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The Koudiat Aïcha Zn-Cu-Pb deposit (3–Mt ore @ 3 wt.% Zn, 1 wt.% Pb, 0.6 wt.% Cu) in the Jebilet massif (Morocco) comprises stratabound lenticular orebodies and crosscutting sulfide-bearing quartz ± carbonate veins in the lower Carboniferous Sarhlef volcano sedimentary succession. The veins are characterized by abundant pyrrhotite, sphalerite, subordinate chalcopyrite and galena and rare Ag and Au minerals. The stratabound massive sulfide ores are attributed to a “VMS” type, whereas the origin of the sulfide–quartz ± carbonate veins remains poorly understood. New mineralogical and microanalytical data (SEM, EPMA and LA-ICP-MS) combined with fluid inclusion results point to two-stage vein formation. The early stage involved C–H–O–N Variscan metamorphic fluids which percolated through fractures and shear zones and deposited pyrite at >400 °C, followed by the formation of pyrrhotite and sphalerite (300 ± 20 °C) in quartz veins and in banded and breccia ores. The pyrrhotite–sphalerite mineralization was overprinted by aqueous brines (34 to 38 wt% eq. NaCl + CaCl2) that precipitated carbonate and Cu-Pb sulfides (±Ag-Au) at ~180–210 °C through mixing with low-salinity fluids during tectonic reworking of early-formed structures and in late extension fractures. The latter ore fluids were similar to widspread post-Variscan evaporitic brines that circulated in the Central Jebilet. Overlapping or successive pulses of different ore fluids, i.e., metamorphic fluids and basinal brines, led to metal enrichment in the quartz–carbonate veins compared to the massive sulfide ores. These results underscore that even a single deposit may record several distinct mineralizing styles, such that the ultimate metal endowment may be cumulative over multiple stages.

With mining of seafloor massive sulfides (SMS) coming closer to reality, it is vital that we have a good understanding of the geochemistry of these occurrences and the potential toxicity impact associated with mining them. In this study, SMS samples from seven hydrothermal fields from various tectonic settings were investigated by in-situ microanalysis (electron microprobe (EMPA) and laser ablation inductively coupled plasma mass spectrometry (LA-ICP-MS)) to highlight the distribution of potentially-toxic trace elements (Cu, Zn, Pb, Mn, Cd, As, Sb, Co, Ni, Bi, Ag and Hg) within the deposits, their minerals and textures. We demonstrate that a combination of mineralogy, trace element composition and texture characterisation of SMS from various geotectonic settings, when considered along with our current knowledge of oxidation rates and galvanic coupling, can be used to predict potential toxicity of deposit types and individual samples and highlight which may be of environmental concern. Although we cannot quantify toxicity, we observe that arc-related sulfide deposits have a high potential toxicity when compared with deposits from other tectonic settings based on their genetic association of a wide range of potentially toxic metals (As, Sb, Pb, Hg, Ag and Bi) that are incorporated into more reactive sulfosalts, galena and Fe-rich sphalerite. Thus, deposits such as these require special care when considered as mining targets. In contrast, the exclusive concern of ultra-mafic deposits is Cu, present in abundant, albeit less reactive chalcopyrite, but largely barren of other metals such as As, Pb, Sb, Cd and Hg. Whilst geological setting does dictate metal endowment, ultimately mineralogy is the largest control of trace element distribution and subsequent potential toxicity. Deposits containing abundant pyrrhotite (high-temperature deposits) and Fe-rich sphalerite (ubiquitous to all SMS deposits) as well as deposits with abundant colloform textures also pose a higher ris

We studied the tephra inventory of fourteen deep sea drill sites of three DSDP and ODP legs drilled offshore Guatemala and El Salvador (Legs 67, 84, 138), and one leg offshore Mexico (Leg 66). Marine tephra layers reach back from the Miocene to the Holocene. We identified 223 primary ash beds and correlated these between the drill sites, with regions along the volcanic arcs, and to specific eruptions known from land. In total, 24 correlations were established between marine tephra layers and to well‐known Quaternary eruptions from El Salvador and Guatemala. Additional 25 tephra layers were correlated between marine sites. Another 108 single ash layers have been assigned to source areas on land resulting in a total of 157 single eruptive events. Tephra layer correlations to independently dated terrestrial deposits provide new time markers and help to improve or confirm age models of the respective drill sites. Applying the respective sedimentation rates derived from the age models, we calculated ages for all marine ash beds. Hence, we also obtained new age estimates for eight known, but so far undated large terrestrial eruptions. Furthermore, this enables us to study the temporal evolution of explosive eruptions along the arc and we discovered five pulses of increased activity: 1) a pulse during the Quaternary, 2) a Pliocene pulse between 6 and 3 Ma, 3) a Late Miocene pulse between 10 and 7 Ma, 4) a Middle Miocene pulse between 17–11 Ma, and 5) an Early Miocene pulse (~>21 Ma).

The ultramafic-hosted Kairei vent field is located at 25°19′ S, 70°02′ E, towards the Northern end of segment 1 of the Central Indian Ridge (CIR-S1) at a water depth of ~2450 m. This study aims to investigate the distribution of trace elements among sulfide minerals of differing textures and to examine the possible factors controlling the trace element distribution in those minerals using LA-ICP-MS spot and line scan analyses. Our results show that there are distinct systematic differences in trace element distributions throughout the different minerals, as follows: (1) pyrite is divided into three types at Kairei, including early-stage euhedral pyrite (py-I), sub-euhedral pyrite (py-II), and colloform pyrite (py-III). Pyrite is generally enriched with Mo, Au, As, Tl, Mn, and U. Pyrite-I has high contents of Se, Te, Bi, and Ni when compared to the other types; py-II is enriched in Au relative to py-I and py-III, but poor in Ni; py-III is enriched in Mo, Pb, and U but is poor in Se, Te, Bi, and Au relative to py-I and py-II. Variations in the concentrations of Se, Te, and Bi in pyrite are most likely governed by the strong temperature gradient. There is generally a lower concentration of nickel than Co in pyrite, indicating that our samples precipitated at high temperatures, whereas the extreme Co enrichment is likely from a magmatic heat source combined with an influence of serpentinization reactions. (2) Chalcopyrite is characterized by high concentrations of Co, Se, and Te. The abundance of Se and Te in chalcopyrite over the other minerals is interpreted to have been caused by the high solubilities of Se and Te in the chalcopyrite lattice at high temperatures. The concentrations of Sb, As, and Au are relatively low in chalcopyrite from the Kairei vent field. (3) Sphalerite from Zn-rich chimneys is characterized by high concentrations of Sn, Co, Ga, Ge, Ag, Pb, Sb, As, and Cd, but is depleted in Se, Te, Bi, Mo, Au, Ni, Tl, Mn, Ba, V, and U in comparison with the ot

Highlights • First present seafloor hydrothermal mineralization processes at both Wocan-1 and Wocan-2 on the slow-spreading Carlsberg Ridge. • The Cu-rich chimneys were formed at slightly lower temperatures than Cu-rich and Fe-rich massive sulfides. • The main Ag-carriers were both late-stage Cu sulfides and Fe sulfides, which deposited under low temperatures and oxidized conditions. • Fluid mixing of hydrothermal fluids with seawater might result in significant redistributions of trace metal elements in sulfides. Abstract The basalt-hosted Wocan hydrothermal field (WHF), located on the NW slope of an axial volcanic ridge in a depth of ∼3000 m at 6°22′N on the slow-spreading Carlsberg Ridge, northwest Indian Ocean, was discovered in 2013 during Chinese DY28th cruise. Preliminary investigations show that the field consists of two hydrothermal sites: Wocan-1, which shows indications for recent high-temperature hydrothermal activity, is located near the peak of the axial volcanic ridge in a water depth of 2970-2990 m, and the inactive Wocan-2 site, located at a water depth of 3100 m, ∼1.7 km to the northwest of Wocan-1. The recovered hydrothermal precipitates can be classified into four groups: (i) Cu-rich chimneys; (ii) Cu-rich massive sulfides; (iii) Fe-rich massive sulfides; and (iv) silicified massive sulfides. We conducted mineral texture and assemblage observation and Laser-ablation ICP-MS analyses of the hydrothermal precipitates to study the mineralization processes. Our results show that there are distinct systematic trace element distributions throughout the different minerals in the four sample groups. In general, chalcopyrite from the group (i) is enriched in Pb, As, Mo, Ga, Ge, V, and Sb, metals that are commonly referred to as medium- to low-temperature elements. In contrast these elements are present in low contents in the chalcopyrite grains from other sample groups. Selenium, a typical high-temperature metal, is enriched in chalcopyrite from groups (ii

Highlights • Subplinian to Plinian eruptions from Cocos Island • Tectonically controlled melt ascent • Ocean island evolution without passing typical growth stages Abstract We report a series of fourteen marine tephra layers that are the products of large explosive eruptions of Subplinian to Plinian intensities and magnitudes (VEI > 4) from Cocos Island, Costa Rica. Cocos Island is a volcanic island in the eastern Central Pacific Ocean ~ 500 km offshore Costa Rica, and is situated on the northwestern flank of the aseismic Cocos Ridge. Geochemical fingerprinting of Pleistocene (~ 2.4–1.4 Ma) marine tephra layers from Ocean Drilling Project (ODP) Leg 202 Site 1241 using major and trace element compositions of volcanic glass shards demonstrates unequivocally their origin from Cocos Island rather than the Galápagos Archipelago or the Central American Volcanic Arc (CAVA). Cocos Island and the adjacent seamounts of the Cocos Island Province have alkalic compositions and formed on young (≤ 3 Ma) oceanic crust from an extinct spreading ridge bounded by a transform fault against the older and thicker crust of the aseismic Cocos Ridge. Cocos Island has six times the average volume of the adjacent seamounts although all appear to have formed during the 3–1.4 Ma time period. Cocos Island lies closest to the transform fault and we explain its excessive growth by melts rising from garnet-bearing mantle being deflected from the thick Cocos Ridge lithosphere toward the thinner lithosphere on the other side of the transform, thus enlarging the melt catchment area for Cocos Island compared to the seamounts farther away from the transform. This special setting favored growth above sea level and subaerial explosive eruptions even though the absence of appropriate compositions suggests that the entirely alkalic Cocos Island (and seamounts) never evolved through the productive tholeiitic shield stage typical of other Pacific Ocean islands, possibly because melt production rates remained

Hydrothermal vent deposits form on the seafloor as a result of cooling and mixing of hot hydrothermal fluids with cold seawater. Amongst the major sulfide and sulfate minerals that are preserved at vent sites, barite (BaSO4) is unique because it requires the direct mixing of Ba-rich hydrothermal fluid with sulfate-rich seawater in order for precipitation to occur. Because of its extremely low solubility, barite crystals preserve geochemical fingerprints associated with conditions of formation. Here, we present data from petrographic and geochemical analyses of hydrothermal barite from the Endeavour Segment of the Juan de Fuca Ridge, northeast Pacific Ocean, in order to determine the physical and chemical conditions under which barite precipitates within seafloor hydrothermal vent systems. Petrographic analyses of 22 barite-rich samples show a range of barite crystal morphologies: dendritic and acicular barite forms near the exterior vent walls, whereas larger bladed and tabular crystals occur within the interior of chimneys. A two component mixing model based on Sr concentrations and 87Sr/86Sr of both seawater and hydrothermal fluid, combined with 87Sr/86Sr data from whole rock and laser-ablation ICP-MS analyses of barite crystals indicate that barite precipitates from mixtures containing as low as 17% and as high as 88% hydrothermal fluid component, relative to seawater. Geochemical modelling of the relationship between aqueous species concentrations and degree of fluid mixing indicates that Ba2+ availability is the dominant control on mineral saturation. Observations combined with model results support that dendritic barite forms from fluids of less than 40% hydrothermal component and with a saturation index greater than ∼0.6, whereas more euhedral crystals form at lower levels of supersaturation associated with greater contributions of hydrothermal fluid. Fluid inclusions within barite indicate formation temperatures of between ∼120 °C and 240 °C during barite cr

Matrix effects are one of the frequently observed and discussed issues challenging the accuracy of LA-ICP-MS results. The specific role of the ICP as a source of elemental fractionation seems not fully understood. We report the results of an experiment using six internationally available reference materials (five silicates, one carbonate) measured under 11 different plasma conditions. The thermal/energetic state of the plasma was estimated based on the ratio of Ar-38(+) and Ar-40(2)+ ions. We show that element specific behavior (volatile vs. refractory) dominates at cool but vanishes under hot plasma conditions. For robust (hot) plasma conditions matrix-tolerance seems to be achieved. Additionally we address the problem of matrix-load with respect to the plasma conditions. We've estimated practical limits for the amount of matrix which can be introduced into the ICP without significantly changing the plasma conditions

Author Posting. © The Author(s), 2015. This is the author's version of the work. It is posted here by permission of Elsevier for personal use, not for redistribution. The definitive version was published in Geochimica et Cosmochimica Acta 173 (2016): 64-85, doi:10.1016/j.gca.2015.10.021., Hydrothermal vent deposits form on the seafloor as a result of cooling and mixing of hot hydrothermal fluids with cold seawater. Amongst the major sulfide and sulfate minerals that are preserved at vent sites, barite (BaSO4) is unique because it requires the direct mixing of Ba-rich hydrothermal fluid with sulfate-rich seawater in order for precipitation to occur. Because of its extremely low solubility, barite crystals preserve geochemical fingerprints associated with conditions of formation. Here, we present data from petrographic and geochemical analyses of hydrothermal barite from the Endeavour Segment of the Juan de Fuca Ridge, northeast Pacific Ocean, in order to determine the physical and chemical conditions under which barite precipitates within seafloor hydrothermal vent systems. Petrographic analyses of 22 barite-rich samples show a range of barite crystal morphologies: dendritic and acicular barite forms near the exterior vent walls, whereas larger bladed and tabular crystals occur within the interior of chimneys. A two component mixing model based on Sr concentrations and 87Sr/86Sr of both seawater and hydrothermal fluid, combined with 87Sr/86Sr data from whole rock and laser-ablation ICP-MS analyses of barite crystals indicate that barite precipitates from mixtures containing as low as 17% and as high as 88% hydrothermal fluid component, relative to seawater. Geochemical modelling of the relationship between aqueous species concentrations and degree of fluid mixing indicates that Ba2+ availability is the dominant control on mineral saturation. Observations combined with model results support that dendritic barite forms from fluids of less than 40% hydrothermal component and with a saturation index greater than ~0.6, whereas more euhedral crystals form at lower levels of supersaturation associated with greater contributions of hydrothermal fluid. Fluid inclusions within barite indicate formation temperatures of between ~120 and 240°C during barite crysta, This work was supported by an NSERC PGS scholarship to JWJ and NSERC Discovery Grant to MDH. MKT acknowledges funding from NSF OCE- 1130019. DAB acknowledges funding from NSF OCE-0731947 and the Joint Institute for the Study of the Atmosphere and Ocean (JISAO) under NOAA Cooperative Agreement NA10OAR4320148.

Throughout the transition from the last Glacial to the current Interglacial, rising atmospheric CO2 levels were accompanied by declining atmospheric Δ14C values. A likely mechanism, influencing both components is the deglacial release of CO2, stored for millennia in the deep Ocean, to the atmosphere. Due to its long residence time within the oceans interior this CO2 rich water mass was considerably depleted in radiocarbon. Although a large number of studies address this topic, the extent, location and pathways of the glacial carbon pool are still subjects of an ongoing debate. As deep water masses are upwelled and new intermediate waters are formed around Antarctica, the Southern Ocean is a potential area for the deglacial release of stored CO2. Here we present radiocarbon and carbonate ion data from a transect of sediment cores off New Zealand that covers the major water masses in this area, from the AAIW down to the AABW. During the Glacial, our data locate a significantly 14C depleted pool in a water depth between 2000 and 4500 m. The combination of Δ14C and [CO32-] records provides new insights into the process of oceanic-atmospheric CO2 exchange in the Southern Ocean. In addition, our results yield new implications for contradicting Δ14C records from the Southern Ocean and lower latitudes.

After more than a decade of multidisciplinary studies of the Central American subduction zone mainly in the framework of two large research programmes, the US MARGINS program and the German Collaborative Research Center SFB 574, we here review and interpret the data pertinent to quantify the cycling of mineral-bound volatiles (H2O, CO2, Cl, S) through this subduction system. For input-flux calculations, we divide the Middle America Trench into four segments differing in convergence rate and slab lithological profiles, use the latest evidence for mantle serpentinization of the Cocos slab approaching the trench, and for the first time explicitly include subduction erosion of forearc basement. Resulting input fluxes are 40–62 (53) Tg/Ma/m H2O, 7.8–11.4 (9.3) Tg/Ma/m CO2, 1.3–1.9 (1.6) Tg/Ma/m Cl, and 1.3–2.1 (1.6) Tg/Ma/m S (bracketed are mean values for entire trench length). Output by cold seeps on the forearc amounts to 0.625–1.25 Tg/Ma/m H2O partly derived from the slab sediments as determined by geochemical analyses of fluids and carbonates. The major volatile output occurs at the Central American volcanic arc that is divided into ten arc segments by dextral strike-slip tectonics. Based on volcanic edifice and widespread tephra volumes as well as calculated parental magma masses needed to form observed evolved compositions, we determine long-term (105 years) average magma and K2O fluxes for each of the ten segments as 32–242 (106) Tg/Ma/m magma and 0.28–2.91 (1.38) Tg/Ma/m K2O (bracketed are mean values for entire Central American volcanic arc length). Volatile/K2O concentration ratios derived from melt inclusion analyses and petrologic modelling then allow to calculate volatile fluxes as 1.02–14.3 (6.2) Tg/Ma/m H2O, 0.02–0.45 (0.17) Tg/Ma/m CO2, and 0.07–0.34 (0.22) Tg/Ma/m Cl. The same approach yields long-term sulfur fluxes of 0.12–1.08 (0.54) Tg/Ma/m while present-day open-vent SO2-flux monitoring yields 0.06–2.37 (0.83) Tg/Ma/m S. Input–output comparisons sho

Individual migration behaviour during the juvenile and adult life phase of the anadromous twaite shad Alosa fallax in the Elbe estuary was examined using otolith Sr:Ca and Ba:Ca profiles. Between hatching and the end of the first year of life, juveniles showed two migration patterns. Pattern one exhibited a single downstream migration from fresh water to the sea with no return into fresh water. In contrast, pattern two showed a first migration into the sea, then a return into fresh water and, finally, a second downstream migration into marine water. This first report of migration plasticity for A. fallax points to different exposure times to estuarine threats depending on the migration strategy. In adults, high Sr:Ca and low Ba:Ca in the majority of individuals confirmed prior reports of a primarily marine habitat use. Patterns reflecting spawning migrations were rarely observed on otoliths, possibly due to the short duration of visits to fresh water.

Volatile induced melting processes at mantle depth of convergent margins are triggered by sequential devolatilizing of the subducting oceanic slab. We show that stable chlorine isotopes (37Cl, 35Cl, expressed as 37Cl) can be used to trace each volatile source involved in melt generation and arc volcanism: During dewatering processes in subduction zones, chlorine is strongly partitioned into the aqueous fluid phase, while preserving the distinct ᵟ37Cl values of its volatile sources; Chlorine-isotope fractionation is marginal at high (magmatic) temperatures or during subduction metamorphism and is apparently limited to low temperature processes. Due to limited range of ᵟ37Cl-values in silicate rocks (about ± 2‰) and the relatively imprecise analytical data in earlier studies, few convincing geochemical trends for stable chlorine isotopes have been published so far. To archive the required analytical precision, we developed an alternative and more exact (~0.05‰ 2#) method for ᵟ37Cl determination via LA-MC-ICP-MS. Here we present high-precision ᵟ37Cl data of basaltic to rhyolitic volcanic glasses collected about 700 km along the Central America Volcanic Arc (CAVA). The observed systematic isotopic variations spans a relatively small range in !37Cl values of -1.15 to +0.96‰ and represent systematic changes in volatile sources and depth-dependent zones of fluid release. Our results confirm models for continuous slab dewatering and melt generation and highlight the conservative behavior of stable chlorine isotopes during recycling processes in subduction zones.

The Nicaraguan volcanoes, which are part of the Central American Volcanic Arc (CAVA), have produced 13 highly explosive eruptions within the last 60 ka. All of these “Plinian” eruptions reached well into the stratosphere such that their released volatiles may have induced changes of atmospheric chemistry and climate. While previous research has focussed on the sulfur and chlorine emissions during such large eruptions, we here present measurements of the heavy halogens (bromine, iodine) by means of synchrotron-XRF microanalysis. Spot analyses of pre-eruptive glass inclusions trapped in minerals formed in magma reservoirs were compared with those in matrix glasses of the tephras, which represent the post-eruptive, degassed concentrations. The concentration difference between inclusion and matrix, multiplied by erupted magma mass determined by extensive field mapping, yields an estimate of the degassed mass of heavy halogens. Br and I are probably hundreds of times more effective in destroying ozone than Cl, and can accumulate in the stratosphere over significant time scales. The analysed deposits of 12 large eruptions have bromine and iodine contents in the inclusions of 5 to 27 ppm and 1 to 3 ppm, respectively. Br and I concentrations in matrix glasses are nearly constant at 5 ppm and 0.5 ppm, respectively. Analyses by mass spectrometry of pyrohydrolysed samples of the phenocryst-poor bulk glasses confirm the Br and I concentrations observed for matrix glasses. On average, masses of 50 kilotons of bromine and 27 kilotons of iodine have been released during single eruptions; for the 25 ka eruption of the Upper Apoyo Tephra, however, the released heavy halogen masses are about one order of magnitude larger, reflecting both the larger erupted magma mass and higher magmatic heavy halogen concentrations. Our new data on heavy halogens will be used as input for climate models to evaluate past –and possible future – atmospheric effects.

Mombacho is a deeply dissected volcano belonging to the Quaternary volcanic chain of Nicaragua. The southern, historic collapse crater (El Crater) currently hosts a fumarolic field with a maximum temperature of 121°C. Chemical and isotopic data from five gas-sampling field campaigns carried out in 2002, 2003 and 2005 highlight the presence of high-temperature gas components (e.g. SO2, HCl and HF), which indicate a significant contribution of juvenile magmatic fluids to the hydrothermal system feeding the gas discharges. This is strongly supported by the mantle-derived helium and carbon isotopic signatures, although the latter is partly masked by either a sedimentary subduction-related or a shallow carbonate component. The observed chemical and isotopic composition of the Mombacho fluids seems to indicate that this volcanic system, although it has not experienced eruptive events during the last centuries, can be considered active and possibly dangerous, in agreement with the geophysical data recorded in the region. Systematic geochemical monitoring of the fumarolic gas discharges, coupled with a seismic and ground deformation network, is highly recommended in order to monitor a possible new eruptive phase.