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Chemical weathering in a tropical watershed, Luquillo Mountains, Puerto Rico: I. Long-term versus short-term weathering fluxes

The pristine Rio Icacos watershed in the Luquillo Mountains in eastern Puerto Rico has the fastest documented weathering rate of silicate rocks on the Earth's surface. A regolith propagation rate of 58 m Ma-1 calculated from iso-volumetric saprolite formation from quartz diorite, is comparable to the estimated denudation rate (25-50 Ma-1) but is an order of magnitude faster than the global average weathering rate (6 Ma-1). Weathering occurs in two distinct environments; plagioclase and hornblende react at the saprock interface and biotite and quartz weather in the overlying thick saprolitic regolith. These environments produce distinctly different water chemistries, with K, Mg, and Si increasing linearly with depth in saprolite porewaters and with stream waters dominated by Ca, Na, and Si. Such differences are atypical of less intense weathering in temperate watersheds. Porewater chemistry in the shallow regolith is controlled by closed-system recycling of inorganic nutrients such as K. Long-term elemental fluxes through the regolith (e.g., Si = 1.7 ?? 10-8 moles m-2 s-1) are calculated from mass losses based on changes in porosity and chemistry between the regolith and bedrock and from the age of the regolith surface (200 Ma). Mass losses attributed to solute fluxes are determined using a step-wise infiltration model which calculates mineral inputs to the shallow and deep saprolite porewaters and to stream water. Pressure heads decrease with depth in the shallow regolith (-2.03 m H2O m-1), indicating that both increasing capillary tension and graviometric potential control porewater infiltration. Interpolation of experimental hydraulic conductivities produces an infiltration rate of 1 m yr-1 at average field moisture saturation which is comparable with LiBr tracer tests and with base discharge from the watershed. Short term weathering fluxes calculated from solute chemistries and infiltration rates (e.g., Si = 1.4 ?? 10-8 moles m-2 s-1) are compared to watershed flux rates (e.g., Si = 2.7 ?? 10-8 moles m-2 s-1). Consistency between three independently determined sets of weathering fluxes imply that possible changes in precipitation, temperature, and vegetation over the last several hundred thousand years have not significantly impacted weathering rates in the Luquillo Mountains of Puerto Rico. This has important ramifications for tropical environments and global climate change. Copyright ?? 1998 Elsevier Science Ltd.

Geochimica et Cosmochimica Acta

Chemical weathering in a tropical watershed, Luquillo Mountains, Puerto Rico: II. Rate and mechanism of biotite weathering

Samples of soil, saprolite, bedrock, and porewater from a lower montane wet forest, the Luquillo Experimental Forest (LEF) in Puerto Rico, were studied to investigate the rates and mechanisms of biotite weathering. The soil profile, at the top of a ridge in the Rio Icacos watershed, consists of a 50–100-cm thick layer of unstructured soil above a 600–800 cm thick saprolite developed on quartz diorite. The only minerals present in significant concentration within the soil and saprolite are biotite, quartz, kaolinite, and iron oxides. Biotite is the only primary silicate releasing significant K and Mg to porewaters. Although biotite in samples of the quartz diorite bedrock is extensively chloritized, chlorite is almost entirely absent in the saprolite phyllosilicates. Phyllosilicate grains are present as 200–1000 μm wide books below about 50 cm depth. X-ray diffraction (XRD) and electron microprobe analyses indicate that the phyllosilicate grains contain a core of biotite surrounded by variable amounts of kaolinite. Lattice fringe images under transmission electron microscope (TEM) show single layers of biotite altering to two layers of kaolinite, suggesting dissolution of biotite and precipitation of kaolinite at discrete boundaries. Some single 14-Å layers are also observed in the biotite under TEM. The degree of kaolinitization of individual phyllosilicate grains as observed by TEM decreases with depth in the saprolite. This TEM work is the first such microstructural evidence of epitaxial growth of kaolinite onto biotite during alteration in low-temperature environments. The rate of release of Mg in the profile, calculated as a flux through the soil normalized per watershed land area, is approximately 500 mol hectare −1 yr −1 (1.6 × 10 −9 mol Mg m soil −2 s −1 ). This rate is similar to the flux estimated from Mg discharge out the Rio Icacos (1000 mol hectare −1 yr −1 , or 3.5 × 10 −9 mol Mg m soil −2 s −1 ), indicating that scaling up from the soil to the watershed is possible for Mg release. The rate of Mg release from biotite, normalized to Brunauer-Emmett-Teller (BET) surface area, is calculated using a mass balance equation which includes the density and volume of phyllosilicate grains, porewater chemistry and flux, and soil porosity. The mean rates of biotite weathering calculated from K and Mg release rates are approximately 6 and 11 × 10 −16 mol biotite m biotite −2 s −1 respectively, significantly slower than laboratory rates (10 −12 to 10 −11 mol biotite m biotite −2 s −1 ). The discrepancy in scaling down from the soil to the laboratory is probably explained by (1) differences in weathering mechanism between the two environments, (2) higher solute concentrations in soil porewaters, (3) loss of reactive surface area of biotite in the saprolite due to kaolinite and iron oxide coatings, and/or (4) unaccounted-for heterogeneities in flow path through the soil.

El Yunque, Luquillo Experimental Forest, Luquillo

Hydrogen and oxygen isotope fractionation between brucite and aqueous NaCl solutions from 250 to 450°C

Hydrogen and oxygen isotope fractionation factors between brucite and aqueous NaCl solutions (1000lnα br-sw ) have been calibrated by experiment from 250 to 450°C at 0.5 Kb. For D/H fractionation, 1000lnα br-sw values are as follows: −32 ± 6‰ (250°C, 3.2 wt% NaCl), −21 ± 2‰ (350°C, 10.0 wt% NaCl), and −22 ± 2‰ (450°C, 3.2 wt% NaCl), indicating that brucite is depleted in D relative to coexisting aqueous NaCl solutions. These results are in good agreement with previous D/H fractionation factors determined in the brucite-water system, indicating that any effects of dissolved salt on D/H fractionation are relatively small, particularly in solutions with near seawater salinity. The maximum salt effect (+4‰) was observed in 10.0 wt% NaCl solutions at 350°C, suggesting that the addition of dissolved NaCl increases the amount of deuterium fractionated into mineral structures. For 18 O/ 16 O fractionation, 1000lnα br-sw values in 3.0 wt% NaCl solutions are −6.0 ± 1.3‰, −5.6 ± 0.7‰ and −4.1 ± 0.2‰, at 250, 350, and 450°C, respectively, and −5.8 ± 0.6‰ in 10.0 wt % NaCl at 350°C. These data indicate that brucite is depleted in 18 O relative to coexisting aqueous NaCl solutions and that the degree of depletion decreases slightly with increasing temperature and is not strongly dependent on salinity. We calculated 18 O/ 16 O brucite-water fractionation factors from available calibrations of the salt-effect on 18 O/ 16 O fractionation between coexisting phases. The resulting values were fit to the following equation that is valid from 250 to 450°C 1000ln α br-w = 9.54 × 10 6 T −2 − 3.53 × 10 4 T −1 + 26.58 where T is temperature in Kelvins. These new data have been used to improve the prediction of 18 O/ 16 O fractionation factors in the talc-water and serpentine-water systems by modifying existing empirical bond-water models. The results of this analysis indicate that the δ 18 O composition of talc-brucite and serpentine-brucite pairs could be used as a geothermometer and that these coexisting phases should display the following order of 18 O enrichment: talc > serpentine > brucite.

Geochimica et Cosmochimica Acta

Rare earth element metasomatism in hydrothermal systems: The Willsboro-Lewis wollastonite ores, New York, USA

Wollastonite ores and garnet-pyroxene skarns in the Willsboro-Lewis district, New York, USA were formed in a complex hydrothermal system associated with the emplacement of a large anorthosite pluton. Contact-metamorphic marbles were replaced by wollastonite, garnet, and clinopyroxene during infiltration metasomatism involving large volumes of water of chiefly meteoric origin. Rare earth elements (REE) in these rocks show large departures from the protolith REE distribution, indicative of substantial REE mobility. Three types of chondrite-normalized REE distribution patterns are present. The most common, found in ores and skarns containing andradite-rich garnet, is convex-up in the light REE (LREE) with a maximum at Pr and a positive Eu anomaly. Europium anomalies and Pr/Yb ratios are correlated with X(Ad) in garnet. This pattern (type C) results from uptake of REE from hydrothermal fluids by growing crystals of calcsilicate minerals, principally andradite, with amounts of LREE controlled by the difference in ionic radius between Ca++ and REE3+ in garnet X sites. The Eu anomaly results either from prior interaction of the fluids with plagioclase-rich, Eu-positive anorthositic rocks in and near the ore zone, or by enrichment of divalent Eu on growth surfaces of garnet followed by entrapment, or both. Relative enrichment in heavy REE (type H) occurs in ores and skarn where calcsilicates, including grossularitic garnet, in contact-metamorphic marble have been concentrated by dissolution of calcite. In most cases a negative Eu anomaly is inherited from the marble protolith. Skarns containing titanite and apatite exhibit high total REE, relative light REE enrichment, and negative Eu anomalies (type L). These appear to be intrusive igneous rocks (ferrodiorites or anorthositic gabbros) that have been converted to skarn by Ca metasomatism. REE, sequestered in titanite, apatite, and garnet, preserve the approximate REE distribution pattern of the igneous protolith. Post-ore granulite facies metamorphism homogenized zoned mineral grains without causing complete intergranular reequilibration and does not appear to have significantly affected the whole-rock REE distributions. These results demonstrate that extensive REE metasomatism can occur in hydrothermal systems at shallow to intermediate depths and that REE geochemistry may be useful in discerning the origin of skarns and skarn-related ore deposits.

Geochimica et Cosmochimica Acta

Radioisotope tracer studies of inorganic carbon and Ca in microbially derived CaCO3

Microbial calcification significantly impacts the cycling and deposition of inorganic carbon. This research employs 45 Ca and 14 C techniques as radioisotopic tracers to examine the role of cellular cycling of Ca 2+ and inorganic carbon in CaCO 3 precipitation by the unicellular green alga Nannochloris atomus. Implications of the effects of these physiological aspects on CaCO 3 precipitation and the effects of microbial calcification on CaCO 3 δ 13 C ratios are discussed. Results from pulse/chase experiments indicate that intracellular Ca 2+ is incorporated into extracellular CaCO 3 . Intracellular inorganic carbon leaks from cells within 10 to 12 s after injection of unlabelled NaHCO 3 , providing a source of inorganic carbon for extracellular CaCO 3 . Cellular expulsion of calcium plays a key role in increasing the CaCO 3 saturation state at the site of calcification. The δ 13 C ratios of microbial carbonates may vary depending on the amount of photorespiratory CO 2 incorporated.

Geochimica et Cosmochimica Acta

The absence of lithium isotope fractionation during basalt differentiation: New measurements by multicollector sector ICP-MS

We report measurements of the isotopic composition of lithium in basalts using a multicollector magnetic sector plasma-source mass spectrometer (MC-ICP-MS). This is the first application of this analytical technique to Li isotope determination. External precision of multiple replicate and duplicate measurements for a variety of sample types averages ±1.1‰ (2σ population). The method allows for the rapid (∼8 min/sample) analysis of small samples (∼40 ng Li) relative to commonly used thermal ionization methods. The technique has been applied to a suite of samples from Kilauea Iki lava lake, Hawaii. The samples range from olivine-rich cumulitic lava to SiO 2 − and K 2 O-enriched differentiated liquids, and have δ 7 Li (per mil deviation of sample 7 Li/ 6 Li relative to the L-SVEC standard) of +3.0 to +4.8. The data indicate a lack of per mil-level Li isotope fractionation as a result of crystal–liquid fractionation at temperatures greater than 1050°C. This conclusion has been tacitly assumed but never demonstrated, and is important to the interpretation of Li isotope results from such geochemically complex environments as island arcs.

Hawai'i

Distributions of uronic acids and O-methyl sugars in sinking and sedimentary particles in two coastal marine environments

Although recent research has indicated that bacteria may contribute an important fraction of biochemical residues in terrestrial and marine environments, it is difficult for geochemists to identify contributions from these ubiquitous and biochemically diverse organisms. Previous studies have suggested uronic acids and O -methyl sugars may be useful indicators of microbial abundance and activity, but have been limited primarily to analyses of a small number of isolated samples. We report here comparative distributions of O -methyl sugars, uronic acids, and aldoses in sediment trap material and sediments from Dabob Bay, WA and nearby Saanich Inlet, BC, where temporal and spatial trends may be used together with well-established patterns in other biochemicals to identify bacterial contributions against the background of other carbohydrate sources. O -methyl sugars and uronic acids were important contributors to the overall flux and burial of polysaccharide material in Dabob Bay and Saanich Inlet, composing ≤12 wt% of the total carbohydrate yields from sediment trap and sediment samples. O -methyl sugars accounted for an average of 5% of the carbohydrate yields from sediment trap materials and sediments, but were found rarely and only in low abundance in vascular plant tissues, phytoplankton, and kelp. In contrast, uronic acids were abundant products of sediment trap material and sediments, as well as vascular plant tissues, where in some cases they predominated among all carbohydrates. Uronic acid abundance in sediment trap material averaged 3% and ranged to >6% of total carbohydrate yields. The persistence of total minor sugar yields in water column collections from Dabob Bay throughout the seasonal cycle indicated they had a primary source that was not directly related to plankton bloom cycles nor pulsed inputs of vascular plant remains. Subsurface maxima in total minor sugar yields (and several individual components) within sediment cores from both sites indicate in situ sedimentary sources. Taken together, the observed environmental distributions strongly suggest that the minor sugar abundances in Dabob Bay and Saanich Inlet were controlled by in situ microbial production.

British Columbia, Washington

60 Myr records of major elements and Pb-Nd isotopes from hydrogenous ferromanganese crusts: Reconstruction of seawater paleochemistry

We compare the time series of major element geochemical and Pb- and Nd-isotopic composition obtained for seven hydrogenous ferromanganese crusts from the Atlantic, Indian, and Pacific Oceans which cover the last 60 Myr. Average crust growth rates and age-depth relationships were determined directly for the last about 10 Myr using 10Be/9Be profiles. In the absence of other information these were extrapolated to the base of the crusts assuming constant growth rates and constant initial 10Be/9Be ratios due to the lack of additional information. Co contents have also been used previously to estimate growth rates in Co-rich Pacific and Atlantic seamount crusts (Puteanus and Halbach, 1988). A comparison of 10Be/9Be- and Co-based dating of three Co-rich crusts supports the validity of this approach and confirms the earlier chronologies derived from extrapolated 10Be/9Be-based growth rates back to 60 Ma. Our data show that the flux of Co into Co-poor crusts has been considerably lower. The relationship between growth rate and Co content for the Co-poor crusts developed from these data is in good agreement with a previous study of a wider range of marine deposits (Manheim, 1986). The results suggest that the Co content provides detailed information on the growth history of ferromanganese crusts, particularly prior to 10-12 Ma where the 10Be-based method is not applicable. The distributions of Pb and Nd isotopes in the deep oceans over the last 60 Myr are expected to be controlled by two main factors: (a) variations of oceanic mixing patterns and flow paths of water masses with distinct isotopic signatures related to major paleogeographic changes and (b) variability of supply rates or provenance of detrital material delivered to the ocean, linked to climate change (glaciations) or major tectonic uplift. The major element profiles of crusts in this study show neither systematic features which are common to crusts with similar isotope records nor do they generally show coherent relationships to the isotope records within a single crust. Consequently, any interpretation of time series of major element concentrations of a single crust in terms of paleoceanographic variations must be considered with caution. This is because local processes appear to have dominated over more basin-wide paleoceanographic effects. In this study Co is the only element which shows a relationship to Pb and Nd isotopes in Pacific crusts. A possible link to changes of Pacific deep water properties associated with an enhanced northward advection of Antarctic bottom water from about 14 Ma is consistent with the Pb but not with the Nd isotopic results. The self-consistent profiles of the Pb and Nd isotopes suggest that postdepositional diagenetic processes in hydrogenous crusts, including phosphatization events, have been insignificant for particle reactive elements such as Pb, Be, and Nd. Isotope time series of Pb and Nd show no systematic relationships with major element contents of the crusts, which supports their use as tracers of paleo-seawater isotopic composition.

Geochimica et Cosmochimica Acta

The role of disseminated calcite in the chemical weathering of granitoid rocks

Accessory calcite, present at concentrations between 300 and 3000 mg kg-1, occurs in fresh granitoid rocks sampled from the Merced watershed in Yosemite National Park, CA, USA; Loch Vale in Rocky Mountain National Park CO USA; the Panola watershed, GA USA; and the Rio Icacos, Puerto Rico. Calcite occurs as fillings in microfractures, as disseminated grains within the silicate matrix, and as replacement of calcic cores in plagioclase. Flow-through column experiments, using de-ionized water saturated with 0.05 atm. CO2, produced effluents from the fresh granitoid rocks that were dominated by Ca and bicarbonate and thermodynamically saturated with calcite. During reactions up to 1.7 yr, calcite dissolution progressively decreased and was superceded by steady state dissolution of silicates, principally biotite. Mass balance calculations indicate that most calcite had been removed during this time and accounted for 57-98% of the total Ca released from these rocks. Experimental effluents from surfically weathered granitoids from the same watersheds were consistently dominated by silicate dissolution. The lack of excess Ca and alkalinity indicated that calcite had been previously removed by natural weathering. The extent of Ca enrichment in watershed discharge fluxes corresponds to the amounts of calcite exposed in granitoid rocks. High Ca/Na ratios relative to plagioclase stoichiometries indicate excess Ca in the Yosemite, Loch Vale, and other alpine watersheds in the Sierra Nevada and Rocky Mountains of the western United States. This Ca enrichment correlates with strong preferential weathering of calcite relative to plagioclase in exfoliated granitoids in glaciated terrains. In contrast, Ca/Na flux ratios are comparable to or less than the Ca/Na ratios for plagioclase in the subtropical Panola and tropical Rio Icacos watersheds, in which deeply weathered regoliths exhibit concurrent losses of calcite and much larger masses of plagioclase during transport-limited weathering. These results indicate that the weathering of accessory calcite may strongly influence Ca and alkalinity fluxes from silicate rocks during and following periods of glaciation and tectonism but is much less important for older stable geomorphic surfaces.

Geochimica et Cosmochimica Acta

Calcite crystal growth inhibition by humic substances with emphasis on hydrophobic acids from the Florida Everglades

The crystallization of calcium carbonate minerals plays an integral role in the water chemistry of terrestrial ecosystems. Humic substances, which are ubiquitous in natural waters, have been shown to reduce or inhibit calcite crystal growth in experiments. The purpose of this study is to quantify and understand the kinetic effects of hydrophobic organic acids isolated from the Florida Everglades and a fulvic acid from Lake Fryxell, Antarctica, on the crystal growth of calcite (CaCO 3 ). Highly reproducible calcite growth experiments were performed in a sealed reactor at constant pH, temperature, supersaturation (Ω = 4.5), P CO 2 (10 −3.5 atm), and ionic strength (0.1 M) with various concentrations of organic acids. Higher plant-derived aquatic hydrophobic acids from the Everglades were more effective growth inhibitors than microbially derived fulvic acid from Lake Fryxell. Organic acid aromaticity correlated strongly with growth inhibition. Molecular weight and heteroatom content correlated well with growth inhibition, whereas carboxyl content and aliphatic nature did not.

Florida

D/H isotope ratios of kerogen, bitumen, oil, and water in hydrous pyrolysis of source rocks containing kerogen types I, II, IIS, and III

Immature source rock chips containing different types of kerogen (I, II, IIS, III) were artificially matured in isotopically distinct waters by hydrous pyrolysis and by pyrolysis in supercritical water. Converging isotopic trends of inorganic (water) and organic (kerogen, bitumen, oil) hydrogen with increasing time and temperature document that water-derived hydrogen is added to or exchanged with organic hydrogen, or both, during chemical reactions that take place during thermal maturation. Isotopic mass-balance calculations show that, depending on temperature (310–381°C), time (12–144 h), and source rock type, between ca. 45 and 79% of carbon-bound hydrogen in kerogen is derived from water. Estimates for bitumen and oil range slightly lower, with oil–hydrogen being least affected by water-derived hydrogen. Comparative hydrous pyrolyses of immature source rocks at 330°C for 72 h show that hydrogen in kerogen, bitumen, and expelled oil/wax ranks from most to least isotopically influenced by water-derived hydrogen in the order IIS > II ≈ III > I. Pyrolysis of source rock containing type II kerogen in supercritical water at 381°C for 12 h yields isotopic results that are similar to those from hydrous pyrolysis at 350°C for 72 h, or 330°C for 144 h. Bulk hydrogen in kerogen contains several percent of isotopically labile hydrogen that exchanges fast and reversibly with hydrogen in water vapor at 115°C. The isotopic equilibration of labile hydrogen in kerogen with isotopic standard water vapors significantly reduces the analytical uncertainty of D/H ratios when compared with simple D/H determination of bulk hydrogen in kerogen. If extrapolation of our results from hydrous pyrolysis is permitted to natural thermal maturation at lower temperatures, we suggest that organic D/H ratios of fossil fuels in contact with formation waters are typically altered during chemical reactions, but that D/H ratios of generated hydrocarbons are subsequently little or not affected by exchange with water hydrogen at typical reservoir conditions over geologic time. It will be difficult to utilize D/H ratios of thermally mature bulk or fractions of organic matter to quantitatively reconstruct isotopic aspects of paleoclimate and paleoenvironment. Hope resides in compound-specific D/H ratios of thermally stable, extractable biomarkers (“molecular fossils”) that are less susceptible to hydrogen exchange with water-derived hydrogen.

Geochimica et Cosmochimica Acta

The effect of temperature on experimental and natural chemical weathering rates of granitoid rocks

The effects of climatic temperature variations (5-35??C) on chemical weathering are investigated both experimentally using flow-through columns containing fresh and weathered granitoid rocks and for natural granitoid weathering in watersheds based on annual solute discharge. Although experimental Na and Si effluent concentrations are significantly higher in the fresh relative to the weathered granitoids, the proportional increases in concentration with increasing temperature are similar. Si and Na exhibit comparable average apparent activation energies (E(a)) of 56 and 61 kJ/mol, respectively, which are similar to those reported for experimental feldspar dissolution measured over larger temperature ranges. A coupled temperature-precipitation model, using an expanded database for solute discharge fluxes from a global distribution of 86 granitoid watersheds, produces an apparent activation energy for Si (51 kJ/mol), which is also comparable to those derived from the experimental study. This correlation reinforces evidence that temperature does significantly impact natural silicate weathering rates. Effluent K concentrations in the column study are elevated with respect to other cations compared to watershed discharge due to the rapid oxidation/dissolution of biotite. K concentrations are less sensitive to temperature, resulting in a lower average E(a) value (27 kJ/mol) indicative of K loss from lower energy interlayer sites in biotite. At lower temperatures, initial cation release from biotite is significantly faster than cation release from plagioclase. This agrees with reported higher K/Na ratios in cold glacial watersheds relative to warmer temperate environments. Increased release of less radiogenic Sr from plagioclase relative to biotite at increasing temperature produces corresponding decreases in 87Sr/86Sr ratios in the column effluents. A simple mixing calculation using effluent K/Na ratios, Sr concentrations and 87Sr/86Sr ratios for biotite and plagioclase approximates stoichiometric cation ratios from biotite/plagioclase dissolution at warmer temperatures (35??C), but progressively overestimates the relative proportion of biotite with decreasing temperature. Ca, Mg, and Sr concentrations closely correlate, exhibit no consistent trends with temperature, and are controlled by trace amounts of calcite or exchange within weathered biotite. The inability of the watershed model to differentiate a climate signal for such species correlates with the lower temperature dependence observed in the experimental studies.

Geochimica et Cosmochimica Acta

Direct measurement of the combined effects of lichen, rainfall, and temperature onsilicate weathering

A key uncertainty in models of the global carbonate-silicate cycle and long-term climate is the way that silicates weather under different climatologic conditions, and in the presence or absence of organic activity. Digital imaging of basalts in Hawaii resolves the coupling between temperature, rainfall, and weathering in the presence and absence of lichens. Activation energies for abiotic dissolution of plagioclase (23.1 ?? 2.5 kcal/mol) and olivine (21.3 ?? 2.7 kcal/mol) are similar to those measured in the laboratory, and are roughly double those measured from samples taken underneath lichen. Abiotic weathering rates appear to be proportional to rainfall. Dissolution of plagioclase and olivine underneath lichen is far more sensitive to rainfall.

Geochimica et Cosmochimica Acta

Selenium isotope ratios as indicators of selenium sources and oxyanion reduction

Selenium stable isotope ratio measurements should serve as indicators of sources and biogeochemical transformations of Se. We report measurements of Se isotope fractionation during selenate reduction, selenite sorption, oxidation of reduced Se in soils, and Se volatilization by algae and soil samples. These results, combined with previous work with Se isotopes, indicate that reduction of soluble oxyanions is the dominant cause of Se isotope fractionation. Accordingly, Se isotope ratios should be useful as indicators of oxyanion reduction, which can transform mobile species to forms that are less mobile and less bioavailable. Additional investigations of Se isotope fractionation are needed to confirm this preliminary assessment. We have developed a new method for measurement of natural Se isotope ratio variation which requires less than 500 ng Se per analysis and yields ±0.2‰ precision on 80 Se/ 76 Se. A double isotope spike technique corrects for isotopic fractionation during sample preparation and mass spectrometry. The small minimum sample size is important, as Se concentrations are often below 1 ppm in solids and 1 μg/L in fluids. The Se purification process is rapid and compatible with various sample matrices, including acidic rock or sediment digests.

Geochimica et Cosmochimica Acta

The boron isotope systematics of Icelandic geothermal waters: 1. Meteoric water charged systems

We have measured the boron isotope composition and boron and chloride concentrations of 27 Icelandic geothermal fluids from both high- and low-temperature systems. The δ 11 B values range from −6.7‰ in the Krafla system, to +25.0‰ in a warm spring from the Southern Lowlands. In addition, we have also determined the δ 11 B values of basaltic glass from Nesjavellir (−5.3 ± 1.4‰) and travertine from Snaefellsnes (−22 ± 0.5‰). The B isotope and Cl/B systematics of the high-temperature systems are dominated by the composition of the local basalts. The lower temperature systems show evidence for mixing with B and Cl of a marine origin, together with some uptake of B into secondary mineral phases. The data from the Snaefellsnes geothermal system indicate that the fluids have undergone interaction with basalts that have undergone significant low-temperature alteration by seawater.

Geochimica et Cosmochimica Acta

Age determinations and growth rates of Pacific ferromanganese deposits using strontium isotopes

87Sr 86Sr ratios, trace element and REE compositions, and textural characteristics were determined for three hydrogenetic Fe-Mn crusts, one hydrothermal deposit, and two mixed hydrothermalhydrogenetic crusts from the Pacific. The Sr isotope data are compared to the Sr seawater curve for the Cenozoic to determine the ages and growth rates of the crusts. The 87Sr 86Sr in the crusts does not increase monotonically with depth as expected if the Sr were solely derived from seawater and perfectly preserved since deposition. This indicates post-depositional exchange of Sr or heterogeneous sources for the Sr originally contained in the crusts. Textures of hydrogenetic crusts generally correlate with Sr isotopic variations. The highest porosity intervals commonly exhibit the highest 87Sr 86Sr ratios, indicating exchange with younger seawater. Intervals with the lowest porosity commonly have lower 87Sr 86Sr and may preserve the original Sr isotopic ratios. Minimum ages of crust growth inception were calculated from dense, low porosity intervals. Growth of the hydrogenetic crusts began at or after 23 Ma, although their substrates are Cretaceous. Estimated average growth rates of the three hydrogenetic crusts vary between 0.9 and 2.7 mm/Ma, consistent with published rates determined by other techniques. Within the Marshall Islands crust, growth rates for individual layers varied greatly between 1.0 and 5.4 mm/Ma. For one crust, very low 87Sr 86Sr ratios occurred in detrital-rich intervals. Hydrothermal Fe-Mn oxide from the active Lau Basin back-arc spreading axis (Valu Fa Ridge) has an 87Sr 86Sr ratio with a predominantly seawater signature ( 87Sr 86Sr 0.709196), indicating a maximum age of 0.9 Ma. One crust from an off-axis seamount west of Gorda Ridge may have begun precipitating hydrogenetically at 0.5 Ma (0.709211), and had increasing hydrothermal or volcanic input in the top half of the crust, indicated by a significantly lower 87Sr 86Sr ratio (0.709052). ?? 1990.

Geochimica et Cosmochimica Acta