon isotopes in quartz from sandstones in southern france the results showing greater silicon 30 depletion than in any previously reported terrestrial samples suggest that silicified rocks formed from quartz precipitates in soils and groundwaters can account for the missing reservoir silicon is the second most abundant element on earth it is an important nutrient for phytoplankton1 and is readily absorbed by terrestrial vegetation2 it also assists the removal of carbon dioxide from the atmosphere through the weathering of silicates3 but the continental cycle of silicon is not well known and only a few studies have attempted to use silicon stable isotopes 28si 29si and 30si 4 5 6 7 8 9 10 11 12 13 to quantify the continental silicon reservoirs dissolved silicon in sea and river waters forms a reservoir of mean isotopic value 1 1 refs 7 10 it is enriched in 30si with respect to the igneous rocks reservoir which has a mean isotopic value of 0 3 refs 4 9 this enrichment can only be produced by a major fractionation during weathering and should result in the formation of a continental 30si depleted reservoir such a reservoir however has not been identified to date here we analyse silicon isotopes of in situ quartz from a sandstone series in france using a new generation secondary ion mass spectrometry apparatus we show that quartz that precipitates as siliceous cements forms a strongly 30si depleted reservoir with isotopic values down to 5 7 a more negative value than any previously published for terrestrial samples our findings suggest that quartz re precipitation plays an important role in the biogeochemical cycle of silicon

conditions for pore water convection within carbonaceous chondrite parent bodies implications for planetesimal size and heat production abstract the critical rayleigh number for convective flow of pore water through a permeable spherical body is derived the result affords constraints on carbonaceous chondrite planetesimal sizes and rates of heat production if the chemical compositions of carbonaceous chondrites are taken as evidence against flow of pore water then the present calculations suggest that the parent bodies were less than 80 km in diameter the maximum diameter for absence of flow depends in part on the high permeabilities required by estimates of high water rock ratios in altered carbonaceous chondrites pore water would have flowed through parent bodies larger than 120 km in diameter with typical rock like permeabilities convective flow and isochemical alteration are not compatible and our calculations can be used to identify the combinations of parent body size and heat generation consistent with one or the other

groundwater flow characterization in a fractured bedrock aquifer using active dts tests in sealed boreholes summary in recent years wireline temperature profiling methods have evolved to offer new insight into fractured rock hydrogeology important advances in wireline temperature logging in boreholes make use of active line source heating alone and then in combination with temporary borehole sealing with flexible impervious fabric liners to eliminate the effects of borehole cross connection and recreate natural flow conditions here a characterization technique was developed based on combining fiber optic distributed temperature sensing dts with active heating within boreholes sealed with flexible borehole liners dts systems provide a temperature profiling method that offers significantly enhanced temporal resolution when compared with conventional wireline trolling based techniques that obtain a temperature depth profile every few hours the ability to rapidly and continuously collect temperature profiles can better our understanding of transient processes allowing for improved identification of hydraulically active fractures and determination of relative rates of groundwater flow the advantage of a sealed borehole environment for dts based investigations is demonstrated through a comparison of dts data from open and lined conditions for the same borehole evidence for many depth discrete active groundwater flow features under natural gradient conditions using active dts heat pulse testing is presented along with high resolution geologic and geophysical logging and hydraulic datasets implications for field implementation are discussed

carbonate compositions in cm and ci chondrites and implications for aqueous alteration abstract carbonate minerals in fourteen cm chondrites and two ci chondrites have been analyzed by electron microprobe to provide a better understanding of the aqueous processes that affected carbonaceous chondrite parent bodies calcites in cm chondrites and dolomites and magnesites in ci chondrites display the compositions expected of stable phases formed at low temperatures dolomites in cm chondrites identified here for the first time in five members of the group have small amounts of excess ca which may reflect metastable growth the distribution of fe between dolomite and coexisting serpentine differs in the two chondrite groups if the distributions reflect an approach to chemical equilibrium then the difference implies higher alteration temperatures for the ci group than the cm group in agreement with the results of previously published oxygen isotope thermometry and mineral solubility modeling of the alteration process dolomite fe contents are relatively uniform in the two chondrite groups dolomite mn contents by contrast vary widely the variations may reflect transport controlled coprecipitation of mn resulting from a heterogeneous distribution of the element in the anhydrous precursor material if this interpretation is correct then the altering fluids were essentially immobile while hydration reactions proceeded on the meteorite parent bodies the near closed system character of the alteration process long known from bulk chemical analyses of the meteorites is a direct consequence of the limited mobility of dissolved species

progressive aqueous alteration of cm carbonaceous chondrites abstract cm chondrites are aqueously altered rocks that contain 9 wt h 2 o i e indigenous water bound in phyllosilicates also present are clumps of serpentine tochilinite intergrowths previously called poorly characterized phases or pcp pentlandite and ni bearing pyrrhotite we studied 11 cm chondrites that span the known range from least altered to most altered we used various petrologic properties many previously identified that provide information regarding the degree of aqueous alteration there are no known unaltered or slightly altered cm chondrites e g rocks containing numerous chondrules with primary igneous glass some cm properties result from processes associated with early and intermediate stages of the alteration sequence i e hydration of matrix alteration of chondrule glass and production of large pcp clumps other petrologic properties reflect processes active throughout the alteration sequence these include oxidation of metallic fe ni alteration of chondrule phenocrysts changes in pcp composition reflecting an increase in the phyllosilicate sulfide ratio and changes in carbonate mineralogy reflecting the development of dolomite and complex carbonates at the expense of ca carbonate on the basis of these parameters we propose a numerical alteration sequence for cm chondrites because there are no known cm samples that display only incipient alteration the least altered sample was arbitrarily assigned to subtype 2 6 the most altered cm chondrites currently classified cm1 are assigned to subtype 2 0 these highly altered rocks have essentially no mafic silicates they contain chondrule pseudomorphs composed mainly of phyllosilicate however their bulk compositions are cm like and they are closer in texture to other c2 chondrites than to ci1 chondrites which lack chondrule pseudomorphs using several diagnostic criteria we assigned petrologic subtypes 0 1 to every cm chondrite in our study que 97990 cm2 6 murchison cm2 5 kivesvaara cm2 5 murray cm2 4 2 5 y 791198 cm2 4 que 99355 cm2 3 nogoya cm2 2 cold bokkeveld cm2 2 que 93005 cm2 1 lap 02277 cm2 0 met 01070 cm2 0 the proposed cm numerical alteration sequence improves upon the existing scheme of browning et al 1996 in that it does not require a complicated algorithm applied to electron microprobe data to determine the average matrix phyllosilicate composition the new sequence is more comprehensive and employs petrologic subtypes that are easier to use and remember than mineralogic alteration index values new neutron activation analyses of que 97990 que 93005 met 01070 murchison and crescent together with literature data confirm the compositional uniformity of the cm group different degrees of alteration among cm chondrites do not lead to resolvable bulk compositional differences this suggests that the textural differences among individual cm chondrites reflect progressive alteration of similar hypothetical cm3 0 starting materials in different regions of the same parent body with minimal aqueous transport of materials over appreciable e g meters distances

a field example of measuring hydrodynamic dispersion in a single fracture a field example of measuring the dispersive properties of a single fracture in fractured plutonic rock is presented the experimental technique involves injecting a slug of conservative tracer into a steady groundwater flow field established between a pumping and recharging borehole and monitoring the tracer breakthrough by sampling the withdrawal water directly the breakthrough curves from two experiments were analyzed with a model which describes the flow field geometry either analytically or numerically and solves for hydrodynamic dispersion analytically a longitudinal dispersivity of 1 40 m was estimated by fitting the model to each set of field data the magnitude of the dispersion was determined to be independent of dispersive effects created by flow through the borehole instrumentation and thought to be purely hydrodynamic in nature

oxygen isotope systematics of chondrule phenocrysts from the co3 0 chondrite yamato 81020 evidence for two distinct oxygen isotope reservoirs high precision oxygen three isotope measurements of olivine and pyroxene were performed on 33 chondrules in the yamato 81020 co3 0 chondrite by secondary ion mass spectrometry in chondrules where oxygen isotopes were measured in both olivine and pyroxene the majority of grains have similar values indicating co magmatic crystallization however many chondrules contain relict grains with unique oxygen isotope ratios a striking feature of yamato 81020 chondrules is a bimodal distribution of oxygen isotope ratios as those with mg 97 phenocrysts range in 17o from 4 8 to 6 5 5 5 group and those with mg 96 36 phenocrysts have 17o values of 2 1 to 3 0 2 5 group a single mg 99 6 barred olivine chondrule has a 17o of 3 3 we discuss that 17o 5 5 chondrules are derivative of a reservoir with limited dust enrichment 100 solar system which yielded a relatively reduced chondrule forming environment in contrast the 17o 2 5 chondrules may have been influenced by 16o poor h2o ice that sublimed and then homogenized with precursor material the addition of h2o when combined with high dust enrichment 1000 solar system and greater bulk fe content could have induced an oxidized environment at high temperatures forming mg 96 36 chondrules among the 33 chondrules studied the al mg relative ages of 20 had been obtained previously comparing the oxygen isotope ratios and the 26al ages of these chondrules it is likely that the 5 5 and 2 5 oxygen isotope reservoirs existed contemporaneously this implies that the snow line was spatially fixed during chondrule formation and separated the co chondrite accretion region into two distinct volumes of precursors

micro scale tracing of fe and si isotope signatures in banded iron formation using femtosecond laser ablation we have detected micrometre scale differences in fe and si stable isotope ratios between coexisting minerals and between layers of banded iron formation bif using an uv femtosecond laser ablation system connected to a mc icp ms in the magnetite carbonate chert bif from the archean old wanderer formation in the shurugwi greenstone belt zimbabwe magnetite shows neither intra nor inter layer trends giving overall uniform d 56 fe values of 0 9 but exhibits intra crystal zonation bulk iron carbonates are also relatively uniform at near zero values however their individual d 56 fe value is highly composition dependent both siderite and ankerite and mixtures between both are present and d 56 fe end member values are 0 4 for siderite and 0 7 for ankerite the data suggest either an early diagenetic origin of magnetite and iron carbonates by the reaction of organic matter with ferric oxyhydroxides catalysed by fe iii reducing bacteria or more likely an abiotic reaction of organic carbon and fe iii during low grade metamorphism si isotope composition of the old wanderer bif also shows significant variations with d 30 si values that range between 1 0 and 2 6 for bulk layers these isotope compositions suggest rapid precipitation of the silicate phases from hydrothermal rich waters interestingly fe and si isotope compositions of bulk layers are covariant and are interpreted as largely primary signatures moreover the changes of fe and si isotope signatures between bulk layers directly reflect the upwelling dynamics of hydrothermal rich water which govern the rates of fe and si precipitation and therefore also the development of layering during periods of low hydrothermal activity precipitation of only small amounts of ferric oxyhydroxide was followed by complete reduction with organic carbon during diagenesis resulting in carbonate chert layers during periods of intensive hydrothermal activity precipitation rates of ferric oxyhydroxide were high and subsequent diagenesis triggered only partial reduction forming magnetite carbonate chert layers we are confident that our micro analytical technique is able to detect both the solute flux history into the sedimentary bif precursor and the bif s diagenetic history from the comparison between coexisting minerals and their predicted fractionation factors

groundwater recharge assessment in an upland sandstone aquifer of southern california abstract the chloride mass balance cmb method was used to obtain long term recharge values for the santa susana field laboratory ssfl site which features a groundwater flow system beneath an upland ridge formed of sandstone and shale beds in the simi hills ventura county southern california this application relied on the availability of on site measurements of bulk atmospheric chloride deposition comprised of dry fallout and wet concentration a large number of groundwater samples 1490 collected over three decades from 206 wells spanning a depth range from 10 to 360 m and measurements of chloride in surface runoff during rain events the use of the cmb method is suited to the assessment of recharge for the study area because the mean chloride values in groundwater show minimal spatial trends indicating no sources other than atmospheric in addition the cl br ratio was used to exclude wells with possible anthropogenic chloride the site wide average recharge ranges between 1 8 and 9 5 of the mean annual precipitation 455 mm with a mean value of 4 2 the measured surface runoff varies from 2 3 to 10 2 with mean value of 6 1 28 mm and therefore the volume of water lost to evapotranspiration is between 95 9 and 80 3 with a mean value of 89 6 408 mm the long term recharge calculated using the cmb method is consistent with tritium distribution based on a subset of groundwater monitoring wells and with an analysis of steady flow in the groundwater mound beneath the ssfl furthermore the recharge value matches those in the literature for sandstone aquifers in arid and semi arid climates this recharge estimate has important relevance for site characterization in terms of constraining the volumetric groundwater flow rates and water balance and understanding the mechanisms of transport towards the water table moreover this is the first application of the cmb in an upland area of california hence the method is demonstrated to be robust and applicable to many upland bedrock areas in southern california and similar regions around the world and can be used to quantify groundwater flow rates and supplies relevant to water resource management

microplate capture rotation of the western transverse ranges and initiation of the san andreas transform as a low angle fault system tectonic rotation of the western transverse ranges block is explained by capture of the partially subducted monterey microplate by the pacific plate at about anomaly 6 time ca 20 ma as pacific monterey spreading slowed and eventually ceased the slip vector along the gently northeast dipping subduction interface beneath the california margin changed from slightly oblique subduction to transtensional dextral transform motion this change in slip vector and a shift of pacific plate motion eastward along the already subducted monterey plate interface imply that the san andreas transform began as a system of low angle faults that locally subjected the overriding continental margin to distributed basal shear and crustal extension this basal shear produced the rotated western transverse ranges this model helps explain the timing of initial rotation and basin formation the sudden appearance of widely distributed transform motion well inland of the margin in early miocene time why the western transverse ranges uniquely rotated as a large coherent crustal block and several fundamental structural characteristics of central and southern california the model also provides major constraints on the amount of pacific north america strike slip motion the position through time of offshore oceanic plates relative to onshore geology and a general explanation for what may happen as a spreading ridge approaches a trench and the subduction zone evolves into a transform system

combined use of straddle packer testing and flute profiling for hydraulic testing in fractured rock boreholes summary a combination of high resolution hydraulic tests using straddle packers and transmissivity t profiling using the flute flexible liner method liner profiling in densely fractured rock boreholes is shown to be efficient for the determination of the vertical distribution of t along the entire hole the liner t profiling method takes a few hours or less to scan the entire borehole length resulting in a t profile under favorable conditions this method has good reliability for identifying the highest t zones identified by distinct decreases in liner velocity when these zones are covered by the descending liner in contrast for one short test interval e g 1 2 m the multiple test straddle packer method takes a few hours to measure t with good precision and accuracy using a combination of steady state and transient tests e g constant head step tests slug tests and constant rate pumping tests because of the time consuming aspect of this multiple test method it is most efficient in each borehole to conduct straddle packer testing only in priority zones selected after assessment of other borehole data collected prior to packer testing the t profile from the liner method is instrumental in selecting high permeable zones for application of the multiple test method using straddle packers which in turn refines the t estimation from the liner profile results from three boreholes in densely fractured sandstone demonstrate this approach showing the synergistic use of the methods with emphasis on information important for determining hydraulic apertures

anomalous 17o compositions in massive sulphate deposits on the earth the variation of 18o that results from nearly all physical biological and chemical processes on the earth is approximately twice as large as the variation of 17o this so called mass dependent fractionation is well documented in terrestrial minerals1 2 evidence for mass independent fractionation 17o 17o 0 52 18o where deviation from this tight relationship occurs has so far been found only in meteoritic material and a few terrestrial atmospheric substances3 in the rock record it is thought that oxygen isotopes have followed a mass dependent relationship for at least the past 3 7 billion years ref 4 and no exception to this has been encountered for terrestrial solids5 here however we report oxygen isotope values of two massive sulphate mineral deposits which formed in surface environments on the earth but show large isotopic anomalies 17o up to 4 6 these massive sulphate deposits are gypcretes from the central namib desert and the sulphate bearing miocene volcanic ash beds in north america the source of this isotope anomaly might be related to sulphur oxidation reactions in the atmosphere and therefore enable tracing of such oxidation these findings also support the possibility of a chemical origin of variable isotope anomalies on other planets such as mars6

the silicon isotope composition of the upper continental crust the upper continental crust ucc is the major source of silicon si to the oceans and yet its isotopic composition is not well constrained in an effort to investigate the degree of heterogeneity and provide a robust estimate for the average si isotopic composition of the ucc a representative selection of well characterised continentally derived clastic sediments have been analysed using high precision mc icpms analyses of loess samples define a narrow range of si isotopic compositions 30si 0 28 to 0 15 this is thought to reflect the primary igneous mineralogy and predominance of mechanical weathering in the formation of such samples the average loess 30si is 0 22 0 07 2 s d identical to average granite and felsic igneous compositions therefore minor chemical weathering does not resolvably affect bulk rock 30si and loess is a good proxy for the si isotopic composition of unweathered crystalline continental crust the si isotopic compositions of shales display much more variability 30si 0 82 to 0 00 shale si isotope compositions do not correlate well with canonical proxies for chemical weathering such as cia values but do correlate negatively with insoluble element concentrations and al si ratios this implies that more intensive or prolonged chemical weathering of a sedimentary source with attendant desilicification is required before resolvable negative si isotopic fractionation occurs shale 30si values that are more positive than those of felsic igneous rocks most likely indicate the presence of marine derived silica in such samples using the data gathered in this study combined with already published granite si isotope analyses a weighted average composition of 30si 0 25 0 16 2 s d for the ucc has been calculated

identifying hydraulically conductive fractures with a slow velocity borehole flowmeter the u s geological survey used a recently developed heat pulse flowmeter to measure very slow borehole axial water velocities in granitic rock at a site near lac du bonnet manitoba canada the flowmeter was used with other geophysical measurements to locate and identify hydraulically conducting fractures contributing to the very slow vertical water flow in the two boreholes selected for study the heat pulse flowmeter has no moving parts and operates on the tag trace principle it is an improved version of the flowmeter developed by the water research centre in england in 1975 the u s geological survey s heat pulse flowmeter has a flow measuring range in water of 0 06 6 m min and can resolve velocity differences as slow as 0 01 m min this is an order of magnitude slower than the stall speed of spinner flowmeters the flowmeter is 1 16 m long and 44 mm in diameter it was calibrated in columns of 76 and 152 mm diameter to correspond to the boreholes studied the heat pulse flowmeter system is evalu

fluid flow and chemical alteration in carbonaceous chondrite parent bodies abstract carbonaceous chondrites are a class of primitive meteorites that likely represent early solar system materials thus providing critical insights about planetary evolution however evidence shows that they have undergone considerable processing elucidating the complex formation history of aqueously altered chondrite groups has been a principal objective of cosmochemistry fulfilling this objective requires understanding the nature of the water rock interactions involved many current alteration models are generally founded upon an assumption of uniform alteration in a closed system in these models different chondrite groups must originate on separate parent bodies contrary to this common view we show that chondrite data are consistent with non uniform alteration in a convecting system so that multiple chondrite groups can form within a single body

an oxygen isotope dichotomy in cm2 chondritic carbonates a sims approach abstract we present petrologic and secondary ion mass spectrometry sims oxygen isotope analyses of ca carbonate within a group of paired antarctic cm2 chondrites the carbonates can be grouped into two isotopically and morphologically distinct populations type 1 grains small matrix grains possess average 18 o of 33 7 2 3 1 and average 17 o of 0 81 0 90 1 type 2 grains calcite aggregates possess distinct oxygen isotopic compositions average 18 o of 19 4 1 5 1 and average 17 o of 1 98 0 9 1 these differences are interpreted to indicate that the two populations of calcite formed under different conditions at different times the carbonates have textural features that suggest an extraterrestrial origin the data presented here fall within error of a previously measured array for carbonates from cm falls benedix et al 2003 the presence of two generations of carbonate suggests carbonate formation in two discrete events on the parent body of these meteorites the oxygen isotopic data presented here deviate from prior bulk carbonate measurements undertaken for these meteorites most likely this deviation is because bulk carbonate analyses included vein carbonate which formed during terrestrial weathering

the silica cycle in the precambrian abstract whereas the modem silica cycle is heavily dependent on the biology of silica secreting organisms such as the diatoms the precambrian silica cycle was dominated by inorganic reactions among dissolved silica clay and zeolite minerals and organic matter there is no evidence for deposition of a layered amorphous silica but abundant evidence for diagenetic silicification in the neoproterozoic the time period chosen for this analysis the influx of silica to the neoproterozoic ocean would have been governed as today by the balance among tectonism weathering and hydrothermal input the evidence of neoproterozoic rocks favors tectonic and weathering regimes not very dissimilar to those of the early phanerozoic and hydrothermal inputs significantly altered at certain periods one flux would have been very different the present diffusional influx of silica from interstitial waters into the oceans would have been altered to an efflux from the oceans to interstitial waters reactions of dissolved silica with inorganic phases would have controlled silica concentrations at a level of about 60 ppm this figure is based on experimental determinations of solubility and silica sorption on clay minerals and zeolites as silica in interstitial waters was lowered by opal ct precipitation a diffusional efflux from the ocean into the sediment was set up silicification would have started in early diagenesis as opal ct precipitated from interstitial waters diffusion of silica from overlying seawater declined as the sediment was buried a few hundred meters and the diffusion path lengthened during this still relatively shallow burial silicification continued but this time powered by hydrologie transport of dissolved silica from coastal plain sediments during transgressions and regressions thus the major removal of silica from the neoproterozoic ocean took place by diagenetic reactions

sensitivity of silicon isotopes to whole ocean changes in the silica cycle a 2 box model has been used to assess the impact of both long and short term budgetary imbalance in the silica cycle on the average silicon isotopic composition 30si of the ocean and marine sediments over a 100 ky time span such as a quaternary glacial cycle a sustained change in the riverine flux of silicon to the oceans could alter the average 30si of seawater and the average 30si of opal outputs by a few hundredths to a few tenths of permil this would be largely tied to a change in the 30si of silicon entering the ocean due to a shift in the proportion of riverine and non riverine sources of silicon a doubling of the riverine flux of silicon would have little impact on average marine 30si but a sustained halving of river inputs could interfere with use of 30si as a tracer of nutrient utilization studies on the longer term focussed on the transition from a high silicic acid to low silicic acid ocean associated with the rise of the diatoms this transition is marked by drop in the average 30si of seawater from greater than 1 9 down to about 0 8 the isotopic composition of diatom opal however has an isotopic composition that sticks close to the 0 8 of the inputs and is thus unlikely to provide information about the transition to the low silicic acid ocean of the modern day however the 30si of opal produced in the deep sea for example by sponges should document this transition

matrix mineralogy of the orgueil ci carbonaceous chondrite a petrographic and transmission electron microscopic study of the orgueil ci carbonaceous chondrite shows that the matrix consists mainly of fe bearing mg rich serpentine and smectite saponite as well as a poorly crystallized fe rich material that contains minor variable s and ni the fe rich material is probably ferrihydrite a ferric hydroxide the ferrihydrite occurs in small particles 80 a in diameter and the s and ni are probably adsorbed on its surfaces the serpentine and saponite occur in poorly crystallized fine crystallites fine phyllosilicates that are intimately associated with the ferrihydrite coarsely crystallized phyllosilicates coarse phyllosilicates occur in clusters relatively free of ferrihydrite the ferrihydrite is a major matrix constitutent and probably accounts for most of the fe3 as well as the superparamagnetic fraction in the orgueil matrix the textures suggest that the fine phyllosilicates resulted from alteration of the coarse phyllosilicates the alteration probably involved a substantial amount of water and coincided with the period of sulfate vein formation during the aqueous alteration magnetite grains disaggregated from framboids and fe ni sulfides were replaced by ferrihydrite simultaneously aqueous solutions reacted with the coarse phyllosilicates and precipitated ferrihydrite producing intimate pervasive mixtures with the fine phyllosilicates the matrix mineralogy of the orgueil chondrite suggests that orgueil experienced considerably different alteration conditions from the cm chondrites the mineralogical and petrological differences between ci and cm chondrites can not simply be explained as the result of different degrees of aqueous alteration

oxygen isotopes in separated components of ci and cm meteorites oxygen isotopic compositions have been determined for whole rock and separated components from the ci chondrites alais ivuna and orgueil and from the atypical cm chondrites bells and essebi the composition of ci matrix is in agreement with previous measurements and is systematically different from that of cm matrix probably due to warmer and wetter conditions of aqueous alteration for ci matrix although bells matrix is like that of other cm chondrites the matrix of essebi falls in the ci field essebi also contains abundant magnetite like cis and unlike other cms the isotopic compositions of magnetite in alais ivuna orgueil and essebi define a trend with 17o of 1 3 to 1 8 distinctly out of isotopic equilibrium with the phyllosilicates in each meteorite the magnetite serves as an isotopic tracer for the fluid which brought about aqueous alteration and oxidation and thus provides additional evidence for a gaseous reservoir in the solar nebula which was more 16o depleted than the earth

evidence for aqueous activity on comet 81p wild 2 from sulfide mineral assemblages in stardust samples and ci chondrites abstract the discovery of nickel copper and zinc bearing iron sulfides from comet 81p wild 2 wild 2 represents the strongest evidence in the stardust collection of grains that formed in an aqueous environment we investigated three microtomed tem sections which contain crystalline sulfide assemblages from wild 2 and twelve thin sections of the hydrothermally altered ci chondrite orgueil detailed structural and compositional characterizations of the sulfide grains from both collections reveal striking similarities the stardust samples include a cubanite cufe 2 s 3 grain a pyrrhotite fe ni 1 x s pentlandite fe ni 9 s 8 assemblage and a pyrrhotite sphalerite fe zn s assemblage similarly the ci chondrite sulfides include individual cubanite and pyrrhotite grains cubanite pyrrhotite assemblages pyrrhotite pentlandite assemblages as well as possible sphalerite inclusions within pyrrhotite grains the cubanite is the low temperature orthorhombic form which constrains temperature to a maximum of 210 c the stardust and orgueil pyrrhotites are the 4c monoclinic polytype which is not stable above 250 c the combinations of cubanite and pyrrhotite as well as pyrrhotite and pentlandite signify even lower temperatures the crystal structures compositions and petrographic relationships of these sulfides constrain formation and alteration conditions taken together these constraints attest to low temperature hydrothermal processing our analyses of these minerals provide constraints on large scale issues such as heat sources in the comet forming region aqueous activity on cometary bodies and the extent and mechanisms of radial mixing of material in the early nebula the sulfides in the wild 2 collection are most likely the products of low temperature aqueous alteration they provide evidence of radial mixing of material e g cubanite troilite from the inner solar system to the comet forming region and possible secondary aqueous processing on the cometary body

assessing the validity of the channel model of fracture aperture under field conditions in recent investigations of fluid and solute movement in discrete fractures spatial heterogeneity of the fracture aperture has been conceptualized as a series of noninterconnecting constant aperture flow paths or channels two methods of estimating the distribution of the aperture sizes are presented using information from a single hole pumping test and a radially converging tracer test the first method uses the transmissivity of the fracture and mean arrival time of the tracer while the second method uses the mean and variance of the solute arrival time if the fracture can be conceptualized as a series of nonintersecting flow paths of constant aperture the two methods should yield identical estimates for the parameters of the distribution the validity of the channel model can be assessed by comparing the parameters of the distribution that are estimated by the two methods this technique was demonstrated using hydraulic and tracer tests conducted in a discrete areally extensive horizontal fracture in the silurian dolomite in the northeastern illinois a lognormal and a truncated gamma distribution were used to describe the distribution of constant aperture flow paths the lognormal distribution could not reproduce the abrupt rising limb and maximum rate of mass arrival that characterized the tracer tests the gamma distribution more accurately predicted the shape of the breakthrough curves however the two methods of estimating the parameters of the distribution provided significantly different estimates of the variances of the aperture sizes the mean aperture as estimated by the two methods was similar the difference in the variance of the aperture as estimated by the two methods indicates that alternative conceptual models of aperture heterogeneity are required to more accurately describe both fluid and solute movement in this field situation

enhanced detection of hydraulically active fractures by temperature profiling in lined heated bedrock boreholes summary the effectiveness of borehole profiling using a temperature probe for identifying hydraulically active fractures in rock has improved due to the combination of two advances improved temperature sensors with resolution on the order of 0 001 c and temperature profiling within water inflated flexible impermeable liners used to temporarily seal boreholes from hydraulic cross connection the open hole cross connection effects dissipate after inflation so that both the groundwater flow regime and the temperature distribution return to the ambient background condition this paper introduces a third advancement the use of an electrical heating cable that quickly increases the temperature of the entire static water column within the lined hole and thus places the entire borehole and its immediate vicinity into thermal disequilibrium with the broader rock mass after heating for 4 6 h profiling is conducted several times over a 24 h period as the temperature returns to background conditions this procedure referred to as the active line source als method offers two key improvements over prior methods first there is no depth limit for detection of fractures with flow second both identification and qualitative comparison of evidence for ambient groundwater flow in fractures is improved throughout the entire test interval the benefits of the als method are demonstrated by comparing results from two boreholes tested to depths of 90 and 120 m in a dolostone aquifer used for municipal water supply and in which most groundwater flow occurs in fractures temperature logging in the lined holes shows many fractures in the heterothermic zone both with and without heating but only the als method shows many hydraulically active fractures in the deeper homothermic portion of the hole the identification of discrete groundwater flow at many depths is supported by additional evidence concerning fracture occurrence including continuous core visual inspection acoustic televiewer logs and tests for hydraulic conductivity using straddle packers as well as rock core voc data where available that show deep penetration and many migration pathways confidence in the use of temperature profiles and the conceptual model is provided by numerical simulation and the demonstrated reproducibility of the evolution of the temperature signal measured in the lined holes with and without heating this approach for using temperature profiling in lined holes with heating is a practical advance in fractured rock hydrogeology because the liners are readily available the equipment needed for heating is low cost and rugged and the time needed to obtain the profiles is not excessive for most projects

correlated alteration effects in cm carbonaceous chondrites three parameters are proposed to determine the relative extent of alteration in cm chondrites the mineralogic alteration index monitors the relative progress of coupled substitutions in the progressive alteration of cronstedtite to mg serpentine and increases with increasing alteration to calculate values of this index an algorithm has been developed to estimate the average matrix phyllosilicate composition in individual cm chondrites the second parameter is the volume percent of isolated matrix silicates which decreases with progressive alteration due to mineral hydration finally the volume percent of chondrule alteration monitors the extent of chondrule phyllosilicate production and increases as alteration proceeds these parameters define the first cm alteration scale that relies on multiple indicators of progressive alteration the following relative order of increasing alteration is established by this model murchison bells pollen murray mighei nogoya cold bokkeveld the relative degree of aqueous processing cochabamba and boriskino experienced is less precisely constrained although both fall near the middle of this sequence a comparison between the mineralogic alteration index and literature values for the whole rock chemistry of cm chondrites reveals several correlations a positive nearly linear correlation between bulk h content and progressive cm alteration suggests an approximately constant production rate of new phyllosilicates relative to the mineralogical transition from cronstedtite to mg serpentine the abundance of trapped planetary 36ar decreases systematically in progressively altered cm chondrites suggesting the wholesale destruction of primary noble gas carrier phase s by aqueous reactions because low temperature fluid rock reactions are generally associated with large isotopic mass fractionation factors we also compared our model predictions with 18o values for bulk cm samples although some of these data are poorly resolved the order of increasing 18o values approximates the order of increasing alteration predicted by our model parameters multiple correlations between diverse alteration parameters strongly suggest that a different cm chondrites experienced similar kinds of processes and conditions and b cm materials experienced in situ alteration on the cm parent body or bodies

cm chondrites exhibit the complete petrologic range from type 2 to 1 we have characterized the most phyllosilicate rich members of the cm chondrite group based upon petrographic and compositional factors we conclude that these particular meteorites have experienced pervasive aqueous alteration far beyond that witnessed by typical cms the lack of anhydrous silicates cai and except as relicts chondrules merits the classification of type cmi for three meteorites eet 83334 alh 88045 and one kaidun lithology still other cms notably alh 83100 eet 90047 and yamato 82042 are clearly intermediate between types 1 and 2 brecciated cm chondrites like cold bokkeveld contain all of these varied lithologies the cm chondrites thus exhibit the complete petrologic range from 2 through 1 our results show that progressive aqueous alteration on the parent cm asteroid s was locally accompanied by significant increases in temperature to a peak of 450 c for the kaidun lithology fo2 and locally degree of chemical leaching all well beyond the conditions recorded by typical cm2s the most altered cms also are commonly deformed displaying a distinct lineation probably due to static rather than dynamic forces

origin of the pluto charon system constraints from the new horizons flyby abstract new horizon s accurate determination of the sizes and densities of pluto and charon now permit precise internal models of both bodies to be constructed assuming differentiated rock ice structures we find that pluto is close to 2 3 solar composition anhydrous rock by mass and charon 3 5 solar composition anhydrous rock by mass pluto and charon are closer to each other in density than to other large 1000 km diameter kuiper belt bodies despite this we show that neither the possible presence of an ocean under pluto s water ice shell and no ocean within charon nor enhanced porosity at depth in charon s icy crust compared with that of pluto are sufficient to make pluto and charon s rock mass fractions match all four small satellites styx nix kerberos hydra appear much icier in comparison with either pluto or charon in terms of a giant impact origin both these inferences are most consistent with the relatively slow collision of partly differentiated precursor bodies canup astrophys j 141 35 2011 this is in turn consistent with dynamical conditions in the ancestral kuiper belt but implies that the impact precursors themselves accreted relatively late and slowly to limit 26 al and accretional heating the iciness of the small satellites is not consistent with direct formation of the pluto charon system from a streaming instability in the solar nebula followed by prompt collapse of gravitationally bound pebble piles a proposed formation mechanism for kuiper belt binaries nesvorn et al astron j 140 785 793 2010 growth of pluto scale bodies by accretion of pebbles in the ancestral kuiper belt is not ruled out however and may be needed to prevent the precursor bodies from fully differentiating due to buried accretional heat prior to the charon forming impact

planetesimal sulfate and aqueous alteration in cm and ci carbonaceous chondrites water soluble sulfate salts extracted from six cm chondrites have oxygen isotope compositions that are consistent with an extraterrestrial origin the 17 o of sulfate are correlated with previously reported whole rock 18 o and with an index of meteorite alteration and may display a correlation with the date of the fall the enrichments and depletions for 17 o of water soluble sulfate from the cm chondrites relative to the terrestrial mass dependent fractionation line are consistent with sulfate formation in a rock dominated asteroidal environment and from aqueous fluids that had undergone relatively low amounts of oxygen isotope exchange and little reaction with anhydrous components of the meteorites it is unresolved how the oxidation of sulfide to sulfate can be reconciled with the inferred low oxidation state during the extraterrestrial alteration process oxygen isotope data for two ci chondrites orgueil and ivuna as well as the ungrouped c2 chondrite essebi are indistinguishable from sulfate of terrestrial origin and may be terrestrial weathering products consistent with previous assertions our oxygen isotope data however can not rule out a preterrestrial origin either copyright 2005 elsevier ltd

a terrestrial origin for sulfate veins in ci1 chondrites white sulfate veins are a very well known petrological feature of the chemically primitive ci1 carbonaceous chondrites sulfate veins were first described in the orgueil meteorite in 1961 almost one century after its fall however we have observed such veins to form easily during typical sample storage we suggest that all ci1 sulfate veins formed during the terrestrial residence of these heavily brecciated porous stones reacting with atmospheric water sulfates originally present in the meteorites dissolved and remobilized and or sulfides oxidised filling the many open spaces offered to them by the very porous rock sulfate veins in ci1 chondrites can no longer be used as evidence of a late stage oxidation event in the ci1 parent body or of centimeter scale fluid transport on the parent asteroid

terrestrial alteration of carbonate in a suite of antarctic cm chondrites evidence from oxygen and carbon isotopes the oxygen 18o 17o and carbon 13c fmod14c the fraction of modern 14c isotopic compositions of carbonate were measured for a set of paired antarctic cm chondrites eet 96006 eet 96016 eet 96017 and eet 96019 while the oxygen isotopic compositions do not plot on the terrestrial fractionation line and indicate that a component of the carbonate minerals has an extraterrestrial origin they also do not fall on the array defined for carbonates by cm falls and are thus consistent with the presence of a terrestrial carbonate component the 13c and fmod14c measurements of carbonate suggest the presence of at least two carbon sources carbonate derived from atmospheric co2 that is inferred to have been produced as a result of silicate weathering reactions and carbonate derived from another carbon source that is either old or non atmospheric the relationships between oxygen and carbon isotope data provide additional constraints on the weathering process and allow the possibility that rock dominated weathering of the meteorite caused the oxygen isotopic composition of antarctic water added to the meteorite to evolve away from the terrestrial mass fractionation array leading to formation of low temperature terrestrial alteration products that do not lie on the terrestrial fractionation line

composition and evolution of the early oceans evidence from the tagish lake meteorite abstract laboratory leaching studies of the tagish lake meteorite demonstrate that the most readily leached cations of carbonaceous chondrite meteorites are mg ca na and k with the most readily leached anions being so4 cl and po4 in decreasing order of abundances soluble organics were not analyzed due to limited sample sizes magnesium and sulfate the most abundant solutes leached from tagish lake meteorite are also the most abundant ions of salts lining fractures of aqueously altered meteorites these same ions probably were the most abundant solutes of the first permanent oceans which probably formed during or soon after the late heavy bombardment stage 4 2 to 3 7 ga considering the residence time of cl in modern seawater and the composition of the exposed continental crust to at least 3 3 ga evolution of seawater from mg so4 dominated to nacl dominated would have required about 3 105 yr and could not have been complete until about 3 0 to 3 3 ga the calculations also suggest that the first permanent oceans were more saline than modern seawater and as argued by others these aspects have significant implications for evolution of life many solar system bodies besides earth probably derived a significant proportion of their volatile and soluble constituents from carbonaceous chondrite material therefore primordial solutions similar to those presented here were likely important in the early evolution of aqueous systems throughout the solar system including those present on carbonaceous chondrite parent asteroids and icy outer solar system satellites

using earth tide induced water pressure changes to measure in situ permeability a comparison with long term pumping tests good constraints on hydrogeological properties are an important first step in any quantitative model of groundwater flow field estimation of permeability is difficult as it varies over orders of magnitude in natural systems and is scale dependent here we directly compare permeabilities inferred from tidal responses with conventional large scale long term pumping tests at the same site tidally induced water pressure changes recorded in wells are used to infer permeability at ten locations in a densely fractured sandstone unit each location is either an open hole well or a port in a multilevel monitoring well tidal response is compared at each location to the results of two conventional long term and large scale pumping tests performed at the same site we obtained consistent values between the methods for a range of site specific permeabilities varying from 10 15 m2 to 10 13 m2 for both open wells with large open intervals and multilevel monitoring well we conclude that the tidal analysis is able to capture passive and accurate estimates of permeability

experimental constraints on kinetic and equilibrium silicon isotope fractionation during the formation of non biogenic chert deposits silicon isotopic compositions 30si of modern and ancient siliceous sedimentary rocks provide valuable information on conditions in depositional environments but interpretations are hampered by the lack of experimentally validated fractionation factors here we present new constraints on the magnitudes of kinetic and equilibrium isotope effects during chemical precipitation of amorphous silica in batch reactors at low temperature 10 35 c and near neutral ph 7 5 8 5 as analogue for non biogenic chert formation instantaneous fractionation factors derived from 30si values of the total dissolved sitd silica and mass balance computations with inst 30sippt 1000 30sitd 1000 decrease with progressive precipitation and reduced reaction rates this suggests that silica deposition in the batch reactors is kinetically dominated at the start of the experiments but approaches a metastable equilibrium after ca 400hours modelled kinetic fractionation factors range from 0 9965 at 10 c to 0 9976 at 20 c and 0 9993 at 35 c and ph8 5 whereas equilibrium isotope effects are smaller and range from 0 9995 at 10 c to 1 000 at 20 c and 1 0005 at 35 c our results suggest that large isotope effects are only expressed in natural systems where dissolved and precipitated silica are not equilibrated implying that the kinetic conditions of non biogenic silica precipitation provide important constraints on silicon isotope ratios of siliceous rocks with particular relevance for those preserved in the archean chert record

mechanisms of recharge in a fractured porous rock aquifer in a semi arid region abstract eleven porewater profiles in rock core from an upland exposed sandstone vadose zone in southern california with thickness varying between 10 and 62 m were analyzed for chloride cl concentration to examine recharge mechanisms estimate travel times in the vadose zone assess spatial and temporal variability of recharge and determine effects of land use changes on recharge as a function of their location and the local terrain the profiles were classified into four groups reflecting the range of site characteristics century to millennium average recharge varied from 4 to 23 mm y 1 corresponding to 1 moreover the temporal variability of recharge was estimated and along each profile past recharge rates calculated based on the sequence of cl concentrations in the vadose zone recharge rates increased at specific times coincident with historical changes in land use the consistency between the timing of land use modifications and changes in cl concentration and the match between observed and simulated cl concentration values in the vadose zone provide confidence in porewater age estimates travel times recharge estimates and reconstruction of recharge histories this study represents an advancement of the application of the chloride mass balance method to simultaneously determine recharge mechanisms and reconstruct location specific recharge histories in fractured porous rock aquifers the proposed approach can be applied worldwide at sites with similar climatic and geologic characteristics

flow modeling and permeability estimation using borehole flow logs in heterogeneous fractured formations a numerical model of flow in the vicinity of a borehole is used to analyze flowmeter data obtained with high resolution flowmeters the model is designed to 1 precisely compute flow in a borehole 2 approximate the effects of flow in surrounding aquifers on the measured borehole flow 3 allow for an arbitrary number n of entry exit points connected to m n far field aquifers and 4 be consistent with the practical limitations of flowmeter measurements such as limits of resolution typical measurement error and finite measurement periods the model is used in three modes 1 a quasi steady pumping mode where there is no ambient flow 2 a steady flow mode where ambient differences in far field water levels drive flow between fracture zones in the borehole and 3 a cross borehole test mode where pumping in an adjacent borehole drives flow in the observation borehole the model gives estimates of transmissivity for any number of fractures in steady or quasi steady flow experiments that agree with straddle packer test data field examples show how these cross borehole type curves can be used to estimate the storage coefficient of fractures and bedding planes and to determine whether fractures intersecting a borehole at different locations are hydraulically connected in the surrounding rock mass