Fluoride geochemistry of thermal waters in Yellowstone National Park: I. Aqueous fluoride speciation

Thermal water samples from Yellowstone National Park (YNP) have a wide range of pH (1-10), temperature, and high concentrations of fluoride (up to 50 mg/l). High fluoride concentrations are found in waters with field pH higher than 6 (except those in Crater Hills) and temperatures higher than 50 °C based on data from more than 750 water samples covering most thermal areas in YNP from 1975 to 2008. In this study, more than 140 water samples from YNP collected in 2006-2009 were analyzed for free-fluoride activity by ion-selective electrode (ISE) method as an independent check on the reliability of fluoride speciation calculations. The free to total fluoride concentration ratio ranged from <1% at low pH values to >99% at high pH. The wide range in fluoride activity can be explained by strong complexing with H⁺ and Al³⁺ under acidic conditions and lack of complexing under basic conditions. Differences between the free-fluoride activities calculated with the WATEQ4F code and those measured by ISE were within 0.3-30% for more than 90% of samples at or above 10⁻⁶ molar, providing corroboration for chemical speciation models for a wide range of pH and chemistry of YNP thermal waters. Calculated speciation results show that free fluoride, F⁻, and major complexes (, AlF²⁺, and ) account for more than 95% of total fluoride. Occasionally, some complex species like , FeF²⁺, , MgF⁺ and may comprise 1-10% when the concentrations of the appropriate components are high. According to the simulation results by PHREEQC and calculated results, the ratio of main fluoride species to total fluoride varies as a function of pH and the concentrations and ratios of F and Al.     

More on noble gases in Yellowstone National Park hot waters

Water and gas samples from research wells in hydrothermal areas of Yellowstone National Park, U.S.A., have been mass spectrometrically analyzed for their rare gas contents and isotopic composition. In agreement with previous findings, the rare gases have been found to originate from infiltrating run-off water, saturated with air at 10 to 20°C. The atmospheric rare gas retention values found for the water varied between 3 and 87 per cent. The fine structure of the Ar, Kr and Xe abundance pattern in the water reveals fraotionational enrichment of the heavier gases due to partial outgassing of the waters. Radiogenic He and Ar have been detected. No positive evidence for magmatic water contribution has been found. Nevertheless, additions of magmatic waters free of rare gas can not be excluded, but if present the proportion is significantly less than 13 to 36 per cent.     

Fluorapatite and fluorite solubility controls on geothermal waters in Yellowstone National Park

Potential solubility controls on phosphorus in Yellowstone National Park geothermal waters were investigated using the analytical phosphate estimates of Stauffer and Thompson (1978), the computer program, WATEQF, and adopting the equilibrium constant: $\text{log}\text{K}{}_{\mathrm{25°}}\text{= ?61.4}$ for fluorapatite (FAP = Ca₅(PO₄)₃F) dissolution. The near-boiling high-Cl geyser and spring effluents are at or near saturation with respect to (with) FAP. The sixteen representative springs in this category had FAP saturation indices ($\text{S.I. =}\text{log}\text{IAP/K}{}_{\mathrm{r}}$) ranging from ? 3.2 to +4.9 and averaging +0.9. The strongly positive indices were all associated with the highly alkaline conditions resulting from adiabatic cooling in the near surface environment. Hot spring waters indicating extensive dilution (reduced Cl) by meteoric water have lower pH's, and despite PO₄ and Ca concentrations an order of magnitude higher than the geysers, are still frequently undersaturated with FAP. The travertine-depositing “Mixed-water” springs are invariably supersaturated with FAP at ground surface and at or near saturation with hydroxylapatite. Supersaturation may result from kinetic inhibition of apatite crystallization by the elevated Mg²⁺, HCO₃^?, and lower temperatures in these springs. The phosphates may be residuals of the meteoric dilution water.Separately, if Strübel's temperature-dependent estimates of fluorite (CaF₂) solubility are adopted, the high-Cl geysers and springs on “Geyser Hill” and at Norris are consistently undersaturated with CaF₂ at the 90–100° orifice temperatures. The apparent disequilibrium may reflect fluorite equilibration at the much higher temperatures (> 200°C) in the deeper enthalpy reservoirs.     

Arsenic and antimony in geothermal waters of Yellowstone National Park,Wyoming, USA

A total of 268 thermal spring samples were analyzed for total soluble As using reduced molybdenum-blue; 27 of these samples were also analyzed for total Sb using flame atomic absorption spectrometry. At Yellowstone the $\text{Cl}\text{As}$ atomic ratio is nearly constant among neutral-alkaline springs with Cl > 100 mg L^?1, and within restricted geographic areas, indicating no differential effects of adiabatic vs. conductive cooling on arsenic. The $\text{Cl}\text{As}$ ratio increases with silica and decreases with decreasing $\text{Cl}\text{ΣCO}{}_3$; the latter relationship is best exemplified for springs along the extensively sampled SE-NW trend within the Lone Star-Upper-Midway Basin region. The relationship between $\text{Cl}\text{As}$ and $\text{Cl}\text{ΣCO}{}_3$ at Yellowstone suggests a possible rock leaching rather than magmatic origin for much of the Park's total As flux. Condensed vapor springs are low in both As and Cl. Very high $\text{Cl}\text{As}$ ratios ( > 1000) are associated exclusively with highly diluted (Cl < 100 mg L^?1) mixed springs in the Norris and Shoshone Basins and in the Upper White Creek and Firehole Lake areas of Lower Basin. The high ratios are associated with acidity and/or oxygen and iron; they indicate precipitation of As following massive dilution of the Asbearing high-Cl parent water.Yellowstone Sb ranged from 0.009 at Mammoth to 0.166 mg L^?1 at Joseph's Coat Spring. Within basins, the $\text{Cl}\text{Sb}$ ratio increases as the $\text{Cl}\text{ΣCO}{}_3$ ratio decreases, in marked contrast to As. Mixed springs also have elevated $\text{Cl}\text{Sb}$ ratios. White (1967) and Weissberg (1969) previously reported stibnite (Sb₂S₃), but not orpiment (As₂S₃), precipitating in the near surface zone of alkaline geothermal systems.     

Speciation of volatile arsenic at geothermal features in Yellowstone National Park

Geothermal features in the Yellowstone National Park contain up to several milligram per liter of aqueous arsenic. Part of this arsenic is volatilized and released into the atmosphere. Total volatile arsenic concentrations of 0.5-200 mg/m³ at the surface of the hot springs were found to exceed the previously assumed nanogram per cubic meter range of background concentrations by orders of magnitude. Speciation of the volatile arsenic was performed using solid-phase micro-extraction fibers with analysis by GC-MS. The arsenic species most frequently identified in the samples is (CH₃)₂AsCl, followed by (CH₃)₃As, (CH₃)₂AsSCH₃, and CH₃AsCl₂ in decreasing order of frequency. This report contains the first documented occurrence of chloro- and thioarsines in a natural environment. Toxicity, mobility, and degradation products are unknown.     

Annual precipitation in the Yellowstone National Park region since AD 1173

Cores and cross sections from 133 limber pine (Pinus flexilis James) and Douglas fir (Pseudotsuga menziesii (Mirbel) Franco) at four sites were used to estimate annual (July to June) precipitation in the Yellowstone National Park region for the period from AD 1173 to 1998. Examination of the long-term record shows that the early 20th century was markedly wet compared to the previous 700 yr. Extreme wet and dry years within the instrumental period fall within the range of past variability, and the magnitude of the worst-case droughts of the 20th century (AD 1930s and 1950s) was likely equaled or exceeded on numerous occasions before AD 1900. Spectral analysis showed significant decadal to multidecadal precipitation variability. At times this lower frequency variability produces strong regime-like behavior in regional precipitation, with the potential for rapid, high-amplitude switching between predominately wet and predominately dry conditions. Over multiple time scales, strong Yellowstone region precipitation anomalies were almost always associated with spatially extensive events spanning various combinations of the central and southern U.S. Rockies, the northern U.S.-Southern Canadian Rockies and the Pacific Northwest.     

Sulfur geochemistry of hydrothermal waters in Yellowstone National Park,Wyoming, USA. III. An anion-exchange resin technique for sampling and preservation of sulfoxyanions in natural waters

A sampling protocol for the retention, extraction, and analysis of sulfoxyanions in hydrothermal waters has been developed in the laboratory and tested at Yellowstone National Park and Green Lake, NY. Initial laboratory testing of the anion-exchange resin Bio-Rad™ AG1-X8 indicated that the resin was well suited for the sampling, preservation, and extraction of sulfate and thiosulfate. Synthetic solutions containing sulfate and thiosulfate were passed through AG1-X8 resin columns and eluted with 1 and 3 M KCl, respectively. Recovery ranged from 89 to 100%. Comparison of results for water samples collected from five pools in Yellowstone National Park between on-site IC analysis (U.S. Geological Survey mobile lab) and IC analysis of resin-stored sample at SUNY-Stony Brook indicates 96 to 100% agreement for three pools (Cinder, Cistern, and an unnamed pool near Cistern) and 76 and 63% agreement for two pools (Sulfur Dust and Frying Pan). Attempts to extract polythionates from the AG1-X8 resin were made using HCl solutions, but were unsuccessful. Bio-Rad™ AG2-X8, an anion-exchange resin with weaker binding sites than the AG1-X8 resin, is better suited for polythionate extraction. Sulfate and thiosulfate extraction with this resin has been accomplished with KCl solutions of 0.1 and 0.5 M, respectively. Trithionate and tetrathionate can be extracted with 4 M KCl. Higher polythionates can be extracted with 9 M hydrochloric acid. Polythionate concentrations can then be determined directly using ion chromatographic methods, and laboratory results indicate recovery of up to 90% for synthetic polythionate solutions using AG2-X8 resin columns.     

Magnesium isotope fractionation in silicate melts by chemical and thermal diffusion

Two types of laboratory experiments were used to quantify magnesium isotopic fractionations associated with chemical and thermal (Soret) diffusion in silicate liquids. Chemical diffusion couples juxtaposing a molten natural basalt (SUNY MORB) and a molten natural rhyolite (Lake County Obsidian) were run in a piston cylinder apparatus and used to determine the isotopic fractionation of magnesium as it diffused from molten basalt to molten rhyolite. The thermal diffusion experiments were also run in a piston cylinder apparatus but with a sample made entirely of molten SUNY MORB displaced from the hotspot of the assembly furnace so that the sample would have a temperature difference of about 100-200 °C from one end to the other. The chemical diffusion experiments showed fractionations of ²⁶Mg/²⁴Mg by as much as 7‰, which resulted in an estimate for the mass dependence of the self-diffusion coefficients of the magnesium isotopes corresponding to D_26Mg/D_24Mg=(24/26)^β with β = 0.05. The thermal diffusion experiments showed that a temperature difference of about 100 °C resulted in the MgO, CaO, and FeO components of the basalt becoming slightly enriched by about 1 wt% in the colder end while SiO₂ was enriched by several wt% in the hotter end. The temperature gradient also fractionated the magnesium isotopes. A temperature difference of about 150 °C produced an 8‰ enrichment of ²⁶Mg/²⁴Mg at the colder end relative to the hotter end. The magnesium isotopic fractionation as a function of temperature in molten basalt corresponds to 3.6 × 10⁻²‰/°C/amu.     

Stable isotope fractionation between mollusc shells and marine waters from Martinique Island

Forty-nine aragonitic and calcitic shells from 14 species of marine tropical molluscs (Bivalvia, Gastropoda, Polyplacophora) and ambient waters from Martinique have been analyzed for their carbon and oxygen isotope compositions. Mineralogy of shells was systematically determined by Raman spectroscopy that reveals composite shell structures and early processes of diagenetic alteration. In mangrove, brackish waters result from the mixing between 89±1% of seawater and 11±1% of freshwater, a hydrological budget quantified by both oxygen isotope and salinity mass balance calculations. Mollusc shells from the mangrove environment (S=31‰; δ¹⁸O=0.5‰) are characterized by mean δ¹³C values (−1.2‰) lower than those (+2.6‰) living in the open sea (S=35‰; δ¹⁸O=1‰). These low carbon isotope compositions result from the oxidation of organic matter into bicarbonate ions used in the building of mollusc shells. The oxygen isotope compositions of the studied mollusc species are mainly controlled by the temperature and composition of seawater whereas the role of the so-called “vital effects” is negligible. Contrasting with carbon isotopes, variability in the δ¹⁸O values among and within species of mollusc shells is very low (1σ=0.15) for a given littoral environment. Using ambient temperatures of seawater (28-30 °C), oxygen isotope fractionations between all studied living species and environmental waters match those extrapolated from the fractionation equation established for molluscs by Grossman and Ku [Chem. Geol., Isot. Geosci. Sect. 59 (1986) 59] in the range 3-20 °C. By analyzing calcite and aragonite layers from the same shell or by comparing shells from different species living in the same environment, there is no evidence that oxygen isotope fractionation between aragonite and water differs from that between calcite and water. On the basis of these results, we conclude that the oxygen isotope compositions of shells from most fossil mollusc species are suitable to estimate past seawater temperatures at any paleolatitude.     

Hydrogen-isotopic variability in fatty acids from Yellowstone National Park hot spring microbial communities

We report the abundances and hydrogen-isotopic compositions (D/H ratios) of fatty acids extracted from hot-spring microbial mats in Yellowstone National Park. The terrestrial hydrothermal environment provides a useful system for studying D/H fractionations because the numerous microbial communities in and around the springs are visually distinct, separable, and less complex than those in many other aquatic environments. D/H fractionations between lipids and water ranged from −374‰ to +41‰ and showed systematic variations between different types of microbial communities. Lipids produced by chemoautotrophic hyperthermophilic bacteria, such as icosenoic acid (20:1), generally exhibited the largest and most variable fractionations from water (−374‰ to −165‰). This was in contrast to lipids characteristic of heterotrophs, such as branched, odd chain-length fatty acids, which had the smallest fractionations (−163‰ to +41‰). Mats dominated by photoautotrophs exhibited intermediate fractionations similar in magnitude to those expressed by higher plants. These data support the hypothesis that variations in lipid D/H are strongly influenced by central metabolic pathways. Shifts in the isotopic compositions of individual fatty acids across known ecological boundaries show that the isotopic signature of specific metabolisms can be recognized in modern environmental samples, and potentially recorded in ancient ones. Considering all sampled springs, the total range in D/H ratios is similar to that observed in marine sediments, suggesting that the trends observed here are not exclusive to the hydrothermal environment.     

黄龙与黄石钙华微生物沉积作用比较研究

本文通过调查黄龙风景区水体的环境地质特征与微生物群落结构及多样性,并与黄石公园对比分析,探讨了两种特殊地理环境下的微生物群落结构和多样性及其对钙华沉积的影响。结果表明：黄龙沟泉水属于地下冷泉,且景区内覆盖着大量植被,水体中有大量藻类和细菌;黄石公园猛犸象温泉区泉水属于地下热泉,植被覆盖率很低,泉水中微生物多为嗜热菌,藻类较少。黄龙与黄石钙华主要由方解石组成并且微生物参与了钙华的形成过程。微生物对钙华沉积的作用,主要分为模板作用、产物诱导作用和代谢调控作用,对比探讨了特殊地质环境下的微生物对钙华沉积的贡献,指出微生物沉积作用在钙华沉积过程中的重要性,可为黄龙钙华“黑化”防治提供理论依据。     

Holocene beaver damming, fluvial geomorphology, and climate in Yellowstone National Park, Wyoming

We use beaver-pond deposits and geomorphic characteristics of small streams to assess long-term effects of beavers and climate change on Holocene fluvial activity in northern Yellowstone National Park. Although beaver damming has been considered a viable mechanism for major aggradation of mountain stream valleys, this has not been previously tested with stratigraphic and geochronologic data. Thirty-nine radiocarbon ages on beaver-pond deposits fall primarily within the last 4000 yr, but gaps in dated beaver occupation from ~ 2200–1800 and 950–750 cal yr BP correspond with severe droughts that likely caused low to ephemeral discharges in smaller streams, as in modern severe drought. Maximum channel gradient for reaches with Holocene beaver-pond deposits decreases with increasing basin area, implying that stream power limits beaver damming and pond sediment preservation. In northern Yellowstone, the patchy distribution and cumulative thickness of mostly < 2 m of beaver-pond deposits indicate that net aggradation forced by beaver damming is small, but beaver-enhanced aggradation in some glacial scour depressions is greater. Although 20th-century beaver loss and dam abandonment caused significant local channel incision, most downcutting along alluvial reaches of the study streams is unrelated to beaver dam abandonment or predates historic beaver extirpation.     

Selenium fractionation and speciation in rocks, soils, waters and plants in polluted surface mine environment

A fractionation and speciation was performed to determine the distribution of selenium (Se) species in major components of quartzite surface mine environment (rocks, mine tailings, soils, stream sediments, surface waters and plants) in obov, Slovakia. A three-step sequential extraction procedure was utilised for the fractionation of Se in mine tailings and soils. The first extractant in order to evaluate the soluble and ligand exchangeable fraction of Se (0.1 mol/l K₂HPO₄ + KH₂PO₄ at pH 7.0) solubilized up to 15% of total Se content. The second step (0.1 mol/l K₂S₂O₈ at 90°C) which extracted Se associated or occluded with organic matter released 13 – 45% of total selenium. The decomposition of the residue (HNO₃ + H₂SO₄ 1+1) was used to solubilize the remaining 35–88% of total Se as the final step. The recovery of the procedure was between 97 and 106%. Selenate predominated in natural river and lake waters about pH 7.0 (>95%) but in acid mine leakings up to 40% of selenite was found. In the plants (birch leaves, grass leaves and roots) collected from the area acidified by mine leakings no significant accumulation of selenium was observed. The correlation between total Se and S in the rocks from the mine gives an evidence of the common origin of these elements in the studied area.     

Quantifying inorganic sources of geochemical energy in hydrothermal ecosystems, Yellowstone National Park, USA

Combining analytical data from hot spring samples with thermodynamic calculations permits a quantitative assessment of the availability and ranking of various potential sources of inorganic chemical energy that may support microbial life in hydrothermal ecosystems. Yellowstone hot springs of diverse geochemical composition, ranging in pH from <2 to >9 were chosen for this study, and dozens of samples were collected during three field seasons. Field measurements of dissolved oxygen, nitrate, nitrite, total ammonia, total sulfide, alkalinity, and ferrous iron were combined with laboratory analyses of sulfate and other major ions from water samples, and carbon dioxide, hydrogen, methane, and carbon monoxide in gas samples to evaluate activity products for ∼300 coupled oxidation-reduction reactions. Comparison of activity products and independently calculated equilibrium constants leads to values of the chemical affinity for each of the reactions, which quantifies how far each reaction is from equilibrium. Affinities, in turn, show systematic behavior that is independent of temperature but can be correlated with pH of the hot springs as a proxy for the full spectrum of geochemical variability. Many affinities are slightly to somewhat dependent on pH, while others are dramatically influenced by changes in chemical composition. All reactions involving dissolved oxygen as the electron acceptor are potential energy sources in all hot spring samples collected, but the ranking of dominant electron donors changes from ferrous iron, and sulfur at high pH to carbon monoxide, hydrogen, and magnetite as pH decreases. There is a general trend of decreasing energy yields depending on electron acceptors that follows the sequence: O₂(aq) > NO₃⁻ ≈ NO₂⁻ ≈ S > pyrite ≈ SO₄⁻² ≈ CO(g) ≈ CO₂(g) at high pH, and O₂(aq) ≈ magnetite > hematite ≈ goethite > NO₃⁻ ≈ NO₂⁻ ≈ S ≈ pyrite ≈ SO₄⁻² at low pH. Many reactions that are favorable sources of chemical energy at one set of geochemical conditions fail to provide energy at other conditions, and vice versa. This results in energy profiles supplied by geochemical processes that provide fundamentally different foundations for chemotrophic microbial communities as composition changes.     

Mercury in water and biomass of microbial communities in hot springs of Yellowstone National Park,USA

Ultra-clean sampling methods and approaches typically used in pristine environments were applied to quantify concentrations of Hg species in water and microbial biomass from hot springs of Yellowstone National Park, features that are geologically enriched with Hg. Microbial populations of chemically-diverse hot springs were also characterized using modern methods in molecular biology as the initial step toward ongoing work linking Hg speciation with microbial processes. Molecular methods (amplification of environmental DNA using 16S rDNA primers, cloning, denatured gradient gel electrophoresis (DGGE) screening of clone libraries, and sequencing of representative clones) were used to examine the dominant members of microbial communities in hot springs. Total Hg (THg), monomethylated Hg (MeHg), pH, temperature, and other parameters influential to Hg speciation and microbial ecology are reported for hot springs water and associated microbial mats.Several hot springs indicate the presence of MeHg in microbial mats with concentrations ranging from 1 to 10 ng g⁻¹ (dry weight). Concentrations of THg in mats ranged from 4.9 to 120,000 ng g⁻¹ (dry weight). Combined data from surveys of geothermal water, lakes, and streams show that aqueous THg concentrations range from l to 600 ng L⁻¹. Species and concentrations of THg in mats and water vary significantly between hot springs, as do the microorganisms found at each site.     

Factors governing subaqueous siliceous sinter precipitation in hot springs: examples from Yellowstone National Park, USA

Abstract Siliceous sinter precipitation within hot spring systems has been attributed to a variety of mechanisms: evaporative concentration, cooling, changes in pH and cation effects. Repetitive in situ (T, pH, alkalinity, etc.) and laboratory (major, minor and trace elemental, stable isotopic) analyses of the waters plus observations of silica precipitation on natural (e.g. twigs, pine cones) as well as artificial substrates (glass slides and copper plates) in the waters substantiate that subaqueous precipitation is occurring throughout the vent to distal end of flow in both Cistern Spring (Norris Geyser Basin) and Deerbone Spring (Lower Geyser Basin), Yellowstone National Park, Wyoming, USA. Quartz and sodium–potassium geothermometers indicate that Cistern Spring is fed by a subsurface reservoir that is between 232 and 272 °C. Calculated reservoir temperatures are significantly lower at Deerbone Spring (182–197 °C). Based on a suite of measured and theoretical saturation indices, downflow changes in the system resulting from evaporative concentration (e.g. Cl increases 10%), changes in pH (e.g. 5·6–7·1) and cation effects (Al and Fe) are of negligible importance in the subaqueous precipitation of hot spring opal‐A. Similarly, at the macroenvironmental scale, potential biotic effects on opal‐A precipitation appear to be minimal. Modelling of the two active siliceous sinter precipitating systems indicates that cooling (e.g. 80–17 °C) is the predominant process governing subaqueous mineral precipitation.     

Selective concentration of cesium in analcime during hydrothermal alteration,Yellowstone National Park,Wyoming

Chemical and mineralogical studies of fresh and hydrothermally altered rhyolitic material in Upper and Lower Geyser Basins, Yellowstone National Park, show that all the altered rocks are enriched in Cs and that Cs is selectively concentrated in analcime. The Cs content of unaltered rhyolite lava flows, including those from which the altered sediments are derived, ranges from 2.5 to 7.6 ppm. The Cs content of analcime-bearing altered sedimentary rocks is as high as 3000 ppm, and in clinoptilolite-bearing altered sedimentary rocks Cs content is as high as 180 ppm. Altered rhyolite lava flows which were initially vitrophyres, now contain up to 250 ppm Cs, and those which were crystallized prior to hydrothermal alteration contain up to 14 ppm. Mineral concentrates of analcime contain as much as 4700 ppm Cs. The Cs must have been incorporated into the analcime structure during crystallization, rather than by later cation substitution, because analcime does not readily exchange Cs. The $\text{Cs}\text{Cl}$ of the fluids circulating through the hydrothermal system varies, suggesting that Cs is not always a conservative ion and that Cs is lost from upflowing thermal waters due to water-rock interaction resulting in crystallization of Cs-bearing analcime.The source of Cs for Cs enrichment of the altered rocks is from leaching of rhyolitic rocks underlying the geyser basins, and from the top of the silicic magma chamber that underlies the area.Analcime is an important natural Cs sink, and the high Cs concentrations reported here may prove to be an important indicator of the environment of analcime crystallization.     

Iron speciation and isotope fractionation during silicate weathering and soil formation in an alpine glacier forefield chronosequence

The chemical weathering of primary Fe-bearing minerals, such as biotite and chlorite, is a key step of soil formation and an important nutrient source for the establishment of plant and microbial life. The understanding of the relevant processes and the associated Fe isotope fractionation is therefore of major importance for the further development of stable Fe isotopes as a tracer of the biogeochemical Fe cycle in terrestrial environments. We investigated the Fe mineral transformations and associated Fe isotope fractionation in a soil chronosequence of the Swiss Alps covering 150 years of soil formation on granite. For this purpose, we combined for the first time stable Fe isotope analyses with synchrotron-based Fe-EXAFS spectroscopy, which allowed us to interpret changes in Fe isotopic composition of bulk soils, size fractions, and chemically separated Fe pools over time in terms of weathering processes. Bulk soils and rocks exhibited constant isotopic compositions along the chronosequence, whereas soil Fe pools in grain size fractions spanned a range of 0.4‰ in δ⁵⁶Fe. The clay fractions (<2 μm), in which newly formed Fe(III)-(hydr)oxides contributed up to 50% of the total Fe, were significantly enriched in light Fe isotopes, whereas the isotopic composition of silt and sand fractions, containing most of the soil Fe, remained in the range described by biotite/chlorite samples and bulk soils. Iron pools separated by a sequential extraction procedure covered a range of 0.8‰ in δ⁵⁶Fe. For all soils the lightest isotopic composition was observed in a 1 M NH₂OH-HCl-25% acetic acid extract, targeting poorly-crystalline Fe(III)-(hydr)oxides, compared with easily leachable Fe in primary phyllosilicates (0.5 M HCl extract) and Fe in residual silicates. The combination of the Fe isotope measurements with the speciation data obtained by Fe-EXAFS spectroscopy permitted to quantitatively relate the different isotope pools forming in the soils to the mineral weathering reactions which have taken place at the field site. A kinetic isotope effect during the Fe detachment from the phyllosilicates was identified as the dominant fractionation mechanism in young weathering environments, controlling not only the light isotope signature of secondary Fe(III)-(hydr)oxides but also significantly contributing to the isotope signature of plants. The present study further revealed that this kinetic fractionation effect can persist over considerable reaction advance during chemical weathering in field systems and is not only an initial transient phenomenon.     

Aqueous phase-gaseous phase material balance studies of argon and nitrogen in hydrothermal features at Yellowstone National Park

Quantitative analyses of aqueous phases and gaseous phases, gas flow rates, aqueous flow rates have been performed at twenty-five hydrothermal springs at Yellowstone National Park. Material balance calculations indicate that the inventory of argon and nitrogen in these features can be explained very well in terms of a ground water distillation model. The average rate for the release of nitrogen by both phases is 9.06 micromoles of nitrogen per mole of water discharged, and the average rate of release of argon by both phases is 0.248 micromoles of argon per mole of solution. A Rayleigh type distillation is considered in these calculations, and the distribution of argon and nitrogen between the aqueous and gaseous phases approaches equilibrium in most of the features. It is noted that these data are valid for these samples only at the time of emergence. There is no evidence for the addition of juvenile argon or nitrogen to the atmosphere by these springs at the present.     

Carbon and hydrogen isotopic compositions of algae and bacteria from hydrothermal environments,Yellowstone National Park

Stromatolites forming today on a small scale in hydrothermal environments are chemical and biological analogues of much larger Precambrian formations. Carbon isotopic composition varied as a function of CO₂ concentration, pH, and species composition. Stratiform, layered stromatolites grew in silica-depositing springs at 55° to 70°C; they consisted mainly of a unicellular alga, Synechococcus, and a filamentous, photosynthetic bacterium, Chloroflexus. These thermophiles become enriched in ¹²C as the concentration of carbon dioxide in the effluent waters increases. At a concentration of 40 ppm total inorganic C, and δ¹³C of organic carbon was ～ ?12%., whereas at 900 ppm total inorganic C, the δ¹³C of similar species was ～ ?25%.. Conical stromatolites or conophytons (principally a filamentous, blue-green alga Phormidium and Chloroflexus) grew at 40°-55°C. In older, broader conophytons, Chloroflexus was the dominant organism. Their δ¹³C values were ～ ?18%. in a variety of hot springs. In carbonate-depositing springs, i.e., carbon dioxide saturated, conophytons and stromatolites consisting of a variety of blue-green algae and photosynthetic bacteria had the most negative δ¹³C values (to ?30%.). These carbon isotope ratios are directly comparable to carbon isotope ratios of kerogen from Precambrian stromatolites. The presence and activity of methanogenic bacteria or heterotrophic, aerobic and anaerobic bacteria did not alter significantly the δ¹³C of the original organic matter.The hydrogen isotopic fractionation between thermophilic organisms and water is 0 to ?74 for temperatures of 85° to 46°C, respectively. Acidophilic algae fractionated hydrogen isotopes to a lesser extent than did the photosynthetic organisms inhabiting neutral pH springs. Because organic matter retains some of its original isotopic signature, relationships of CO₂ levels, pH, temperature, and species composition between modern stromatolites and their environment and those of the Precambrian can be inferred.