reply to the comments by marignac and cathelineau on the paper by sanchez espana et al source and evolution of ore forming hydrothermal fluids in the northern iberian pyrite belt massive sulphide deposits sw spain evidence from fluid inclusions and stable isotopes mineralium deposita 38 519 537

seafloor weathering and the oxygen isotope ratio in seawater insight from whole rock δ18o and carbonate δ18o and δ47 from the troodos ophiolite abstract the controls on and history of the oxygen isotope ratio in seawater continue to be debated after many decades of research with the lack of consensus in large part reflecting uncertainty in the role of hydrothermal exchange between seawater and the oceanic crust we have investigated this using new carbonate 47 and 18 o data and whole rock o isotope data for samples from the lava section of the troodos ophiolite carbonate data confirm that fluid to rock ratios in the upper lavas during off axis hydrothermal circulation are generally sufficiently large that both the fluid 18 o and temperature are similar to those of bottom water however some samples require more complicated interpretations that could reflect changes in the rate of calcite formation whole rock data indicate that o isotope exchange in the lavas is directly linked to the major element exchange that leads to alkalinity production i e co2 consumption and both are dependent on bottom water temperature this means that the o isotopic composition of seawater is linked to the long term c cycle the data are used to parameterise a simple model of the evolution of the o isotopic composition of seawater driven by changes in solid earth co2 degassing alkalinity balance links the total extent of weathering of the continents and seafloor which are sinks for high 18 o material to co2 degassing rate and surface temperature the modelling suggests that if solid earth co2 degassing and the rate of formation of oceanic crust are linked the o isotopic composition of the ocean including any ice sheets is unlikely to have varied more than 1 over the phanerozoic

geochemistry of peruvian near surface sediments sixteen short sediment cores were recovered from the upper edge ueo within wo and below bo the oxygen minimum zone omz off peru during cruise 147 of r v sonne solids were analyzed for major trace elements total organic carbon total inorganic carbon total sulfur the stable sulfur isotope composition 34 s of pyrite and sulfate reduction rates srr pore waters were analyzed for dissolved sulfate sulfide and 34 s of sulfate in all cores highest srr were observed in the top 5 cm where pore water sulfate concentrations varied little due to resupply of sulfate by sulfide oxidation and or diffusion of sulfate from bottom water 34 s of dissolved sulfate showed only minor downcore increases strong 32 s enrichments in sedimentary pyrite to 48 vs v cdt are due to processes in the oxidative part of the sulfur cycle in addition to sulfate reduction manganese and co are significantly depleted in peruvian upwelling sediments most likely due to mobilization from particles settling through the omz whereas release of both elements from reducing sediments only seems to occur in near coastal sites cadmium mo and re are exceptionally enriched in wo sediments 600 m water depth high re and moderate cd and mo enrichments are seen in bo sediments 600 m water depth re mo ratios indicate anoxic and suboxic conditions for wo and bo sediments respectively cadmium and mo downcore profiles suggest considerable contribution to ueo wo sediments by a biodetrital phase whereas re presumably accumulates via diffusion across the sediment water interface to precipitation depth uranium is distinctly enriched in wo sediments due to sulfidic conditions and in some bo sediments due to phosphorites silver transfer to suboxic bo sediments is likely governed by diatomaceous matter input whereas in anoxic wo sediments ag is presumably trapped due to sulfide precipitation cadmium cu zn ni cr ag and t1 predominantly accumulate via biogenic pre concentration in plankton remains rhenium sb as v u and mo are enriched in accordance with seawater te availability lead and bi enrichment in ueo surface sediments is likely contributed by anthropogenic activity mining accumulation rates of toc cd mo u and v from peruvian and namibian sediments exceed those from the oman margin and gulf of california due to enhanced preservation off peru and namibia copyright 2004 elsevier ltd

stable isotope compositions of serpentinite seamounts in the mariana forearc serpentinization processes fluid sources and sulfur metasomatism the mariana and izu bonin arcs in the western pacific are characterized by serpentinite seamounts in the forearc that provide unique windows into the mantle wedge we present stable isotope o h s and c data for serpentinites from conical seamount in the mariana forearc and s isotope data for torishima seamount in the izu bonin forearc in order to understand the compositions of fluids and temperatures of serpentinization in the mantle wedge and to investigate the transport of sulfur from the slab to the mantle wedge six serpentine mineral separates have a restricted range of 18o 6 5 8 5 antigorite separates have d values of 29 5 to 45 5 that reflect serpentinization within the mantle wedge whereas chrysotile has low d values 51 8 to 84 0 as the result of re equilibration with fluids at low temperatures fractionation of oxygen isotopes between serpentine and magnetite indicate serpentinization temperatures of 300 375 c two late cross fiber chrysotile veins have higher 18o values of 8 9 to 10 8 and formed at lower temperatures as low as 100 c aqueous fluids in equilibrium with serpentine at 300 375 c had 18o 6 5 9 and d 4 to 26 consistent with sediment dehydration reactions at temperatures 200 c in the subducting slab rather than a basaltic slab source three aragonite veins in metabasalt and siltstone clasts within the serpentinite flows have 18o 16 7 24 5 consistent with the serpentinizing fluids at temperatures 250 c 13c values of 0 1 2 5 suggest a source in subducting carbonate sediments the 34s values of sulfide in serpentinites on conical seamount 6 7 to 9 8 result from metasomatism through variable reduction of aqueous sulfate 34s 14 derived from slab sediments despite sulfur metasomatism serpentinites have low sulfur contents generally 164 ppm that reflect the highly depleted nature of the mantle wedge the serpentinites are mostly enriched in 34s median 34ssulfide 4 5 consistent with a 34s enriched mantle wedge as inferred from arc lavas

controls on the siting and style of volcanogenic massive sulphide deposits abstract volcanogenic massive sulphide vms deposits form in subaqueous environments from circulating hydrothermal fluids heated by volcanic activity these deposits form as sulphide mounds stratiform exhalative and or replacive bodies and commonly have stockwork vein mineralization in their immediate footwall these various styles are essentially facies of mineralization each one being the product of a particular set of conditions that control the ore forming processes and the consequent geometry and architecture style of the deposits these controls include the physical and or chemical nature of the host rocks the temperature and composition of the hydrothermal fluids and the redox state of the depositional environment the style of exhalative deposits is controlled by the salinity of the vented fluids and the redox state at the seafloor hydrothermal fluids with salinities less than twice that of seawater that vented into open oxic oceanic environments typically formed small mound and chimney complexes unless they were rapidly covered by sediments or volcanic rocks the massive sulphides were rapidly oxidized and partly dissolved by seawater in contrast stratiform sheet like deposits are typically formed in anoxic bottom waters anoxic marine conditions were periodically of global extent particularly prior to 2 4 ga or of a regional nature local anoxic conditions can also be self induced by the exhalation of saline and reducing hydrothermal fluids that ponded in bathymetric depressions such as second or third order basins to form a brine pool these exhalative systems may have been initiated as chimney vent complexes and subsequently overlain by stratiform sulphides formed under the self induced anoxic conditions deposits formed in anoxic environments can be significantly larger than those in oxic settings and this is attributed to several factors that include longer lived hydrothermal circulation more efficient sulphide precipitation and reduced or inhibited oxidation thereof replacement of volcanic and sedimentary strata by sulphide typically occurs within the feeder zones beneath the exhalative mineralization however successions with abundant porous permeable and or reactive rocks such as glassy and or pumiceous volcaniclastic rocks and in some cases limestone favoured the development of large replacive deposits that may have had little surficial expression on the sea floor vms deposits at spreading centres within oceanic crust formed almost exclusively as mounds most of them have not been preserved likely due to oxidation of the sulphides in the prevailing oxic environment and or destruction of oceanic crust during subsequent subduction intra continental rifts arc rifts and back arc rifts commonly have more complexity in their structure and facies architecture and environments and can host all styles of vms mineralization in these settings early extension favoured the formation of restricted basins with ideal conditions for the onset of hydrothermal activity and development of anoxic bottom waters whereas in mature rifts the conditions were less conducive for the formation of regionally extensive anoxic environments formation of replacive deposits was permissible in all settings with porous or reactive subsea floor strata replacive mineralization is the most likely to be preserved in the geological record due to the sulphides being physically shielded from oxidative weathering and mechanical erosion at the seafloor the various styles of vms mineralization can rarely be distinguished using a single criterion in most cases multiple criteria are required mound style mineralization is distinguished by a mound or lens shaped morphology b presence of chimney fragments c presence of abundant sedimented sulphide breccias d location on a stratigraphic boundary ore horizon and e association with a thin horizon or thicker stratigraphic interval of fine grained clastic rocks e g shale mudstone that accumulated at slow sedimentation rates stratiform exhalative mineralization is distinguished by a sheet like morphology prior to deformation b presence of fine grained clastic host rocks that accumulated at relatively slow rates e g mudstone c presence of local or extensive planar stratification replacive mineralization is characterized by a irregular geometry and distribution of sulphide bodies b gradation from massive sulphides to semi massive sulphides and disseminated mineralization with relict textures of the host rock and c originally pumiceous glassy or reactive host rocks emplaced at high depositional rates mass flow deposits lavas carbonate altered mass flow deposits or limestone one deposit or district may comprise two or more of these main styles of mineralization in many cases the main styles of vms mineralization present in a particular region can be predicted from examination of the facies architecture and depositional environments of the host succession recognition of the style s of mineralization that occur in a particular basin or mineral belt enables exploration models to be improved and should influence the strategy of exploration for vms deposits

impact of atmospheric co2 and galactic cosmic radiation on phanerozoic climate change and the marine δ18o record 1 a new model is developed and applied to simulate the phanerozoic evolution of seawater composition dissolved ca sr dissolved inorganic carbon alkalinity ph 18o marine carbonates sr ca 87sr 86sr 13c 18o atmospheric co2 and surface temperature the marine carbonate records sr ca 87sr 86sr 13c are used to reconstruct changes in volcanic tectonic activity and organic carbon burial over the phanerozoic seawater ph is calculated assuming saturation with respect to calcite and considering the changing concentration of dissolved ca documented by brine inclusion data the depth of calcite saturation is allowed to vary through time and the effects of changing temperature and pressure on the stability constants of the carbonate system are considered surface temperatures are calculated using the geocarb iii approach considering also the changing flux of galactic cosmic radiation gcr it is assumed that gcr cools the surface of the earth via enhanced cloud formation at low altitudes the 18o of marine carbonates is calculated considering the changing isotopic composition of seawater the prevailing surface temperatures and seawater ph repeated model runs showed that the trends observed in the marine 18o record can only be reproduced by the model if gcr is allowed to have a strong effect on surface temperature the climate evolution predicted by the model is consistent with the geological record warm periods cambrian devonian triassic cretaceous are characterized by low gcr levels cold periods during the late carboniferous to early permian and the late cenozoic are marked by high gcr fluxes and low pco2 values the major glaciations occurring during these periods are the result of carbon cycling processes causing a draw down of atmospheric co2 and a coevally prevailing dense cloud cover at low altitudes induced by strong gcr fluxes the two moderately cool periods during the ordovician silurian and jurassic early cretaceous are characterized by both high pco2 and gcr levels so that greenhouse warming compensated for the cooling effect of low altitude clouds the very high jurassic 18o values observed in the geological record are caused by low ph values in surface waters rather than cold surface conditions

on suspended barite and the oxygen minimum in the southern ocean particulate ba profiles were measured in the indian sector of the southern ocean the largest fraction 80 of this barium is present as barite microcrystals the profiles of total barium are characterized by a subsurface maximum between 200 and 500 m depth in the vicinity of the oxygen minimum highest barium values are found just south of the polar front while lowest values occur close to the antarctic divergence between the divergence and the polar front a tight inverse relationship is observed between oxygen in the oxygen minimum and barium in the barium maximum this relationship disappears north of the polar front since suspended barite is known to be of biological origin the correlation of barite with oxygen suggests that the observed decrease of oxygen in the oxygen minimum between the divergence and the polar front is due to local consumption of oxygen it is proposed that deep low oxygen water is advected towards the divergence where upwelling occurs and where this water subsequently partly spreads out to the north north east as entrained by the antarctic circumpolar current oxidation of locally produced organic matter with which barite crystals are associated consumes oxygen and sets free individual discrete barites as a result oxygen decreases and barite increases away from the divergence with barite integrating former biological processes

sediment cd and mo accumulation in the oxygen minimum zone off western baja california linked to global climate over the past 52 kyr 1 concentrations of organic carbon orgc cadmium cd and molybdenum mo were measured in two sediment cores raised from depths of 430 and 700 m within the oxygen minimum zone omz off southern baja california at a temporal resolution of 0 5 kyr over the past 52 kyr these records are supplemented with diffuse spectral reflectance dsr measurements obtained on board ship soon after collection at a resolution of 0 05 kyr in the core from 700 m depth a component extracted from the dsr data and the three geochemical proxies generally vary in concert with each other and over a wide range 4 22 orgc 1 40 mg kg cd 5 120 mg kg mo intervals of increased orgc cd and mo accumulation generally correspond to warm periods recorded in the oxygen isotopic composition of greenland ice with the exception of the bolling allerod which is only weakly expressed off baja california concentrations of the biogenic proxies are higher in the core from 430 m depth but erratic sediment accumulation before 15 ka precludes dating of the older intervals that are laminated and contain elevated orgc cd and mo concentrations the new data provide further evidence of an intimate teleconnection between global climate and the intensity of the omz and or productivity along the western margin of north america on the basis of a comparison with cd and mo records collected elsewhere in the region we conclude that productivity may actually have varied off southern baja california by no more than a factor of 2 over the past 52 kyr

textures of the hellyer volcanic hosted massive sulfide deposit tasmania the aging of a sulfide sediment on the sea floor the relatively undeformed polymetallic massive sulfide ore of the hellyer deposit retains many textures developed during the early crystallization history common textures in the least modified ore away from the main feeder zone include pyrite framboids concentric and radial textured spheres dendritic and fibrous forms breccias mineral banding veins and reniform and crustification textures many are typical of early crystallization within a medium at high degrees of supersaturation some result from open space filling and others indicate disturbances of the sulfide mass possibly due to tectonic activity and volume adjustment the banding could be due to current winnowing most of these textures are found in modern midocean ridge and kuroko massive sulfide deposits but at hellyer the framboids are much more common hexagonal outlines in ore sphalerite indicate derivation of much of the sphalerite by inversion of wurtzite the high content of chalcopyrite in the wurtzite derived sphalerite appears in most cases to have developed by exsolution rather than replacement or coprecipitation although there is local evidence of both processes having operated possibly resulting from early asymmetrical crystal growth comparison of hellyer ore and typical kuroko ores reveals other differences than framboid abundance e g metal contents and ratios mineralogy and sulfur isotope compositions the most significant of which are the relatively high salinities of the hellyer ore fluids these together with evidence of a coeval basin imply sulfide deposition in a brine pool as previously proposed the development of a quenched sulfide mud at the bottom of a basin filled with spent ore fluid with little or no involvement of seawater explains the different mineral content e g lack of fe oxides scarcity of barite in the massive sulfide and the pyrite arsenopyrite assemblage the high metal content lack of chimney structures and differences in sulfur isotope compositions the sulfide mud dominated by fe s phases would be an ideal growth medium for framboidal pyrite the weight of experimental evidence concerning the development of framboidal pyrite points to involvement of metastable precursor fe s phases such as mackinawite and greigite in a weakly oxidized environment oxygen may have been added to the reduced acid brine pool as a result of inward diffusion of oxygen from overlying seawater which is shown to have been oxic by the presence of sessile benthic dendroids in the shales overlying the ore deposit however the level of oxidation was insufficient to form marcasite

rhenium and molybdenum enrichments in sediments as indicators of oxic suboxic and sulfidic conditions of deposition abstract the trace elements re and mo both behave conservatively in seawater yet are strongly enriched in reducing sediments their potential for authigenic enrichment above crustal concentrations is greater than for many other elements due to the high ratio of metal sw metal crust we present sedimentary re and mo data from box and multi cores spanning a range of redox conditions from well oxygenated sites to locations with substantial sulfide concentrations at the oxic sites re and mo as expected accumulate at concentrations close to their crustal abundances re shows substantial enrichment in suboxic absence of o 2 and h 2 s sediments of the sea of japan in sediments within the oxygen minimum of the pakistan margin as well as in sediments underlying the sulfide bearing waters of the black sea and saanich inlet re enrichment occurs in these cores just below the depths of fe and u reduction only in the sediments underlying the sulfidic waters of the black sea and saanich inlet is there substantial authigenic mo accumulation absence of re and mo enrichments in sediment trap samples from the sulfide bearing basins suggests that the addition of both metals occurs at or below the sediment water interface the re and mo concentration profiles are modeled to hindcast the removal depth of re and mo in the sediments which along with the re mo ratio determine whether oxic suboxic or sulfidic conditions were present in the water column or in the sediments in the past using this approach historical redox conditions can be inferred even in environments such as continental margins where a substantial lithogenic component can obscure authigenic enrichments of other metals

molybdenum and uranium geochemistry in continental margin sediments paleoproxy potential abstract we measured solid phase mo and u concentrations in marine sediments from the california mexico peru and chile margins to ascertain the behavior of mo and u during early diagenesis in continental margin settings at sites along the california mexico and peru margins where there are estimates of mass accumulation rates authigenic u accumulation rates range from 0 50 nmol m 2 day 1 at the california and mexico margin sites mo accumulation rates range from 0 to 134 nmol m 2 day 1 whereas at the peru margin site rates may be as high as 550 nmol m 2 day 1 we observe relationships between metal accumulation rates and the delivery and burial rates of organic carbon corg in the case of mo there appears to be at least two relationships between metal accumulation rate and organic carbon burial for most of the data presented in this manuscript continental margin sediments have a mo corg accumulation rate ratio of 20 mol mol 1 this value is significantly lower however than those reported for anoxic basins 100 mol mol 1 but is consistent with reported mo corg rain ratios from mexico margin sediment traps in contrast to mo there appears to be a single u corg burial ratio of 5 mol mol 1 which includes a range of environments from anoxic basins and open ocean sites we interpret the relationships between metal accumulation and organic carbon to indicate that the reactions that govern authigenic metal accumulation are primarily sensitive to the delivery and burial of organic carbon in these particular settings however we note that any relationship between metal accumulation and organic carbon could be indirect in the particular case of mo based on what is known about mo geochemistry from the literature it is possible that mo authigenesis is coupled to sulfur cycling in many of the environments covered by this study and that the observed association between mo and organic carbon burial is a consequence of the coupling between carbon and sulfur burial using the observed relationships between mo and corg burial as well as constraints from the mo isotope budget we estimate that continental margin sediments are an important sink for mo the magnitude of this sink 0 4 108 mol y 1 or larger may be as much as one quarter of the oceanic removal term and is likely to be larger than the modern anoxic basin sink

the accumulation of silver in marine sediments a link to biogenic ba and marine productivity 1 the concentrations of ag and a suite of redox sensitive trace metals re cd and mo were measured in surface sediments from the western canadian mexican peruvian and chilean continental margins in all regions ag content increases from 80 ng g 1 i e lithogenic values on the shelf up to as high as 1483 ng g 1 on the lower slope however the trend of increasing ag with increasing water depth breaks down at deepwater sites 2500 m where only lithogenic concentrations are documented silver content does not correlate with the distributions of redox sensitive trace metals suggesting that sedimentary redox conditions are not the primary control on ag accumulation instead a positive correlation between ag and ba in surface and near surface sediments suggests that ag is scavenged by and delivered to the sediment with the organic particle flux scavenging probably results from the precipitation of ag2s within the organic particles due to the development of anoxia and sulfate reduction if this hypothesis is correct then ag has the potential to be a paleoproductivity proxy

a new sulphur isotopic study of some iberian pyrite belt deposits evidence of a textural control on sulphur isotope composition the sulphide deposits of the iberian pyrite belt ipb represent an ore province of global importance our study presents 113 new sulphur isotope analyses from deposits selected to represent the textural spectrum of ores measured 34s values range from 26 to 10 mostly for massive and stockwork ores in agreement with data previously published in situ laser 34s analyses reveals a close correlation of 34s with texture primary diagenetic textures are dominated by relatively low 34s 8 to 2 whereas stockwork feeder textures are dominated by higher 34s 3 to 5 intermediate textures mainly coarse textures in stratiform zones have intermediate 34s although they are mostly dominated by the high 34s component rare barite has a homogeneous 34s around 18 which is consistent with direct derivation from lower carboniferous seawater sulphate a dual source of sulphide sulphur in the ipb deposits has been considered a hydrothermal source derived from reduction of coeval seawater sulphate in the convective systems is represented by sulphide in the feeder zones here variations in 34s are caused by variations in the extent of the sulphate reduction which governs the so4 h2s ratio the second end member was derived from the bacterial reduction of coeval seawater sulphate at or near the surface as reflected in the primary textures a distinct geographical variation in 34s and texture from sw more bacteriogenic and primary textures to ne more hydrothermal textures and 34s which reflects a variation in the relative input of each source was likely controlled by local geological environments given that the sulphur isotope characteristics of the ipb deposits are unlike most vms and kuroko deposits and noting the dominance of a mixed reduced sedimentary and volcanic environment we suggest that the ipb could represent an ore style which is intermediate between volcanic and sedimentary hosted massive sulphide types

stable isotopic composition of upper oceanic crust formed at a fast spreading ridge odp site 801 1 odp legs 129 and 185 sampled the upper 474 m of 170 ma ocean crust in the western pacific in order to investigate alteration processes in fast spread crust and to determine inputs to subduction fourteen composite bulk samples of altered upper oceanic crust from site 801 have 18o 8 7 25 7 d 69 4 to 90 4 and 13c 2 7 to 1 8 the intensity of alteration and the amount of sediment within the basement decrease with depth leading to corresponding decreases in 18o and d a super composite constructed to estimate the bulk composition of the upper crust has 18o 12 0 d 87 0 and 13c 0 7 compared to core descriptions and geophysical logs the super composite contains too much 18o rich sediment 18o 25 7 and a corrected 18o value of 10 8 is more reasonable for the upper crust at site 801 these values are higher than those for other bulk upper oceanic basement sections 18o 8 0 10 0 and result in part from 1 intense low temperature 100 c hydrothermal alteration of the upper 100 m of tholeiitic basement at site 801 that may not be representative of material subducting in the western pacific and 2 an aging effect whereby progressive addition of 18o rich secondary carbonate in veins and breccia cements contributed to the high bulk 18o of this old upper crustal section

some comparative marine chemistries of rhenium gold silver and molybdenum abstract four metals re au ag and mo whose dissolved forms in seawater can potentially be reduced to insoluble states have been measured in a variety of solids depositing under anoxic conditions hydrothermal sulfides coastal sediments and phosphorites for comparative purposes these elements have also been determined in ferromanganese minerals and pelagic sediments which have accumulated under oxidizing conditions rhenium appears to be a unique sentinel for identifying reducing depositional environments where enrichments of greater than three orders of magnitude above crustal concentrations are found molybdenum follows re in these sediments but mo is enriched also in those that accumulate under oxidizing conditions the reported mo crustal concentrations appear low in comparison to our measured sedimentary values gold and ag are concentrated in hydrothermal deposits and sulfides appear to be involved in the precipitation of these elements coastal sediments adjacent to a domestic outfall of los angeles california contain extraordinary high accumulations of anthropogenic au ag and pt the study seeks an understanding of the mobilities and sinks of these metals in the marine environment during the major weathering cycle further anthropogenic contributions to their sedimentary concentrations are identified

oxygen isotope study of mid ocean ridge hydrothermal fluids implication for the oxygen 18 budget of the oceans new data are reported for the 18o composition of hot hydrothermal fluids from various sites with different tectonic settings the measured 18o in the range 0 53 2 3 confirm earlier data suggesting that mid ocean ridge hydrothermal vents are a major source of 18o to the ocean in light of this new data we attempt to re evaluate the marine 18o budget from direct quantification of the main sources and sinks of oceanic oxygen 18 within the uncertainty of the flux estimates 18o inputs and outputs are found to balance each other showing that oceanic 18o is presently at a steady state using these present fluxes we examine the past evolution of the 18o composition of the ocean and speculate that the initial 18o oceanic content may have evolved rapidly towards its present value this suggests as already pointed out in previous studies that ocean water may have had a rather constant 18o composition over most of the earth s history and that 18o measurements in ancient cherts and carbonates may primarily record the evolution of the ocean temperature

remobilization of barium in continental margin sediments abstract the rate of ba release from california continental margin sediments has been measured using an in situ benthic flux chamber and the range of values 25 50 nmol cm 2 y 1 is larger than any previously published benthic flux estimate for this element the magnitude of the ba flux suggests that a significant fraction of the ba raining from the euphotic zone is recycled at the seafloor ba si regeneration ratios from these margin sediments increase with depth demonstrating that ba is decoupled from si during the earliest stages of diagenesis on the other hand ba regeneration rates and caco3 dissolution rates covary the coupling between these two constituents is supported by the observation that the ba caco3 dissolution flux ratio 1 7 0 4 10 3 is independent of bottomwater depth even in sediments underlying the oxygen minimum zone along the continental margin furthermore this flux ratio is consistent with both the water column ba alkalinity ratio for the world s ocean as well as the ba caco3 ratio in sediment trap solid phases from the equatorial pacific 1 1 2 2 10 3 however the constancy of the ba alkalinity ratio over geologic time remains in question because the mechanism that controls this relationship remains a mystery our flux measurements suggest that diagenesis does not significantly influence the ba ca ratio in the upper 0 5 mm of pacific sediments thereby supporting the idea of using the ba concentration in surface dwelling benthic forams as a proxy for deep water chemical conditions lea and boyle 1989 1990 on the other hand we predict that if a foraminifer lives 0 5 mm or more below this interface then diagenetic effects could influence the ba ca ratio that foram species would record the carrier phase of the particulate ba reactive during early diagenesis does not appear to be organic matter oxyhydroxides or calcium carbonate but rather a mineral phase related to marine barite or perhaps celestite

intensification of the northeast pacific oxygen minimum zone during the bolling allerod warm period although climate records from several locations around the world show nearly synchronous and abrupt changes the nature of the inferred teleconnection is still poorly understood on the basis of preserved laminations and molybdenum enrichments in open margin sediments we demonstrate that the oxygen content of northeast pacific waters at 800 m depth during the bolling allerod warm period 15 13 kyr was greatly reduced existing oxygen isotopic records of benthic and planktonic foraminifera suggest that this was probably due to suppressed ventilation at higher latitudes of the north pacific comparison with ventilation records for the north atlantic indicates an antiphased pattern of convection relative to the north pacific over the past 22 kyr perhaps due to variations in water vapor transport across central america

shale basins sulfur deficient ore brines and the formation of exhalative base metal deposits abstract the massive sulfide deposits of the iberian pyrite belt are interbedded with felsic volcanic rocks and shale and underlain by several thousand meters of siliciclastic sedimentary rocks known as the pq group isotope geochemistry and regional geology are both consistent with equilibration of the ore forming fluids with the pq group prior to ore deposition near the former seafloor the average cu zn pb ratio of the pq group rocks ca 26 55 19 is similar to the weighted average of all the massive sulfide orebodies combined ca 25 52 23 the genetic relationship between massive sulfide deposits and a siliciclastic sedimentary metal source is explained here by a thermodynamic model proposing that mildly reducing redox conditions imposed by equilibration with the sedimentary rocks are most critical for the formation of an effective ore forming fluid relatively metal rich but organic poor pyrite bearing shale undergoing dewatering of saline pore fluids is an effective source for the generation of sulfur deficient but relatively iron and base metal rich brines thus we propose that the giant deposits of the iberian pyrite belt owe their existence not to exceptionally metal enriched e g magmatic fluids but to the existence of a fairly ordinary but large metal source in reactive siliciclastic sediments combined with an underlying igneous heat source and a particularly efficient mechanism of sulfide precipitation by mixing with h 2 s rich fluids at or near the seafloor essentially similar mineral equilibria are imposed when saline fluids are buffered by typical continental basement rocks leaching of retrograde minerals and possibly residual salts from their magmatic or metamorphic prehistory is expected to generate similar variably metal rich but relatively sulfide deficient fluids thus the existence of mildly reducing rocks can be the dominant chemical control in the source of fluids generating many volcanogenic irish type or sedex deposits many of which are known to precipitate their metal load in response to biogenic sulfide addition at the ore deposition site

oxygen isotope water relations in altered deep sea basalts low temperature mineralogical controls detailed analyses of oxygen isotope water relations in 3 13 and 109 ma old mid ocean ridge basalts reveal that to a first approximation the low temperature alteration of deep sea basalts in the upper few hundred metres of the igneous crust can be modelled as the partial conversion of basalt to smectite formed in isotopic equilibrium with seawater second order variations in 18o versus h2o plots are used to show that this approximation breaks down in detail because secondary mineral assemblages and mass transfer vary widely in response to subtle variations in temperature and or fluid flow strongly oxidized open systems can evolve relatively low i8o hydrous oxide rich assemblages if leaching is efficient dsdp deep sea drilling project site 396 or relatively anhydrous high 18o k feldspar rich assemblages if plagioclase breaks down site 417 compared with the clay mineral dominated assemblages common in somewhat more restricted flow environments zonal distribution and common superposition

geochemical response to pulsed sedimentation implications for the use of mo as a paleo proxy abstract deglacial sediments in piston core jt96 02 from the continental slope off western canada contain numerous centimeter thick iron sulfide rich layers major and minor element chemistry as well as c and n isotopic data suggest that these layers represent background hemipelagic sedimentation intervening gray silty clay layers each of which exhibits a fining upward trend are distal turbidites the iron sulfides precipitated in response to the emplacement of each turbidite which slowed oxygen diffusion into the sediment allowing anoxic conditions to develop in the underlying relatively organic rich deposits resulting sulfate reduction and precipitation of fe sulfide fostered mo enrichment 2 g g it may also explain ni cr v and co enrichments although differences in detrital mineralogy cannot be ruled out particularly for ni and cr rhenium is also enriched albeit slightly within the sulfide layers but low re mo ratios 0 78 ng g g g suggest that anoxic conditions developed very rapidly metals with high lithogenic concentrations cd and u are not obviously enriched in the sulfide layers because there was insufficient time for noticeable authigenic accumulation before deposition of the next turbidite which severed diffusive communication with overlying seawater the primary source of metals silver is also slightly higher in the sulfide layers possibly linked to higher marine organic matter content in summary the pulsed character of sedimentation during the deglaciation led to episodic enrichment of mo and occurred independently of changes in bottom water oxygen or organic carbon content this observation potentially complicates the use of mo as a paleo proxy in some continental margin environments

molybdenum accumulation in cariaco basin sediment over the past 24 k y a record of water column anoxia and climate molybdenum mo concentrations in a sediment core from the cariaco basin on the venezuelan continental shelf can be partitioned between a marine fraction and a terrigenous fraction the accumulation rate of the marine fraction of mo increased abruptly 15 000 calendar years ago 15 ka from 2 yr 1 to 4 g cm 2 yr 1 and then decreased abruptly at 9 ka the accumulation rate remained high throughout this 6 k y period but exhibited maxima at 15 14 and 12 5 ka corresponding in time to meltwater pulse ia into the gulf of mexico and the onset of the younger dryas cold event respectively the marine fraction of mo is interpreted in terms of redox conditions of bottom water as dictated by both the flux of settling organic matter and bottom water residence time correspondence between geochemical extremes in this core with changes in sea level and global climate demonstrates the high degree to which this ocean margin basin has responded to the paleoceanographic regime throughout the past 24 k y

silver in the western equatorial and south atlantic ocean vertical profiles of total dissolved 0 22 m silver concentrations in the equatorial and southwest atlantic ocean provide a new perspective on the processes controlling the element s external fluxes and internal biogeochemical cycling in the world ocean atmospheric inputs of natural and or industrial aerosols appear to elevate silver concentrations in remote surface waters in the south atlantic where silver is effectively scavenged onto and or bioaccumulated by plankton the subsequent remobilization of silver with depth is relatively coincident with that of silicate suggesting much of that silver is sequestered within a refractory organic phase associated with biogenic silica that silver is then remineralized and appears to be conservatively transported in subsurface water masses throughout the world ocean

comparison of rio tinto spain and guaymas basin gulf of california an explanation of a supergiant massive sulfide deposit in an ancient sill sediment complex the volcano sedimentary unit that hosts the stratiform massive sulfide mineralization at rio tinto is reinterpreted as a sill sediment complex that in many respects is analogous to the example that is currently forming in the guaymas basin gulf of california however rio tinto is distinctive because 1 it is a product of bimodal magmatism 2 it has a much higher sill sediment ratio 4 1 lessening the extent of ore forming metal depletion during interaction between hydrothermal fluid and wet sediment and 3 most of the sills were emplaced penecontemporaneously as shown by the ubiquitous development of peperitic sill margins despite the narrowness of the sedimentary screens these data together with evidence for local extrusive behavior imply rapid formation of the complex at exceptionally high levels of emplacement it follows that in the complex variations in thickness of 400 m were directly expressed as basin floor deformation and that troughs in the resultant topography were able to trap exhalative hydrothermal plumes thus preserving the sulfides from dispersion also crucial to the mineralization process was the sheetlike form of the sill complex which by acting as a cap prevented regular convective cell patterns from forming and focused considerable discharge at areas of weakness the intense magmatic pulse the creation of pronounced topography and the capping of the hydrothermal system combined to make a 500 mt supergiant deposit

preservation of particulate non lithogenic uranium in marine sediments particulate non lithogenic uranium pnu excess u above detrital background levels found in marine particulate matter is formed in surface waters throughout the ocean previous studies have shown that pnu is regenerated completely prior to burial of particles in sediments within well oxygenated open ocean regions however the fate of pnu has never been examined in ocean margin regions or in anoxic basins here we evaluate the preservation of pnu in ocean margin sediments and within semi enclosed basins using samples from sediment traps deployed at multiple depths and surface sediments organic carbon fluxes at the sediment trap locations ranged from 0 1 to 4 3 g cm 2 kyr while the dissolved oxygen concentration in the water column ranged from 3 mt o 270 m preservation of pnu increases with decreasing dissolved oxygen concentration approaching 100 preservation at oxygen concentration 25 m pnu contributes as much as 40 to 70 of the total authigenic u in sediments in the santa barbara basin and seasonally anoxic saanich inlet and some 10 to 50 of the total authigenic u in sediments off the central california margin copyright 2002 elsevier science ltd

sedimentary redox conditions in continental margin sediments n e pacific influence on the accumulation of redox sensitive trace metals redox conditions in near surface sediments from the continental margin off western canada were characterized to determine how they influence the accumulation of redox sensitive trace metals despite the development of suboxic conditions within millimeters of the sediment water interface there is little enrichment of re u cd or mo in the upper 10 to 15 cm of the sediment column this observation is consistent with the low extractible solid mn concentrations but high i corg ratios that imply that near surface sediment redox conditions are poised between mn and i reduction in contrast below 15 cm re and to a lesser extent cd and u are enriched e g up to 65 ng g re but only in those cores collected from within and below the oxygen minimum zone molybdenum concentrations remain low b1 5 g g in all cores indicating that these near surface sediments never became fully anoxic

sediment geochemical records of productivity and oxygen depletion along the margin of western north america during the past 60 000 years teleconnections with greenland ice and the cariaco basin abstract many sediment records from the margins of the californias alta and baja collected in water depths between 60 and 1200 m contain anoxic intervals laminated sediments that can be correlated with interstadial intervals as defined by the oxygen isotope composition of greenland ice dansgaard oeschger d o cycles these intervals include all or parts of oxygen isotope stage 3 ois3 60 24 cal ka the bolling allerod warm interval b a 15 13 cal ka and the holocene this study uses organic carbon corg and trace element proxies for anoxia and productivity namely elevated concentrations and accumulation rates of molybdenum and cadmium in these laminated sediments to suggest that productivity may be more important than ventilation in producing changes in bottom water oxygen bwo conditions on open highly productive continental margins the main conclusion from these proxies is that during the last glacial interval lgi 24 15 cal ka and the younger dryas cold interval yd 13 11 6 cal ka productivity was lower and bwo levels were higher than during ois3 the b a and the holocene on all margins of the californias the corg and trace element profiles in the lgi b a holocene transition in the cariaco basin on the margin of northern venezuela are remarkably similar to those in the transition on the northern california margin correlation between d o cycles in greenland ice with gray scale measurements in varved sediments in the cariaco basin also is well established synchronous climate driven changes as recorded in the sediments on the margins of the californias sediments from the cariaco basin and in the gisp 2 greenland ice core support the hypothesis that changes in atmospheric dynamics played a major role in abrupt climate change during the last 60 ka millennial scale cycles in productivity and oxygen depletion on the margins of the californias demonstrate that the california current system was poised at a threshold whereby perturbations of atmospheric circulation produced rapid changes in circulation in the eastern north pacific ocean it is likely that the pacific and atlantic oceans were linked through the atmosphere warmer air temperatures during interstadials would have strengthened hadley and walker circulations which in turn would have strengthened the subtropical high pressure systems in both the north pacific and the north atlantic producing increased rainfall over the cariaco basin and increased upwelling along the margins of the californias

reconstructing the rise of recent coastal anoxia molybdenum in chesapeake bay sediments abstract sporadic direct observations over a 50 yr period inadequately characterize the history of seasonal hypoxia and anoxia in chesapeake bay a large estuary threatened by eutrophication here we undertake a reconstruction of 20th century oxygen depletion in this estuary using mo concentrations in 210pb dated sediments cu concentrations are used to control for anthropogenic influences cores from the central channel display mild mo enrichments above crustal backgrounds up to 5 g g and strong cu enrichments up to 35 g g temporally cu enrichment mostly anthropogenic began earlier and stabilized in the last two thirds of the 20th century in contrast mo enrichment has grown during the last two thirds of the century molybdenum enrichment is mostly hydrogenic except in a section of the channel that receives additional mo from erosion of early miocene shore deposits two geochemical mechanisms promote mo enrichment manganese refluxing concentrates dissolved moo42 at the sediment water interface and sulfide substitution into moo42 produces thiomolybdates which can be fixed by particles the mo enrichment mechanisms operate primarily during periods when bottom waters are anoxic and thiomolybdate formation can occur near the sediment water interface this implies a temporal coupling between water column anoxia and mo fixation even though fixation occurs only within sediments the mo enrichment profiles suggest that chesapeake bay has experienced growing o2 depletion since the first half of the 20th century but especially after 1960

a complete oxygen isotope profile through the lower oceanic crust odp hole 735b abstract odp hole 735b located on the southwest indian ridge at 57 e is an in situ sampled long continuous section of lower oceanic crust oxygen isotope compositions of constituent minerals of leg 176 gabbros have been measured by uv laser oxygen isotope microprobe together with existing data from leg 118 a complete oxygen isotope profile through the lower oceanic crust has been obtained most clinopyroxenes and olivines have normal mantle values of 5 5 and 5 2 respectively while plagioclases show slight 18 o enrichment relative to its mantle value of 6 1 down hole variations of hole 735b gabbro indicate a downward decreasing 18 o profile with a kink at a depth of about 800 m below sea floor above this depth gabbros are depleted in 18 o relative to unaltered basalts while below 800 m they show nearly unmodified 18 o values abundant seawater penetration appears to be limited to the upper part of the lower crust at odp site 735 800 m into the gabbroic layer and 2 2 5 km into the oceanic crust from the top of pillow basalts mass balance calculations show that the lower crust formed under this ultra slow spreading ridge has an average 18 o value of 5 5 the whole crust at site 735 has an overall 18 o enrichment with 18 o values of 6 0 to 7 8 depending on the possible variation of the 18 o values of the upper pillow basalts and sheeted dykes the apparent difference in oxygen isotope compositions of ocean crusts formed with different spreading rates has important implications on the buffering of ocean water over geological time as well as on the oxygen recycling between crust and mantle through subduction the difference of seawater penetration between fast and slow spreading ridges could be related to their particular magmatic tectonic history during the formation and aging of the crust however more analyses on continuous sections through oceanic and ophiolitic crust in different tectonic settings are required to derive any predictive models

anomalous nitrogen isotopes in ultrahigh pressure metamorphic rocks from the sulu orogenic belt effect of abiotic nitrogen reduction during fluid rock interaction modern nitrogen n fixation is primarily mediated by biological processes however in the early earth where biological activity was absent or limited abiotic n reduction in hydrothermal systems is thought to be a key process to transform atmospheric n2 and nox to ammonium an essential nutrient to support the emergence of life and also an n form that can be incorporated into rocks surprisingly evidence for abiotic n reduction in the rock record has not been clearly identified in this study we reported anomalously low n isotope compositions n15 values as low as 15 8 15 8 of mica samples in ultrahigh pressure metamorphic rocks from the donghai area in the sulu orogenic belt eastern china compared with mica samples with typical crustal n15 values 3 9 3 9 in similar metamorphic rocks from the western dabie orogen the 15n depleted mica samples from the sulu orogen are characterized by significant n enrichment 10 times higher and extreme 18o depletion o18 values as low as 9 9 these features can be best explained by assimilation of n from a source characterized by extremely low n15 values less than 16 16 the extremely low n15 value would be produced by abiotic n reduction during reaction of a meteoric hydrothermal fluid with crustal rocks before subduction this observation provides a clue to the occurrence of abiotic n reduction in continental supracrustal rocks and infer that abiotic n reduction process could be a fundamental process driving the geological n cycling in early earth

hydrothermal alteration of felsic volcanic rocks associated with massive sulphide deposition in the northern iberian pyrite belt sw spain abstract massive sulphide deposits of the northern iberian pyrite belt ipb are mainly hosted by felsic volcanic rocks of rhyolitic to dacitic composition beneath most of the massive ores of this area e g concepcion san miguel aguas tenidas este or san telmo deposits there is usually a wide hydrothermal alteration halo associated with stockwork type mineralization within these alteration envelopes there are two principal rock types 1 chlorite rich rocks linked to the inner and more intensely altered zones and dominantly comprising chlorite pyrite quartz sericite carbonate rutile zircon chalcopyrite and 2 sericite rich rocks more common in the peripheral zones and showing a dominant paragenesis of sericite quartz pyrite chlorite carbonate rutile zircon sphalerite mass balance calculations comparing altered and least altered felsic volcanic rocks suggest that sericitization was accompanied by moderate enrichment in mg fe and h 2 o with depletion in si na and k and a slight net mass loss of about 3 chloritization shows an overall pattern which is similar to that of the sericitic alteration but with large gains in fe mg and h 2 o and minor enrichment in si s and mn and a significant loss of na and k and a minor loss of ca and rb however chloritization has involved a much larger net mass change mass gain of about 28 only a few elements such as nb y zr ti p and lree appear to have remained inert during hydrothermal alteration whilst ti and al have undergone very minor mobilization the results point to the severity of the physico chemical conditions that prevailed during the waxing stage of the ore forming hydrothermal systems further mineralogical and geochemical studies of the altered footwall rocks in the studied deposits indicate that hydrothermal ore bearing fluids reacted with host rocks in a multi stage process which produced a succession of mineralogical and chemical changes as the temperature increased

oxygen isotope composition of a section of lower oceanic crust odp hole 735b 1 the oxygen and hydrogen isotope compositions of vein minerals and 18o values of 64 whole rocks from the deeper kilometer of the 1 5 km lower crustal section of odp hole 735b in the sw indian ocean were analyzed in order to investigate seawater penetration into and reaction with the lower oceanic crust vein amphiboles have d values of 35 to 65 indicating formation from seawater fluids and hydrothermal fluids containing a component of low d magmatic fluid crystal plastic shear zones reacted with 18o enriched fluids at high temperatures and have 18o values of 6 0 7 0 indistinguishable from surrounding rocks reaction with seawater dominated fluids over a range of temperatures 350 700 c led to local 18o depleted rocks but much of the section exhibits 18o enrichment 18o up to 7 6 as the result of static alteration of plagioclase over a range of temperatures 250 to 600 c and fluid compositions chloritic veins and associated alteration by 18o enriched fluids occurred at temperatures of 150 250 c and late carbonates and fe oxyhydroxides formed from cold 10 seawater associated with open fault related fractures bulk rock 18o values of the lower 1 km range from 3 7 to 10 2 but are mostly 5 6 7 6 and the section has a mean bulk 18o of 6 5 1 0 in contrast rocks from the shallower 500 m exhibit net 18o depletion 5 1 1 0 reflecting high temperature deformation and seawater hydrothermal alteration stakes 1991 the weighted average 18o for the entire gabbro section of hole 735b is 6 0 exhibiting little or no change compared to unaltered crust although tectonism at slow spreading rates may allow exposure of lower crust to greater amounts of low temperature alteration and 18o enrichment there is no evidence for a consistent difference in the bulk 18o of the plutonic sections of oceanic crust formed at fast versus slow spreading rates

fluid temperature and salinity characteristics of the matagami volcanogenic massive sulfide district quebec fluid inclusions hosted within various lithologic units of the 40 million metric ton mt matagami district abitibi greenstone belt preserve samples of archean volcanogenic massive sulfide vms and postvolcanogenic massive sulfide hydrothermal fluid microthermometric measurements on ore hosted primary two phase liquid vapor inclusions from matagami s south limb deposits indicate that the vms hydrothermal fluid was highly saline 16 2 4 7 wt nacl cacl2 equiv 1 n 230 and of moderate temperature trapping temperature tt 208 32 c 1 n 230 a fluid with these characteristics is capable of transporting 5 10 4 m 30 ppm zn as zncl3 and zncl4 2 chloride complexes however the low temperature of this fluid precluded efficient cu transport 3 ppm which may in part explain the relatively cu poor nature of the matagami deposits calculated densities of this ore fluid as high as 1 10 g cm3 are consistent with a bottom hugging brine model however a subset of the data indicate a fluid less dense than ambient seawater suggesting that buoyant hydrothermal plumes were also present a microthermometrically determined high cacl2 content xnacl 0 55 molar na ca 2 3 1 for the vms ore hosted primary fluid is consistent with an archean hydrothermal fluid more ca rich than modern day seawater quartz epidote veins located in the hydrothermal cracking zone of the bell river complex host primary liquid vapor halite inclusions these inclusions are interpreted to be samples of the deep seated equivalent to the vms ore hosted hydrothermal fluid described above microthermometry indicates that these inclusions trapped a high temperature brine tt 373 44 c 1 n 92 38 2 1 9 wt nacl equiv 1 n 92 we interpret this brine to be a phase separated product of modified model seawater 3 2 wt nacl an exsolved magmatic fluid or a combination thereof deep within the hydrothermal system at 650 to 670 c and a near lithostatic pressure of 90 mpa phase separation and subsequent convection lowered the temperature of the brine prior to its entrapment within the hydrothermal cracking zone the occurrence of high temperature brine overlain by lower temperature salinity fluid suggests a two cell convection model consistent with metal mass balance calculations for the south limb the high salinity of the ore hosted fluid inclusions indicates two possibilities 1 a significant amount of brine was incorporated into the upper cell and mixed with heated seawater during convection 2 archean seawater itself was very saline and of variable salinity with the cooling of the bell river complex lower temperature fluids dominantly of seawater origin circulated deep within the hydrothermal system modified by water rock interaction yet not phase separated these fluids sealed off the remnant permeability of the fracture network of the hydrothermal cracking zone and were locally trapped as secondary liquid vapor fluid inclusions homogenization temperature th 242 17 c 9 1 1 6 wt nacl equiv 1 n 14 hosted within the bell river complex quartz epidote vein material post and or waning stage vms hydrothermal activity is evident from the presence of quartz epidote veins crosscutting wabassee group hanging wall rocks microthermometry on quartz hosted primary liquid vapor fluid inclusions suggests that this activity occurred at relatively low temperatures th 76 177 c n 212 over a wide range of salinity 6 0 32 4 wt nacl cacl2 equiv n 212 and with a high apparent cacl2 content xnacl 0 06 these fluid inclusion data illustrate the importance of subsea floor chemical and physical processes directly related to metal transport and deposition in vms systems in particular phase separation deep within the hydrothermal system is interpreted as a key process for generating saline brines capable of forming significant ore deposits

agents of low temperature ocean crust alteration 18o and87sr 86sr isotopic data from smectites calcites and whole rocks together with published isotopic age determinations alkali element concentration data and petrographic observations suggest a sequential model of ocean floor alteration the early stage lasts about 3 m y and is characterized by palagonite and smectite formation and solutions with a large basaltic component increasing with temperature which varies from 15 to 80 c at dsdp site 418a most carbonates are depositedafter this stage from solutions with a negligible basaltic sr component and temperatures of 15 to 40 c water of seawater sr and o isotopic composition is shown to percolate to at least 500 m into the basaltic basement no evidence was found for continuing exchange of strontium or oxygen after 3 m y

the ibero armorican arc a collision effect against an irregular continent the ibero armorican arc is the main variscan macrostructure in western europe although it was recognized in the 1920s its genesis is still debatable and the proposed models for its generation questionable however even if some doubts persist it seems that most agree on the general geodynamic evolution of this virgation in both branches in the middle to late devonian iberia was deformed by a sinistral transpressive regime while in the northern branch thrusting events were predominant in the carboniferous a dextral transpression begins to predominate in the armorican branch while the southern branch was deformed by southward thrusting in an attempt to correlate these events we propose that during the late devonian a cantabrian indentor moved northward producing the oblique closure of the southern part of the rheic ocean and an almost orthogonal closure in central europe in the carboniferous the collision with the irregular margin of laurasia induced a rotation of the indentor the intracontinental deformation was then achieved by dextral transpression in the northern branch and thrusting in the southern one

intensification of the oxygen minimum zone in the northeast pacific off vancouver island during the last deglaciation ventilation and or export production 1 the oxygen minimum zone omz off vancouver island was more oxygen depleted relative to modern conditions during the allerod 13 5 to 12 6 calendar kyr and again from 11 to 10 kyr the timing of omz intensification is similar to that seen throughout the north pacific although the onset appears to have been delayed by 1500 years off vancouver island radiocarbon dating of coeval benthic and planktonic foraminifera shows that between 16 0 and 12 6 kyr the age contrast between surface and intermediate waters 920 m depth off vancouver island was similar to or slightly less than that today there is no evidence of an increased age difference i e decreased ventilation during the deglaciation particularly during the allerod however sedimentary marine organic carbon concentration and mass accumulation rate increased substantially in the allerod suggesting that increased organic matter export was the principal cause of late pleistocene omz intensification off vancouver island

geochemical characteristics of chilean upwelling sediments at 36 s abstract we examined the cycling of c s fe and the trace elements te ag cd mo mn re and se in chilean upwelling sediments from water depths of 127 2744 m at 36 s the sediments are clay rich with moderate total organic carbon toc and low biogenic caco3 contents for the shallow site within oxygen minimum zone omz which shows some thioploca biomass highest observed toc contents correspond to highest productivity induced toc flux and or enhanced preservation under o2 deficient conditions pyrite formation may be restricted by the concurrent presence of elemental s in thioploca and or the availability of reactive iron in the other sediments 370 m water depth pyrite formation is strongly restricted due to the low availability of metabolizable toc for sulfate reduction calculations of the degree of bacterially mediated remineralization suggest that more nitrogen than toc was remineralized by sulfate reduction than expected from redfield c n relationship manganese is significantly depleted due to reductive dissolution of mn hydr oxides within all sediments mo is only significantly enriched vs the lithogenic background in the shallow core implying anoxic conditions contents of re and mo as well as re mo ratios indicate suboxic conditions for the other cores cd and re contents decrease with increasing water depth reflecting decreasing reducing conditions in contrast authigenic ag contents increase with water depth suggesting enrichment controlled by seawater availability and or opaline input and not redox conditions elevated se contents in all cores may be either due to bio detrital input or diffusion from seawater accumulation rates of toc ts and te off chile are in the same order as those from the gulf of california and lower than those off peru distinct seasonality in upwelling and dilution of chilean sediments with terrigenous material lead to rather low metabolizable toc contents and lower te trapping capacity

hydrogen isotope systematics of submarine basalts the d h ratios and water contents in fresh submarine basalts from the mid atlantic ridge the east pacific rise and hawaii indicate that the primary d h ratios of many submarine lavas have been altered by processes including 1 outgassing 2 addition of seawater at magmatic temperature and 3 low temperature hydration of glass decreases in d and h2o from exteriors to interiors of pillows are explained by outgassing of water whereas inverse relations between d and h2o in basalts from the galapagos rise and the famous area are attributed to outgassing of ch4 and h2 a good correlation between d values and h2o is observed in a suite of submarine tholeiites dredged from the kilauea east rift zone where seawater added directly to the magma affected only the isotopic compositions of hydrogen and argon analyses of some glassy rims indicate that the outer millimeter of the glass can undergo lowtemperature hydration by hydroxyl groups having d values as low as 100 d values vary with h2o contents of subaerial transitional basalts from molokai hawaii and subaerial alkali basalts from the society islands indicating that the primary d values were similar to those of submarine lavas extrapolations to possible unaltered d values and h2o contents indicate that the primary d values of most thoteiite and alkali basalts are near 80 5 the weight percentages of water are variable 0 15 0 35 for mor tholeiites about 0 25 for hawaiian tholeiites and up to 1 1 for alkali basalts the primary d values of 80 for most basalts are comparable to those measured for deep seated phlogopites these results indicate that hydrogen in marked contrast to other elements such as sr nd pb and o has a uniform isotopic composition in the mantle this uniformity is best explained by the presence of a homogeneous reservoir of hydrogen that has existed in the mantle since the very early history of the earth

4 transpressional tectonics lower crust decoupling and intrusion of deep mafic sills a model for the unusual metallogenesis of sw iberia abstract sw iberia is interpreted as an accretionary magmatic belt resulting from the collision between the south portuguese zone and the autochthonous iberian terrane in variscan times 350 to 330 ma in the south portuguese zone pull apart basins were filled with a thick sequence of siliciclastic sediments and bimodal volcanic rocks that host the giant massive sulphides of the iberian pyrite belt massive sulphides precipitated in highly efficient geochemical traps where metal rich but sulphur depleted fluids of dominant basinal derivation mixed with sulphide rich modified seawater massive sulphides formed either in porous reactive volcanic rocks by sub seafloor replacement or in dark shale by replacement of mud or by exhalation within confined basins with high biogenic activity crustal thinning and magma intrusion were responsible for thermal maturation and dehydration of sedimentary rocks while magmatic fluids probably had a minor influence on the observed geochemical signatures the ossa morena zone was a coeval calc alkaline magmatic arc it was the site for unusual mineralization particularly magmatic ni cu and hydrothermal fe oxide cu au ores iocg most magmatism and mineralization took place at local extensional zones along first order strike slip faults and thrusts the source of magmas and iocg and ni cu deposits probably lay in a large mafic ultramafic layered complex intruded along a detachment at the boundary between the upper and lower crust here juvenile melts extensively interacted with low grade metamorphic rocks inducing widespread anatexis magma contamination and further exsolution of hydrothermal fluids hypersaline fluids 18 o fluid 5 4 to 12 were focused upward into thrusts and faults leading to early magnetite mineralization associated with a high temperature 500 c albite actinolite salite alteration and subsequent copper gold bearing vein mineralization at somewhat lower temperatures assimilation of sediments by magmas led in turn to the formation of immiscible sulphide and silicate melts that accumulated in the footwall of the layered igneous complex further injection of both basic and sulphide rich magmas into the upper crust led to the formation of ni cu rich breccia pipes younger 330 to 280 ma peraluminous granitoids probably reflect the slow ascent of relatively dry and viscous magmas formed by contact anatexis these granitoids have w sn and pb zn related mineralization that also shows geochemical evidence of major mantle crust interaction late epithermal hg cu sb and pb zn ag mineralization was driven by convective hydrothermal cells resulting from the high geothermal gradients that were set up in the zone by intrusion of the layered igneous complex in all cases most of the sulphur seems to have been derived from leaching of the host sedimentary rocks 34 s 7 to 20 with only limited mixing with sulphur of magmatic derivation the metallogenic characteristics of the two terranes are quite different in the ossa morena zone juvenile magmatism played a major role as the source of metals and controlled the styles of mineralization in the south portuguese zone magmas only acted as heat sources but seem to have had no major influence as sources of metals and fluids which are dominated by crustal signatures most of the magmatic and tectonic features related to the variscan subduction and collision seem to be masked by those resulting from transpressional deformation and deep mafic intrusion which led to the development of a metallogenic belt with little resemblance to other accretionary magmatic arcs

alteration and mineralization of an oceanic forearc and the ophiolite ocean crust analogy mineralogical chemical and isotopic o c s and sr analyses were performed on minerals and bulk rocks from a forearc basement section to understand alteration processes and compare with mid ocean ridges mor and ophiolites ocean drilling program hole 786b in the izu bonin forearc penetrates 103 m of sediment and 725 m into volcanic flows breccias and basal dikes the rocks comprise boninites and andesites to rhyolites most of the section was affected by low temperature 100 c seawater alteration with temperatures increasing downward the rocks are partly 5 25 altered to smectite fe oxyhydroxide calcite and phillipsite and exhibit gains of k rb and p loss of ca variable changes in si na mg fe sr and y and elevated 18o and 87sr 86sr higher temperatures 150 c in the basal dikes below 750 m led to more intense alteration and formation of chlorite smectite corrensite albite k feldspar and quartz chlorite a 5 m thick hydrothermally altered and pyritized zone at 815 m in the basal dikes reacted with mixtures of seawater and hydrothermal fluids to mg chlorite albite and pyrite and gained mg and s and lost si and ca focused flow of hydrothermal fluids produced serialization halos na k sericite quartz pyrophyllite k feldspar and pyrite along quartz veins at temperatures of 200 250 c high 87sr 86sr ratios of chloritized 0 7055 and sericitized 0 7065 rocks indicate involvement of seawater via mixing with hydrothermal fluids low 34s of sulfide 2 to 5 5 and sulfate 12 5 are consistent with input of magmatic so2 into hydrothermal fluids and disproportionation to sulfide and sulfate alteration processes were generally similar to those at mors but the arc section is more intensively altered in part because of the presence of abundant glassy rocks and mafic phases the increase in alteration grade below 750 m and the mineralization in the basal dikes are analogous to changes that occur near the base of the volcanic section in mor and the troodos ophiolite

distinctive features of late palaeozoic massive sulphide deposits in south china abstract more than 20 sediment hosted massive sulphide deposits occur in late palaeozoic basins in south china these deposits are accompanied by a certain amount of volcanic rocks in the host sequence and are economically important for their cu pb zn au and ag reserves the deposits and their host strata were commonly intruded by mesozoic granitoids remobilisation of sedimentary ores and magmatic hydrothermal overprinting processes resulted in the coexistence of massive sulphides with vein skarn and porphyry type orebodies in the same region or within a single deposit the ore containing basins occur in different tectonic settings the lower yangtze basin occurs on a passive continental margin where the deposits are high in cu and au with minor pb and zn and recoverable ag co and mo the ores have a lower concentration of radiogenic lead and 34s values close to zero fluid inclusions are highly saline and na rich fluids and metals of the lower yangtze region are interpreted to have been derived essentially from deep sources including the precambrian basement by contrast basins of the nanling region formed in an intracontinental setting developed on a folded caledonian basement these deposits are higher in pb zn sn and w as well as cu with recoverable ag sb hg u bi tl and mo the ores are characterised by a higher concentration of radiogenic lead and a wide variation of 34s composition fluid inclusions have lower salinities and higher k na ratios fluids are considered to have been sourced substantially from seawater by convection metals for the nanling deposits were essentially derived from the caledonian basement by leaching the contrast in ore composition between these two regions appears to have been controlled by differences in basement composition of the ore forming basins

ore deposit types and tectonic evolution of the iberian pyrite belt from transtensional basins and magmatism to transpression and inversion tectonics abstract a new interpretation of the structural evolution of the iberian pyrite belt ipb and volcanogenic massive sulfide mineralization vms is presented in this work based on a review of the ore deposit types the analysis of the hosting volcanic sequences and the tectonic evolution the vms deposits of the ipb are hosted by volcanic and siliciclastic rocks four main volcano sedimentary sequences vsc from vsc0 to vsc3 have been assumed the main deposits being located in the vsc0 and at the top of the vsc2 we have defined three main sectors oriented approximately e w and hosting the vms deposits in the northern sector which is mostly located in spain graben basins and local pull aparts are the main structures in this sector two belts can be distinguished the deposits being located at the top of the vsc2 felsic volcanism rio tinto type ipb deposits in the central sector both in spain and portugal half graben basins are the most common structures and the deposits are mostly located in the vsc0 andesitic volcanic sedimentary sequence tharsis type ipb deposits in the southern sector which is only located in portugal a graben basin with a pull apart is again the main structure and the deposits are located in black slates and at the top of a felsic volcanism strunian in age vsc0 the deposits located in graben basin with a pull apart are essentially felsic volcanic hosted with some siliciclastic material mostly black shales by contrast those located in half graben basins are mainly hosted by black shales with minor amounts of andesitic rocks the tectonic evolution shows that as a result of a counterclockwise rotation of the stress axes the formation of the ipb and the associated ore deposits took place during several episodes from transtension with the development of both graben with pull aparts and half graben basins through left lateral e w shearing to transpression at the beginning of the transtensional process several extensional roughly e w trending faults that developed graben and half graben basins were generated and the first volcanic andesite rhyolite rocks vsc0 formed the tharsis type deposits mainly hosted by black slates with some volcanic rocks were formed in the central sector while the neves corvo type deposit hosted by black slates and felsic volcanism formed in the southern one after a period characterized by barren mafic volcanism vsc1 a sinistral shear affected the previous fractures due to the stress axis rotation and felsic crustal volcanism started vsc2 rhyolites and dacites were particularly abundant in two graben basins which developed rollovers in pull apart zones forming the rio tinto type deposits in the northern sector the thermal increase associated with vsc0 and vsc2 gave rise to the development of crustal scale hydrothermal convective cells which generated both types of deposits after a barren vsc3 felsic volcanism subsequently during the variscan transpressional phase the e w extensional faults were reactivated as reverse faults affecting the volcanic sequence vsc0 to vsc3 as well as the interbedded sedimentary rocks mostly black shales as has been recognized at the rio tinto deposit buttressing must have played a significant role in the geometry of inverted structures and the vms ores were intensely recrystallized it should be emphasized that this new regional geological model for the ipb is an approach to provide a better insight into vms deposits and could be a key point for further studies providing a new tool to improve knowledge of the vms mineralizations and exploration guidelines elsewhere in the ipb

geometry and genesis of feeder zones of massive sulphide deposits constraints from the rio tinto ore deposit spain vein related data have been collected around the giant rio tinto orebody in southern spain within the root zones of the massive sulphide deposits here we report the main results of this study concerning the geometry of the stockwork and the conditions of formation although field and thin section studies have shown that a wide range of vein configurations exist from micro cracks fluid inclusion planes to large paleo flow channels two groups seem to dominate the first corresponds to small constricted micro cracks and capillary flow channels now mainly filled with quartz whereas the veins of the second group have large widths are continuous over several meters and are filled with quartz and sulphides most are tension veins and only very few quartz tends to post date the quartz dominated veins quartz pyrite the vein thickness and spacing distribution is modal rather than logarithmic and their densities are not fractal but are characterized by a poisson distribution from the immediate sub surface zone to more than 100 m below the base of the massive sulphide deposits most hydrothermal quartz sulphide stockwork veins are sub parallel to the base of the massive sulphide deposit the assumption that the base of this deposit corresponds to a paleo horizontal plane implies that most veins were sub horizontal this is particularly evident for small veins but the larger ones can be strongly oblique to the base of the deposit the hydrothermal fluids that generated the massive sulphide deposits and underlying stockworks were very saline and probably underwent sub or super critical phase separation in the root zones of the system this phase separation was the probable mechanism producing the periodic over pressures of at least 20 mpa that were necessary to generate the sub horizontal veins of the stockworks

no slab derived co2 in mariana trough back arc basalts implications for carbon subduction and for temporary storage of co2 beneath slow spreading ridges the southern mariana trough is particularly well suited to study mass balance in subduction zones because the flux of material recycled from the subducted slab has been shown to diminish to negligible levels in the southernmost part of the area we present new he and ar concentration and isotopic data for 16 back arc basaltic glasses and combine these with previously published co2 and h2o concentration and 13c data to explore the recycling of carbon and light noble gases in the mariana back arc degassing has affected all samples and is particularly extensive in more water rich samples i e those containing the largest recycled component the degassing history features three stages 1 deep degassing which commenced when the melt reached saturation of co2 and noble gases in the mantle 2 preeruptive degassing during storage in the crust mantle transition zone which involved addition of extraneous co2 to the vapor phase and 3 eruption co2 released during stage 1 was at least partially incorporated into wall rock and subsequently remobilized during stage 2 degassing of later magma batches reconstructed parental values for 3he 4he 13c co2 3he and co2 40ar are indistinguishable from those of mid ocean ridge basalt this implies that there is negligible recycling of subducted carbon helium or argon into the source of mariana trough basalt

explanation for many of the unusual features of the massive sulfide deposits of the iberian pyrite belt newly published fluid inclusion data from quartz in stockwork veins beneath seven massive sulfide lenses in the iberian pyrite belt suggest that the lenses were formed from fluids that on reaching the sea reversed buoyancy and ponded in basins sulfides quenched in the resulting brine pool would have settled to form a sulfide mud this process provides a relatively efficient trapping mechanism for metal in the fluids and effectively excludes ambient seawater accounting for the deposits tending to have the characteristics of large size sheet like form absence of relict chimney structures and a mineral content characterized by pyrite arsenopyrite and absence or scarcity of barite marcasite and fe oxides if total s was less than total metals in the stockwork fluids some or all of the more soluble zn and pb could have been swept from the basin at the overflow accounting for the variable but generally low zn and pb contents of the ores the lack of sedimentary source for the high salinities implicates magmatic intrusions possibly similar to those related to sn w mineralization

the impact of sediment provenance on barium based productivity estimates abstract biogenic barium in marine sediments has been suggested to be a reliable proxy of export productivity from the surface ocean and algorithms have been developed to link these properties however problems arise when the proposed algorithms are applied to predominantly terrigenous sediments a major source of error is incorrect estimates of the terrigenous ba al ratio in normative calculations of the amount of biogenic barium in the sediment compared to an often used global average ba al ratio much better results can be obtained by estimating the terrigenous ba al ratio from exponential regression of the ba al ratios of surface sediments obtained from continental slope transects this method has been applied to surface sediments from the chilean continental slope the calculated regional terrigenous ba al ratios could be verified with purely terrigenous samples from chilean rivers the resulting accumulation rates of biogenic barium on the chilean continental slope reliably reproduce the regional pattern of primary productivity in the southern peru chile current indicating the potential of biogenic barium as a useful paleo productivity proxy

brine pool deposition for the zn pb cu massive sulphide deposits of the bathurst mining camp new brunswick canada i comparisons with the iberian pyrite belt abstract the ordovician zn pb cu massive sulphide ore deposits of the bathurst mining camp share many features with those of the devonian carboniferous iberian pyrite belt particularly the tendency to large size tonnage and metal content shape as far as can be determined after allowing for deformation metal content particularly fe cu pb zn and sn mineral assemblages pyrite arsenopyrite pyrrhotite and lack or rarity of sulphates sulphide textures particularly framboidal pyrite lack of chimney structures and rubble mounds irregular metal or mineral zoning and the low degree of zone refining compared to hokuroku ores the major differences between the provinces are the lack of vent complexes and the presence of sn cu ores in the iberian pyrite belt there are also similarities in the geological setting of the two camps both lie within continental terranes undergoing arc continent and continent continent collision and in each case massive sulphide mineralisation followed ophiolite obduction the ore deposits are associated with bimodal volcanic rocks derived from morb and continental crust and marine shales and mineralisation was locally accompanied or followed by deposition of iron formations fluid inclusion data from veins in stockworks from at least six of the iberian massive sulphide deposits point to sulphide deposition having taken place in basins containing mostly spent saline ore forming fluids brine pools and it is suggested that most of the major features of the bathurst deposits can be explained by similar processes the proposed model is largely independent of ocean sulphate and o 2 content whereas low values of each are requisites for the current spreading plume model of sulphide deposition in the bathurst camp

authigenic cadmium enrichments in suboxic sediments precipitation and postdepositional mobility the postdepositional mobility of cd and u has been investigated in north atlantic turbidites in order to validate their utility as proxies of paleo organic carbon fluxes in this region pelagic sediments are interspersed with relatively organic rich turbidites following instantaneous emplacement of turbidite units an oxidation front progressively migrated downwards into the suboxic turbidite thereby leading to redistribution of authigenic phases according to their affinity to different redox conditions authigenic cd concentrations show a large peak at the redox boundary and are significantly lower in the oxidized portion than in the deeper unoxidized part of the turbidite this distribution indicates that cd has been continuously remobilized by the oxidation front thereby suggesting high sensitivity of the cd species to the redox state and an efficient immobilization mechanism for cd under reducing conditions we propose the precipitation of cds as a plausible mechanism for removal of cd in reducing sediments rather than adsorption onto mineral surfaces this proposal is consistent with porewater data indicating diffusion of cd toward and uptake by suboxic sediments solubility calculations suggest that precipitation of cds may occur in suboxic sediments in the presence of trace levels of h2s below routine detection limits there is no evidence for release of cd or u back into seawater upon oxidation of reducing sediments the strong coupling between precipitation of authigenic cd and u and the early diagenetic degradation of organic carbon offers the potential of reconstructing paleo productivity using records of cd and u however postdepositional redistribution of authigenic cd and u may significantly alter records of authigenic cd and u thereby rendering paleo productivity reconstructions uncertain we propose that the cd u authigenic ratio may provide a qualitative indicator to assess the relative role of steady state incorporation relative to transient burn down enrichments

water depth and diagenetic constraints on the use of barium as a palaeoproductivity indicator sediments underneath the high productivity areas of the coastal upwclling and equatorial divergence zones in the pacific and indian oceans are enriched in barium and on this basis the barium content of the sediments has long been suggested as a potential palaeoproductivity indicator analyses of sediments from the peru margin corroborate the pattern of enhanced barium accumulation in areas of high primary productivity in the deep ocean but also show that this pattern cannot be extended to shallow water deposits sediments from the peru shelf lack any barium enrichment whereas this element is significantly enriched in slope and basinal deposits in water columns deeper than 2000 m this depth effect is further illustrated at site 682 located in the rapidly subsiding lima basin the quaternary sequence deposited at water depths 3000 m is enriched in organic carbon opal and biogenic barium the miocene sediments although deposited under highly productive waters associated with a coastal upwclling centre do not show an enrichment in the barium record corresponding to the very high organic carbon and opal levels a pattern that is consistent with deposition in shallow basins in addition to the effect of water depth on the barium distribution overprinting of primary signals can be observed in sediments from upwclling areas undergoing strong anoxic diagenesis microcrystalline barite is partly dissolved in intervals depleted in interstitial sulphate as shown for sediments from the peru margin dissolution of barite in sulphate depleted intervals of deep water sections leads to high barium concentrations near the termination of the sulphate reducing zone where downward sulphate and upward barium diffusion foster local barite precipitation in diagenetic fronts the barium distribution in sedimentary oxic and suboxic environments at deep water depositional sites has a high potential as a palaeoproductivity indicator however barium accumulation as a proxy for ocean fertility should be used with caution in areas of varying water depths and in anoxic diagenetic environments where sulphate depletion undcrsatur ates the interstitial waters with respect to barite

a new 3d geological model and interpretation of structural evolution of the world class rio tinto vms deposit iberian pyrite belt spain abstract a new 3d geological model and interpretation of structural evolution of the rio tinto world class vms deposit are presented in this work the rio tinto volcanogenic massive sulfide vms deposit is located in the spanish segment of the iberian pyrite belt and is hosted by felsic porphyritic volcanic rocks and tuffs computer generated 3d modeling of the different orebodies and host rocks has been carried out using data from around 3000 drill core logs allowing us to build 93 cross sections and 6 plants both 50 m spacing this has enabled us to recognize the geometry and relationships between the mineralization and the earliest carboniferous transtensional tectonics through the development of an extensional pull apart basin with two sub basins separated by the nw se trending eduardo fault the sub basins cerro colorado and san dionisio were limited by two e w strike slip faults the northern and southern faults and bounded in the east and west by the nw se trending nerva and western faults respectively the generated pull apart basin was first filled by a basaltic magmatism of mantle origin and later following the deposition of the intermediate complex sedimentary unit by rhyodacitic volcanic rocks of crustal origin the evolution of the subsiding basins caused the development of an e w oriented rollover anticline that affected these filling rocks as a result of a counterclockwise rotation of the stress axes the primitive pull apart basin evolved into a basin affected by e w transtensional sinistral shearing its northern and southern limits were favorable areas for increased hydrothermal fluid flow which gave way to the huge concentration of vms mineralization located near the limits the northern and to a lesser degree the southern extensional faults thus become channel areas for feeding and discharging of the vms and stockwork ores the main mineralizing period was related to this stage subsequently during the variscan transpressional phase the e w extensional faults were reactivated as inverse faults affecting the volcanic sequence of mafic to felsic composition and the intermediate complex sedimentary unit fault propagation folds developed above these faults affecting the massive sulfides the transition series and the culm flysch sediments with buttressing playing a significant role in the geometry of tectonically inverted structures the vms mineralization and cupriferous stockworks were folded and dismembered from the original conduits in the volcanic series and a dextral reactivation of the nw se trending faults also developed finally it should be emphasized that this new 3d geological model is an approach to provide a better insight into the 3d structure of the world class vms rio tinto deposit and could be a key point for further studies providing a new tool to increase knowledge of the vms mineralizations and exploration guidelines elsewhere in the ipb

are early cretaceous environmental changes recorded in deposits of the western part of the silesian nappe a geochemical approach abstract the organic matter om rich relatively monotonous sequence of upper barremian albian deposits in the western part of the silesian nappe in the polish outer carpathians was investigated using geochemical proxies to show environmental changes the amounts of organic carbon 0 4 4 32 wt of toc co vary with the concentration of s and or redox sensitive trace elements rste mo u co v as kerogen is present as type iii and mixed type ii iii maceral assemblages consist of vitrinite inertinite and liptinite the carbon isotopic composition of the organic matter 13 c org varies between 25 38 and 21 31 with an outlier at 15 14 during the early cretaceous the proto silesian basin was the site of om accumulation in a detrital oceanic anoxic event as a result of increased sedimentation rates of terrestrial organic matter runoff of terrestrial organic matter was accompanied by the production of plankton on an occasional basis the marine matter contribution is inferred from occurrence of siliceous microfauna the domination of short chain n alkanes the distribution of sterane and prevalence of cholestane and enrichment in nutrient elements p 2 o 5 ba ag cd the bottom waters could have been dysoxic to anoxic with a mid water oxygen minimum zone omz developed owing to the oxidation of organic matter anoxia is inferred from the lamination pyritization patterns rste concentration and low pr ph and c 23 t c 30 h ratios intervals enriched in toc and rste in the ve ovice formation record pulses of marine productivity preceded by volcanic teshenite and hydrothermal activity they are referable to the following episodes the taxy barremian aptian early aptian selli fallot and paquier during the late aptian and at the aptian albian boundary the initiation of turbidite deposition during the albian led to bottom ventilation the lhoty formation records the late albian toolebuc episode marked by a toc peak which resulted from the detrital flux acidic solution was responsible for reducing conditions in the sediment

generation of layering in the lower stratosphere by a breaking rossby wave 1 an airborne ozone lidar has been used to observe layering in the ozone field between 350 and 400 k northward of the subtropical jet stream an ozone poor layer between 370 and 400 k was observed over western europe on 21 april 1999 on this day a rossby wave was observed to be breaking over the eastern north atlantic and western europe with both poleward and equatorward components we propose that the low ozone at 400 k was caused by a poleward breaking rossby wave stretching from spain to the south coast of britain isentropic back trajectory calculations suggest a tropical upper tropospheric origin for the air within this wave over north america we suggest that rossby waves generate layering in the lower stratosphere because of vertical gradients in the background wind fields which govern the growth in amplitude and breaking characteristics of the waves

the cu stockwork and massive sulfide ore of the feitais volcanic hosted massive sulfide deposit aljustrel iberian pyrite belt portugal a mineralogical fluid inclusion and isotopic investigation the variscan feitais volcanic hosted massive sulfide deposit in the aljustrel district of the iberian pyrite belt consists of 55 million metric tons of zn pb cu massive sulfide overlying a cu rich stockwork the massive ore is overlain by up to 30 m of feldspar phyric rhyolitic volcaniclastic rock and locally by a jasper and or chert layer up to 15 m thick the massive sulfide orebody consists dominantly of pyrite sphalerite galena chalcopyrite tetrahedrite tennantite arsenopyrite and bournonite together with minor quartz chlorite sericite carbonate and barite the orebody is up to 100 m thick and is underlain by a tabular alteration zone of chloritedominated locally silicified felsic volcanic rock the upper 30 to 60 m of which contains chalcopyrite quartzchlorite sericite carbonate bearing stockwork vein let s that prior to deformation were at a shallow angle to the base of the massive orebody chloritized footwall rocks extend up to 20 m below the cu stockwork zone and are underlain by up to 50 m of quartz sericite pyrite altered rhyolitic rock the stockwork veins also contain pyrite tetrahedrite tennantite sphalerite and arsenopyrite pyrite both in stockwork and massive ore locally displays partly recrystallized framboidal reniform and cellular textures two generations of quartz q1 and q2 and carbonate in the stockwork veins contain primary in growth zones and pseudosecondary fluid inclusions with homogenization temperatures of 270 to 315 c and salinities of 2 2 to 8 1 wt percent nacl equiv the 34s cdt values of massive and stockwork ores range from 15 4 to 4 7 mean 2 8 and 11 2 to 11 9 mean 0 4 per mil respectively the lowest values from colloformtextured pyrite with no evidence of oxidation of sulfide sulfur during mineralization the most negative values indicate an origin by biogenic reduction of seawater sulfate the 13c pdb values for carbonates 7 5 to 13 7 and 9 3 to 14 3 per mil in massive and stockwork ore respectively indicate an origin mostly by oxidation of methane derived from organic matter in underlying sedimentary rocks and possibly a contribution of magmatic carbon there are no significant lateral or vertical variations in s isotope values in sulfides or c o isotope values in carbonates either in massive or stockwork ore the 18o smow values for quartz in stockwork and massive sulfide are 11 6 to 13 9 and 16 7 to 17 9 per mil respectively coexisting and texturally contemporaneous carbonate and quartz in stockwork veins are not in isotopic equilibrium indicating that the c o isotope values may have been reset the 18o values of fluid calculated to be in equilibrium with quartz at fluid inclusion homogenization temperatures are 4 2 to 5 2 per mil barite from the hanging wall and massive ore yields 34s values 21 9 27 9 equal to or slightly higher than those of coeval seawater 87sr 86sr ratios 0 708438 0 709063 are slightly more radiogenic than those of coeval seawater 0 7080 0 7085 and much more radiogenic than those of coeval volcanic rocks 0 703304 0 706642 probably representing mixtures between seawater sr and radiogenic sr in fluids sourced in the crustal pile deposition of the massive sulfide on the sea floor is suggested by its stratiform nature the stronger alteration of footwall relative to hanging wall rocks the stockwork system terminating sharply at the base of the massive sulfide the presence of sedimentary like textures in the massive sulfide the absence of replacement fronts and the presence of framboidal and other sea floor depositional textures indicative of fluid quenching the sheetlike form lack of rubble mounds and chimneys scarcity of barite reduced mineral assemblage and metal zoning distinguish feitais from kuroko type deposits it shares most of the characteristics of those iberian pyrite belt deposits for which a brine pool origin has been proposed based on fluid inclusion data

suboxic trace metal geochemistry in the eastern tropical north pacific abstract we analyzed al ti fe mn cu ba cd u mo v and re in water column settling particulate and sediment 0 to 22 cm samples from the intense oxygen minimum zone omz of the eastern tropical north pacific near mazatlan mexico the goal was to determine how the geochemistry of these elements was influenced by suboxic water column conditions and whether the sediments have a unique suboxic geochemical signature the water column was characterized by a mn maximum reaching 8 nmol kg 1 at 400 m concentrations of cu ba cd mo re u and v were unaffected by the low o2 conditions and were comparable to those of the open ocean sinking particles were composed of lithogenic particles of detrital origin and nonlithogenic particles of biogenic origin al ti and fe were mostly at least 79 lithogenic about 75 of the mn was nonlithogenic significant amounts at least 58 of cu ba cd and mo were nonlithogenic sediment geochemistry varied across the continental shelf and slope cadmium u and re have prominent maxima centered at 310 m with 12 3 ppm 10 9 ppm and 68 3 ppb respectively at the core top high values of mo averaging 6 8 ppm and v averaging 90 ppm are seen in omz surface sediment additional down core enrichment occurs for all redox sensitive elements in the top 10 cm for u mo v and re surface sediments are a poor indicator of metal enrichment comparison of the nonlithogenic composition of sediments with sinking particles suggests that direct input of plankton material enriched in metals makes a significant contribution to the total composition especially for cd u and mo we evaluated re mo and cd u ratios as tracers for redox environments rhenium and mo concentrations and re mo ratios do not lead to consistent conclusions concurrent enrichments of re and mo are an indicator of an anoxic depositional environment in contrast high re mo ratios are an indicator of suboxic conditions cadmium is enriched in surface sediments while u has considerable down core enrichment the concentrations of cd and u and the cd u ratio do not follow patterns predicted from thermodynamics though the water column is suboxic these four redox sensitive elements indicate that the sediments are anoxic the implication for paleostudies is that a trace metal sediment signature that indicates anoxic conditions is not necessarily attributable to an anoxic water column

glacial interglacial variability in the eastern tropical north pacific oxygen minimum zone recorded by redox sensitive trace metals 1 changes in the intensity of the oxygen minimum zone omz in the eastern tropical north pacific over the past 140 kyr are recorded as enrichments and depletions of redox sensitive metals in sediments of two piston cores one within and one below the modern omz from the continental margin off mazatlan mexico 22 41 n 106 28 w concentrations of al 7 7 0 6 ti 0 37 0 03 fe 3 1 0 25 mn 320 31 ppm and ba 560 82 ppm in core nh15p within the omz at 420 m water depth were relatively constant over the last 110 kyr in contrast concentrations of cd 4 8 2 ppm cu 29 8 9 1 ppm u 9 1 3 7 ppm mo 12 1 5 0 ppm v 138 2 51 9 ppm and re 45 8 25 5 ppb were all at least 30 higher in interglacial stages compared to glacial stages concentrations of al 7 4 0 3 ti 0 35 0 03 fe 3 5 0 4 and mn 385 77 ppm in core nh22p below the omz at 2025 m water depth were comparable to those in core nh15p while concentrations of ba 1662 292 ppm were about a factor of three higher in contrast concentrations of cd 0 9 0 3 ppm u 6 6 0 9 ppm mo 3 2 1 2 ppm v 81 8 10 1 ppm and re 25 4 12 ppb were lower in sediments of comparable age than the concentrations of these same metals in the omz core and the differences in their concentrations over glacial interglacial cycles were less pronounced than those in shallower core comparison of the nonlithogenic fraction of metals in the sediments with their estimated contribution from plankton suggests that organic matter is probably the major source of cu ba and perhaps cd to the sediment whereas the indirect effects of organic carbon and low bottom water oxygen concentrations on sediment redox state appear to be more important controls on the distributions u re mo and v changes in the depth at which re and mo precipitated in the sediments and in the re mo ratio suggest that the redox state of the surface sediment and overlying water at both core depths varied over time re and mo removal depths were shallower and re mo ratios were lower at the omz site than in deeper water suggesting that a more reducing environment prevailed over time at the shallower site although the redox state of the waters and sediment at both sites varied over glacial interglacial cycles the omz likely was never anoxic in the last 140 kyr this variability in redox state could be attributed to changes in regional export productivity changes in ocean circulation or a combination of both processes a paleoproductivity reconstruction from biogenic ba data suggests that glacial productivity was considerable lower than it was during interglacial stages model results suggest that the oxygen penetration depth an indicator of sediment redox state changed less than 1 cm as a result of the change in productivity changes in oxygen penetration depth estimated from re and u removal depths are significantly larger suggesting that changes in ventilation are a more important control on sediment redox state overall trace metal results confirm the tight coupling between ocean circulation marine productivity and global change

barium accumulation in the arabian sea controls on barite preservation in marine sediments in this study a new sequential extraction technique is used to investigate the particulate barium ba phases in sediments from the arabian sea to determine the processes controlling ba accumulation in marine sediments the total solid phase ba concentration in arabian sea surface sediments increases with water depth from 200 ppm at 500 meters below sea surface mbss to 1000 ppm at 3000 mbss the sedimentary ba composition consists of three major fractions barite ba incorporated in aluminosilicates and ba associated with mn fe oxides accumulation of barite which is the most important ba fraction in sediments located below 2000 mbss increases gradually with water depth the ba al ratio of the terrigenous fraction varies significantly across the arabian basin as the result of differences in grain size and provenance of the terrigenous sediment ba associated with mn oxides is a relatively minor fraction compared with bulk ba concentrations and it only accumulates in well oxygenated sediments below the present day oxygen minimum zone the water depth dependent accumulation of barite in the arabian sea is not related to the continuous formation of barite in settling organic particles or ba scavenging by mn oxyhydroxides but is primarily controlled by differences in ba preservation upon deposition a good correlation between the barite saturation index and the barite accumulation rate in the upper 2000 m of the water column may indicate that the degree of barite saturation of the bottom water is the main environmental factor regulating the burial efficiency of barite organic matter degradation bioturbation diagenetic mn cycling and the crystallinity of the accumulating barite may play additional roles copyright 2001 elsevier science ltd

formation on the sea floor of the hellyer volcanogenic massive sulfide deposit new fluid inclusion data from the stockwork veins beneath the hellyer orebody a relatively undeformed late cambrian polymetallic volcanogenic massive sulfide deposit allow semiquantitative modeling of the behavior of the ore fluids on the sea floor and the manner of growth of the massive sulfide the earliest cool fluids may have been denser than seawater and ponded in a basin identified by sedimentological and structural studies subsequent vent fluids buoyant with respect to the brine pool and subsequently at higher temperature with respect to seawater mixed with the cooler brine during and after filling the basin to the level of its lowest outlet density inhomogeneities within the brine pool were reduced by double diffusive convection across the brine seawater interface and internal boundaries and mixing by currents within the brine pool estimates of likely temperatures and salinities in the brine pool for the first main mineralization stage avg 200 c 11 wt salinity assuming a steady or quasisteady state had been established and using volume fluxes similar to those observed in modern oceans indicate temperatures 100 c sulfides mostly pyrite sphalerite and galena precipitated from the vent fluids after mixing with cooler basin fluid settled from the gravity current to the basin floor a pattern that would have continued whether or not a true steady state was reached if the early fluids were buoyant in seawater they ponded after mixing forming a hybrid brine pool that would have required longer periods to homogenize at the peak temperature 300 c and volume flux the salinity of the vent fluids fell to 7 5 wt percent but the flow paths would have been maintained unless the brine pool had been drained at this time that part of the massive sulfide body over the vent the cu core grew by dilatational veining together with leaching cavity infilling replacement and recrystallization chalcopyrite was deposited both in the cu core and probably at the same time in a layer over the flanking massive sulfide in the final stage as temperature fell and salinity rose avg 250 c 11 wt salinity the fluid oxidation potential increased so that barite precipitation dominated resulting in a formation of a discontinuous barite rich cap over the massive sulfide the brine pool model explains several features of the hellyer ore that differ from those of the ores of the hokuroko basin namely the large metal content high zn cu ratio low aspect ratio absence of chimney fragments presence of mineral banding and high barite sulfur isotope values features seen in many other massive sulfide orebodies

the filon norte orebody tharsis iberian pyrite belt a proximal low temperature shale hosted massive sulphide in a thin skinned tectonic belt the filon norte orebody tharsis iberian pyrite belt is one of the largest pyrite rich massive sulphide deposits of the world the present structure of the mineralization consists of an internally complex low angle north dipping thrust system of variscan age there are three major tectonic units separated by thick fault zones each unit with its own lithologic and hydrothermal features they are internally organized in a hinterland dipping duplex sequence with high angle horses of competent rocks igneous and detritic rocks and massive sulphides bounded by phyllonites the mineralization is within the lower unit and is composed of several stacked sheets of massive sulphides and shales hosting a stockwork zone with no obvious zonation the intermediate unit is made up of pervasively ankeritized shales and basalts spilites here hydrothermal breccias are abundant the upper unit is the less hydrothermally altered one and consists of silicified dacites and a diabase sill the tectonic reconstruction suggests that the sequence is inverted and the altered igneous rocks were originally below the orebody carbon oxygen and sulphur isotopes in the massive sulphides and hydrothermal rocks as well as the mineral assemblage and the paragenetic succession suggest that the sulphide precipitation in the sea floor took place at a low temperature 150 c without indication at least in the exposed section of a high temperature copper rich event sporadic deep subsea floor boiling is probably responsible for the formation of hydrothermal breccias and the wide extension of the stockwork its co au enrichment is interpreted as being related with the superposition of some critical factors such as the relationship with black shales the low temperature of formation and the boiling of hydrothermal fluids the present configuration and thickness of the orebody is due to the tectonic stacking of a thin and extensive blanket 2 4 km2 of massive sulphides with low aspect ratio they were formed by poorly focused venting of hot modified seawater equilibrated with underlying rocks into the seafloor massive sulphide precipitation took place by hydrothermal fluid quenching bacteriogenic activity and particle settling in an unusual restricted euxinic and shallow basin brine pool with a low detritic input but with important hydrothermal activity related to synsedimentary extensional faulting resedimentation of sulphides seems to be of major importance and responsible for the observed well mixed proximal and distal facies the tectonic deformation is largely heterogeneous and has been mostly channelled along the phyllonitic tectonized shales deformation bands thus sedimentary and diagenetic textures are relatively well preserved outside the deformation bands in the massive sulphides superimposed variscan recrystallization is not very important and only some early textures are replaced by metamorphic tectonic ones the stockwork is much more deformed than the massive sulphides the deformation has a critical effect on the present morphology of the orebody and the distribution of the ore minerals this deposit is a typical example of the sheet like shale hosted anoxic low temperature and zn rich massive sulphides developed in a ensialic extensional basin

microthermometry and chemical composition of fluid inclusions from the mt chalmers volcanic hosted massive sulfide deposits central queensland australia implications for ore genesis mt chalmers is a mound style volcanic hosted massive sulfide vhms deposit in central queensland australia the ore lenses are hosted by rhyolitic volcanics and sedimentary rocks of early permian age the two ore lenses main lode and west lode consist of cu zn pb massive sulfide underlain by cu rich stringer mineralization textural and petrographic investigations of fluid inclusions indicate that primary type i inclusions up to 25 microns are found in quartz from the stringer mineralized zone and microthermometric studies of these inclusions yielded homogenization temperatures of 160 285 degrees c and salinities of 5 10 5 nacl equiv wt laser raman spectroscopic lrs analysis indicates the presence of co2 0 1 1 mol in the mt chalmers vhms systems semiquantitative sem wds microprobe analyses of fluid inclusion decrepitates indicate that the mt chalmers ore fluids were enriched in potassium and calcium but depleted in magnesium relative to seawater pixe microanalysis of fluid inclusions in quartz from the stringer zone also indicates a significant base metal concentration in these fluids cation composition and higher salinities relative to seawater suggest that recycled seawater cannot be the sole source of the ore fluids high base metal content and the presence of co2 in the fluid inclusions imply that magmatic input of ore metals copper in particular accompanying seawater leaching of the footwall volcanic pile is a distinct possibility in terms of fluid composition the k ca fe variation of the mt chalmers ore fluid is comparable with those of typical epithermal deposits e g thames new zealand and porphyry copper deposits bingham ut the cu zn fe 10 plot of the mt chalmers ore fluids indicates that there is significant copper in the system comparable to copper enrichment in a porphyry copper system the mt chalmers ore fluids also show similar copper content with the cu rich end member ore fluid composition of the mineralized stage 2b veins of the hellyer vhms deposit whereas the stage 2a veins of hellyer are more enriched in lead and zinc overall the ore fluids have a variable chemistry with a continuum of compositional data from vhms to epithermal porphyry style ore fluids shallow water emplacement 300 m for the vhms mineralization has been postulated for the mt chalmers deposit based on the presence of trace fossils in the footwall and hanging wall sedimentary rocks and volcanic facies studies however fluid inclusion studies do not rule out a moderate to deeper submarine environment as there is no fluid inclusion evidence of boiling at mt chalmers boiling of ore fluids would probably have occurred as in most epithermal systems if the ore fluid exhaled onto the seafloor under a shallow environment

isotope geochemistry tracks the maturation of submarine massive sulfide mounds iberian pyrite belt the massive sulfide deposits of the southern iberian pyrite belt ipb occur as shale hosted exhalative mounds or shallow sub seafloor replacive bodies that formed at the devonian carboniferous boundary in anoxic bottoms the geochemistry of the mineralization and the host shale from some of the major deposits including a detailed 50 m thick section through the migollas orebody shows a marked textural and vertical zonation that is also reflected in the chemical textural and isotopic variations of pyrite and carbonates pyrite evolves from primary framboids and colloform aggregates to late euhedral crystals which accompanies a redistribution of the contained base metals and grain coarsening sims analyses depict an extreme variability of 34s values from 42 3 to 4 4 with a gradual increase that is related to the textural maturation there is also a systematic rise in the 87sr 86sr ratios 0 70846 to 0 71354 13c 12 2 to 5 2 and 18o values 14 1 to 27 8 of the associated carbonates which evolve from early dolomite to late siderite this evolution evidences the maturation of the exhalative mineralization during mixing between two fluids modified seawater enriched in biogenically derived reduced sulfur and upflowing hydrothermal fluids early sulfides precipitated in the seawater mound interface towards the core of the mounds there was an increasing influence of deep fluids that modified the early mineral textures and the isotopic signatures this evolution is similar to that observed in modern submarine hydrothermal systems and confirms the importance of mound refining in the evolution of fossil exhalative mounds and the formation of economic ores

the pulpi gigantic geode almeria spain geology metal pollution microclimatology and conservation the discovery of the giant geode of pulpi almeria spain was considered as an important highlight in the geological heritage of spain projects developed for their conser vation were immediately initiated with legal figures of protection and tourist projects the geode has a tourist interest which must be tem pered by environmental restrictions limiting the public visits first results demonstrate that a continuous visit of two or three people for more than 10 min provokes the appearance of condensation and risks corrosion of the gypsum crystals in addition the electron microprobe analyses con firms 1 the hydrothermal phases of iron manganese in carbonated host rock 2 the presence of sulphides with fe zn pb ag sb cu hg as te se and 3 ba ca and sr sulphates with mercury traces the present proposal to label the geode and the mining environment as geological natural heritage is feasi ble although any tourist adaptation must not permit visits to the geode indoor and hg levels must be con trolled

the geochemistry of redox sensitive trace metals in sediments abstract we analyzed the redox sensitive elements v mo u re and cd in surface sediments from the northwest african margin the u s northwest margin and the arabian sea to determine their response under a range of redox conditions where oxygen penetrates 1 cm or less into the sediments mo and v diffuse to the overlying water as mn is reduced and remobilized authigenic enrichments of u re and cd are evident under these redox conditions with the onset of sulfate reduction all of the metals accumulate authigenically with re being by far the most enriched general trends in authigenic metal accumulation are described by calculating authigenic fluxes for the 3 main redox regimes oxic reducing where oxygen penetrates 1 cm and anoxic conditions using a simple diagenesis model and global estimates of organic carbon rain rate and bottom water oxygen concentrations we calculate the area of sediments below 1000 m water depth in which oxygen penetration is 1 cm to be 4 of the ocean floor we conclude that sediments where oxygen penetrates 1 cm release mn v and mo to seawater at rates of 140 260 60 150 and 5 10 of their respective riverine fluxes using the authigenic metal concentrations and accumulation rates from this work and other literature these sediments are sinks for re cd and u with burial fluxes of 70 140 30 80 and 20 40 respectively of their dissolved riverine inputs we modeled the sensitivity of the response of seawater re cd and v concentrations to changes in the area of reducing sediments where oxygen penetrates 1 cm our analysis suggests a negligible change in seawater re concentration whereas seawater concentrations of cd and v could have decreased and increased respectively by 5 10 over 20 kyr if the area of reducing sediments increased by a factor of 2 and by 10 20 if the area increased by a factor of 3 the concentration variations for a factor of 2 increase in the area of reducing sediments are at about the level of uncertainty of cd ca and v ca ratios observed in foraminifera shells over the last 40 kyr this implies that the area of reducing sediments in the ocean deeper than 1000 m 4 has not been greater than twice the present value in the recent past

giant pyritic base metal deposits the example of feitais aljustrel portugal detailed study of hanging wall rocks and alteration above the giant feitais orebody of aljustrel iberian pyrite belt portugal shows that cherts that constitute the immediate hanging wall to the sulfide deposit result from hydrothermal alteration of laterally equivalent fe and or mn rich jaspers textures geochemistry and lack of fossil radiolarians indicate that these jaspers are hydrothermal precipitates hydrothermal alteration of the jaspers took place concomitantly with sulfide precipitation through reaction with hot 150 c reduced fluids with replacement of hematite by magnetite pyrite and fe2 phyllosilicates on the basis of the above and considering also the results of previous studies on hydrothermal activity in the aljustrel volcanic rocks and sulfide ores we propose that sulfide precipitation may have taken place under a thin veneer of siliceous sediments present day massive sulfide formation in the guaymas basin and in the salton sea under hundreds of meters of sediments may be approximate analogues in the sense that the presence of a caprock reduces dispersion of black smoke and causes more efficient precipitation

helium 3 and deuterium in back arc basalts lau basin and the mariana trough samples of fresh basalt glass from the mariana trough and the lau basin were analyzed for their isotopic composition of water and helium in order to identify the sources of the volatiles in back arc basin basalts in the mariana trough basalts the concentration 0 64 2 1 wt and d h ratio d 46 to 32 of the water provide important evidence for a water rich component from the subducting lithosphere extrapolation to infinite water content gives an end member d h ratio of d 25 3he 4he ratios are in general similar to morb values 8 ra and indicate that mariana trough basalts represent a mixture of a morb type mantle and an alkali and water rich component from the descending slab in contrast the lau basin produces both hydrous 1 3 wt h2o and relatively anhydrous 0 12 0 35 wt basalts the d h ratio d 43 in the hydrous lau basin basalt resembles those of mariana trough lavas the low water contents 0 12 0 35 wt and morb like d h ratios d 63 to 70 in three of five lau basin samples show that the water rich component observed in all mariana trough lavas is absent in some lau basin lavas and not essential for the production of back arc basalts the high3he 4he ratio of rochambeau bank in the northern lau basin 11 ra confirms an earlier analysis by lupton and craig and provides evidence for an enriched mantle source region beneath the lau basin which is perhaps related to the high 3he samoan hotspot

zn pb cu massive sulfide deposits brine pool types occur in collisional orogens black smoker types occur in backarc and or arc basins volcanic hosted massive sulfide deposits of zn pb cu type were derived either from seawater dominated buoyant fluids that built mounds on the seafloor e g the ores of the hokuroku basin japan or from saline fluids that reversed buoyancy on mixing with seawater and filled basins on the seafloor e g several ores of the iberian pyrite belt and the mount read province in tasmania the hokuroku ores formed above subduction zones during protracted periods of regional extension but both the iberian pyrite belt and the mount read province formed under extensional stress during continent continent iberia or arc continent mount read collision and orogenesis in the iberian pyrite belt oblique convergence resulted in transcurrent faulting and this may also be the case for the mount read province transcurrent faulting may have allowed easy vertical access for the ore related magmas some of which were sourced in the asthenosphere as well as the blueschist and eclogitic facies emplaced in adjacent terrains and possibly also saline fluids exsolved from the magmas

late hercynian polymetallic vein type base metal mineralization in the iberian pyrite belt fluid inclusion and stable isotope geochemistry s o h cl late variscan vein type mineralization in the iberian pyrite belt related to the rejuvenation of pre existing fractures during late variscan extensional tectonism comprises pyrite chalcopyrite quartz galena sphalerite quartz stibnite arsenopyrite quartz pyrite quartz cassiterite scheelite fluorite galena sphalerite chalcopyrite and quartz manganese oxide mineral assemblages studies of fluid inclusions in quartz stibnite and barite as well as the sulfur isotopic compositions of stibnite galena and barite from three occurrences in the central part of the iberian pyrite belt reveal compelling evidence for there having been different sources of sulfur and depositional conditions quartz stibnite mineralization formed at temperatures of about 200 c from fluids which had undergone two phase separation during ascent antimony and sulfide are most probably derived by alteration of a deeper lying volcanic hosted massive sulfide mineralization as indicated by 34s signatures from 1 45 to 2 74 sub critical phase separation of the fluid caused extreme fractionation of chlorine isotopes 37cl between 1 8 and 3 2 which correlates with a fractionation of the cl br ratios the source of another high salinity fluid trapped in inclusions in late stage quartz from quartz stibnite veins remains unclear by contrast quartz galena veins derived sulfide and metals by alteration of a sedimentary source most likely shale hosted massive sulfides the 34s values in galena from the two study sites vary between 15 42 and 19 04 barite which is associated with galena has significantly different 34s values 0 2 to 6 44 and is assumed to have formed by mixing of the ascending fluids with meteoric water

compositions of foraminifera rich turbidite sediments from the shenhu area on the northern slope of the south china sea implication for the presence of deep water bottom currents abstract the sediments in gravity core dh 1 collected from shenhu area on the northern slope of the south china sea are composed of two dark grey clay silt layers a1 and a3 and two foraminifera rich layers a2 and a4 a1 is the top layer and a4 is the bottom layer major and trace metal contents along with grain size and mineralogic data suggest that these silt layers represent background hemipelagic sedimentation unlike silt layers the intervening foraminifera rich layera4 exhibits a fining upward trend is distal turbidite grain size cm diagram and the sharp contacts between the foraminifera rich layer a2 and the upper and lower layers suggest layer a2 is the result of depositional interaction between turbidite and bottom currents ams 14c dating of planktonic foraminifera indicate the age of the turbidite in a2 is between15 3 ka and 22 6 ka we hypothesize that turbidite formation in this period was related to the increase supply of terrigenous matter since the last glacial maximum the rapid deposition of each turbidite led to reduced rates of oxygen diffusion into the sediment allowing anoxic conditions develop in sediments and fostering u enrichment 3 1 g g in foraminifera rich layer a4b in contrast decrease concentration of u and u mo ratios in foraminifera rich layera2 which is possibly due to u remobilization as a consequence of downward penetration of the oxidation front from the oxygen rich bottom currents these new data suggest that authigenic u was quite sensitive to the inflow of bottom currents and u mo ratios may indicate the depositional environmental change in relation to the bottom current action on the turbidite

silver in the north pacific ocean 1 the distribution of silver in the north pacific determined using a suite of surface and subsurface samples was found to be controlled by both natural and anthropogenic processes within the water column silver was distributed as a typical nutrient type element as was previously observed in other oceanic waters however surface water concentrations of silver near japan were the highest ever measured for the open ocean up to 12 pm and are considered evidence of anthropogenic contamination since prevailing wind flow during this study was westerly this enrichment is attributed to aeolian fluxes of asian industrial aerosols to north pacific surface waters additional evidence of the impact atmospheric inputs of silver have on the north pacific water column is shown by comparisons of intermediate depth waters analyzed during this study and during a study carried out 20 years previously that indicate temporal increases in industrial silver fluxes to these waters measurements from this study also confirm that silver is significantly correlated with dissolved silica although the correlations are measurably different between the atlantic and pacific basins and that the ratio of silver to copper is diagnostic of individual water masses in the pacific and can be used as a geochemical tracer of ocean circulation overall data obtained during this study enable a complete preliminary survey of silver in the world ocean

mobility of authigenic rhenium silver and selenium during postdepositional oxidation in marine sediments sedimentary records of redox sensitive trace elements hold significant potential as indicators of paleoceanographic environmental conditions records of re can reveal the intensity of past reducing conditions in sediments at the time of deposition whereas records of ag may record the magnitude of past diatom fluxes to the seafloor confidence in paleoenvironmental reconstruction from records of either metal however requires it to have experienced negligible redistribution since deposition this study examines diagenetic rearrangements of re and ag that occur in response to exposure to bottom water o2 in environments of low sedimentation rate including madeira abyssal plain turbidites and eastern mediterranean basin sapropels authigenic re was remobilized quantitatively by oxidation but poorly retained by the underlying sediments all records are consistent with previous work demonstrating that only a limited reimmobilization of re occurs preferentially in corg rich reducing sediments silver was also mobilized quantitatively by oxidation but it was subsequently immobilized more efficiently in all cases as sharp peaks immediately into anoxic conditions below active oxidation fronts and these peaks remain immobile in anoxic conditions during long term burial comparison of ag s and se records from various cores suggests that ag is likely to have been immobilized as a selenide a mechanism previously proposed for hg in similar situations mercone et al 1999 coexisting narrow peaks of ag and hg with se offer a means of assessing whether oxidative burndown has ever occurred at the top of corg and sulfide rich sedimentary units although these results suggest that caution must be used when inferring paleoenvironmental information from records of ag and re in cores with low sediment accumulation rates 5 cm ka 1 they should not affect the promise that authigenic ag and re records hold for paleoenvironmental reconstruction in sediments with higher accumulation rates and where anoxic conditions have been maintained continuously

228ra 226ra and 226ra ba ratios to track barite formation and transport in the water column abstract we measured 228 ra ex 226 ra ex and 226 ra ex ba ex ratios in suspended and sinking particles collected at the oceanic flux program ofp time series site in the western sargasso sea and compared them to seawater ratios to provide information on the origin and transport of barite baso 4 in the water column the 228 ra ex 226 ra ex ratios of the suspended particles down to 2000 m are nearly identical to those of seawater at the same water depth these ratios are much lower than expected if suspended barite was produced in surface waters and indicate that barite is produced throughout the mesopelagic layer the 228 ra ex 226 ra ex activity ratios of sinking particles collected at 1500 and 3200 m varied mostly between 0 1 and 0 2 which is intermediate between the seawater ratio at these depths ex ba total ba lithogenic considered to be mainly barite present in the sinking flux is a mixture of crystals formed recently in the upper water column formed several years earlier in the upper water column or formed recently in deeper waters we observe a sizeable temporal variability in the 228 ra ex 226 ra ex ratios of sinking particles which indicates temporal variability in the relative proportion of barite crystals originating from surface with a high 228 ra ex 226 ra ex ratio and mesopelagic with a low 228 ra ex 226 ra ex ratio sources however we could not discern a clear pattern that would elucidate the factors that control this variability the 226 ra ba ratios measured in seawater are consistent with the value reported from the geosecs expeditions 2 3 dpm mol 1 below 500 m depth but are significantly lower in the upper 500 m high 226 ra ex ba ex ratios and elevated sr concentrations in suspended particles from the upper water column suggest preferential uptake of 226 ra over ba during formation of srso 4 skeletons by acantharians which must contribute to barite formation in shallow waters deeper in the water column the 226 ra ex ba ex ratios of suspended particles are lower than those of seawater since 228 ra ex 226 ra ex ratios demonstrate that suspended barite at these depths has been produced recently and in situ their low 226 ra ex ba ex ratios indicate preferential uptake of ba over ra in barite formed in mesopelagic water

architecture of the volcanic layer from the costa rica rift constraints from core log integration 1 an understanding of the architecture of the ocean crust s volcanic layer is critical since this records the variations in volcanic activity during formation and subsequently controls the movement of hydrothermal fluids through this layer unfortunately core recovery in the majority of ocean drilling program odp deep sea drilling program basement holes is generally low and biased toward more massive lithologies consequently the identification and estimation of lithological diversity within the volcanic layer is only possible through the integration of core and wire line logging results wire line logging provides nearly continuous records of both physical and chemical properties of the borehole wall which can be used to identify the various volcanic sedimentary lithologies which then can be calibrated in regions of enhanced core recovery using this approach the architecture of the volcanics from odp hole 896a has been reconstructed this new model illustrates a hiatus in volcanism marked by a thick breccia horizon which probably marks the transition from axis to off axis volcanism

determining the influences of late quaternary ventilation and productivity variations on santa barbara basin sedimentary oxygenation a multi proxy approach abstract a correlation between warm interstadials implied by 18oice in the gisp greenland ice core and anoxic events recorded by the sediments drilled at odp site 893 in santa barbara basin sbb has been used previously to relate variations in bottom water oxygenation to high frequency changes in the ventilation of the sbb nature 379 1996 243 however an additional control on the oxygen content at depth is the local settling flux of metabolizable organic matter to assess the impact of oxygen consumption related to this source mo cd re and u concentration data are used here in conjunction with corg and 15n to deduce past redox conditions variations in the sedimentary redox boundary depth and the impact of local organic flux on the oxygenation of sbb deep waters comparisons between odp sites 893 1017 and 1019 allow the differentiation of regional signals dominated by ventilation changes from local signals dominated by vertical organic flux it is concluded that prior to the holocene local productivity changes in the santa barbara basin are not solely the cause of sedimentary anoxia episodic injections of low oxygen intermediate water identified on the regional scale strongly influenced the oxygen content of the sbb during this time however over the last 10 000 years the influence of local productivity has increased and the regional similarity among the three sites is complicated by local signals

major and trace element characterization of oceanic anoxic event 1d oae 1d insight from the umbria marche basin central italy abstract the pialli level in the umbria marche basin central italy correlates with the lowermost part of the positive carbon isotopic excursion characterizing the late albian early cenomanian oceanic anoxic event 1d oae 1d high resolution litho bio and chemostratigraphic data from the monte petrano and le brecce sections allow for a bed by bed comparison of the two successions and discriminate local from basin scale signals we present new x ray fluorescence icp ms and toc data for both the limestones and the pialli level shales integrated with available carbonate carbon isotopes and nannofossil temperature and nutrient indices data indicate a homogenous background sedimentation dominated by pelagic carbonates biogenic silica with little contribution by clays the limited variation in lithogenic elements points to an essentially homogeneous detrital source area with limited fluvial terrigenous input higher mn concentrations coupled with low enrichments in redox sensitive elements such as u fe s re mo ag suggest that the pialli level shales represent temporary suboxia without reaching anoxia furthermore p authigenic ba cd and ni enrichments together with nannofossil nutrient index indicate generally low primary productivity conditions along the entire succession with only minor increases for some of the black to dark grey shales of the pialli level the nannofossil temperature index highlights a warm climate during the oae 1d with the warmest conditions experienced during the deposition of the pialli level shales during the late albian the warm and humid climate was interrupted by brief episodes of relatively warmer and less saline surface waters ensuring slower rates of bottom water renewal and producing temporary suboxic conditions such paleoceanographic dynamics would be the continuation of episodic warmer and humid pulses characterizing the late albian interval in the umbria marche basin as such the pialli level can be considered the result of a last episode closing a cycle before the establishment of a steadier climate during the early cenomanian

sulfate reduction and methanogenesis in a thioploca dominated sediment off the coast of chile continental shelf sediments of the central chile upwelling area are dominated by the presence of dense mats of the filamentous sulfur depositing bacterium thioploca spp we examined rates and pathways of s and methane cycling in these sediments along a transect from the bay of concepcion to the continental slope sulfate reduction rates 170 4670 nmol cm 3 d 1 were equal to or exceeded rates reported for other subtidal marine sediments elemental s and pyrite were the dominant end products of sulfate reduction in thioploca mats on the continental shelf whereas in the highly reducing beggiatoa dominated sediments of the nearby bay of concepcion acid volatile s was the principal end product dissolved organic c values were lowest at the stations with the highest sulfate reduction rates and increased offshore sediment porewater methane concentrations in all surface sediments were low 12 nmol cm 3 and methane production rates at the station most dominated by thioploca were extremely low 0 5 nmol cm 3 d 1 low methane production rates and concentrations were matched by low methane oxidation rates 0 1 nmol cm 3 d 1 radio tracer studies showed that methane production was almost exclusively from methylamines substrates which are noncompetitive with sulfate reduction rather than from acetate or co2 h2 bacterial mpn most probable number counts also indicated the presence of a methylotrophic population of methanogens surprisingly high numbers of autotrophic acetogenic bacteria were found suggesting that the bacterial population involved in anaerobic doc degradation is more complex than expected in spite of the high sulfate reduction rates sulfide concentrations in the shelf and slope were low or undetectable 0 5 m and sulfate concentrations were never depleted below bottom water levels down to depths of 25 30 cm calculations suggest that thioploca were oxidizing a maximum of 35 of sulfide production not enough to prevent sulfate depletion either other sulfide oxidizers were also present or transient hydrodynamic conditions coupled with bioturbation resulted in oxidation of the sediments