Improving noble gas based paleoclimate reconstruction and groundwater dating using Ne/Ne ratios

The interpretation of noble gas concentrations in groundwater with respect to recharge temperature and fractionated excess gas leads to different results on paleo-climatic conditions and on residence times depending on the choice of the gas partitioning model. Two fractionation models for the gas excess are in use, one assuming partial re-equilibration of groundwater supersaturated by excess air (PR-model, Stute et al., 1995), the other assuming closed-system equilibration of groundwater with entrapped air (CE-model, Aeschbach-Hertig et al., 2000). In the example of the Continental Terminal aquifers in Niger, PR- and CE- model are both consistent with the data on elemental noble gas concentrations (Ne, Ar, Kr, and Xe). Only by including the isotope ratio ²⁰Ne/²²Ne it can be demonstrated that the PR-model has to be rejected and the CE-model should be applied to the data. In dating applications ³He of atmospheric origin (³He_atm) required to calculate ³H-³He water ages is commonly estimated from the Ne excess presuming that gas excess is unfractionated air (UA-model). Including in addition to the Ne concentration the ²⁰Ne/²²Ne ratio and the concentration of Ar enables a rigorous distinction between PR-, CE- and UA-model and a reliable determination of ³He_atm and of ³H-³He water ages.     

Coprecipitation in the barite isostructural family: 1. binary mixing properties

This study attempts to provide a theoretical evaluation of coprecipitation and fundamental data of binary mixing properties in the barite isostructural family. Mixing properties of binary solid solutions in the barite isostructural family were derived from evaluation of coprecipitation experiments and partitioning coefficients reported in the literature. The Margules parameters, W, for these binary systems correlate well through the relationship,

     

Uplift rate and landscape development in southwest Fiordland, New Zealand, determined using Be and Al exposure dating of marine terraces

We demonstrate that cosmogenic nuclide surface exposure dating can be used to provide the first well-constrained age for a Fiordland bedrock surface that was created by coastal erosion and has since been uplifted. Tight clustering of ¹⁰Be and ²⁶Al apparent exposure ages between 102-119 kyr on a terrace with strandline at 65 ± 8 m gives a last interglacial age of terrace formation of 130-120 ka, and an uplift rate of 0.52 ± 0.08 mm/yr. Apparent exposure ages from a higher (92-130 m), more incised region of remnant coastal morphology fall in the range 53-111 kyr. The anomalously low ages and large variance demonstrate that weathering and fluvial or rockfall erosion rates are too extreme at the higher sites to determine an age of coastal erosion. Sea level samples have apparent exposure ages in the range 2-11 kyr, with an uncertainty of about 3 kyr. This is consistent with surface exposure during the present sea level high-stand, indicates minimal inheritance of ancient cosmogenic nuclides, and is in accord with geomorphic arguments. Mean ²⁶Al/¹⁰Be ratios of 6.6 for each sample set is consistent with the actively exhuming late Quaternary tectonic setting. Large boulders and gently convex rocky outcrops formed during coastal erosion preserve surfaces that are least modified during later uplift, and are hence the best sites for determining the age of coastal erosion.     

Stable isotope variations in modern tropical speleothems: Evaluating equilibrium vs. kinetic isotope effects

Applications of speleothem calcite geochemistry in climate change studies require the evaluation of the accuracy and sensitivity of speleothem proxies to correctly infer paleoclimatic information. The present study of Harrison’s Cave, Barbados, uses the analysis of the modern climatology and groundwater system to evaluate controls on the C and O isotopic composition of modern speleothems. This new approach directly compares the δ¹⁸O and δ¹³C values of modern speleothems with the values for their corresponding drip waters in order to assess the degree to which isotopic equilibrium is achieved during calcite precipitation. If modern speleothems can be demonstrated to precipitate in isotopic equilibrium, then ancient speleothems, suitable for paleoclimatic studies, from the same cave environment may also have been precipitated in isotopic equilibrium. If modern speleothems are precipitated out of isotopic equilibrium, then the magnitude and direction of the C and O isotopic offsets may allow specific kinetic and/or equilibrium isotopic fractionation mechanisms to be identified.Carbon isotope values for the majority of modern speleothem samples from Harrison’s Cave fall within the range of equilibrium values predicted from the combined use of (1) calcite-water fractionation factors from the literature, (2) measured temperatures, and (3) measured δ¹³C values of the dissolved inorganic carbon of drip waters. Calcite samples range from ∼0.8‰ higher to ∼1.1‰ lower than predicted values. The ¹³C depletions are likely caused by kinetically driven departures in the fractionation between HCO₃⁻ (aq) and CaCO₃ from equilibrium conditions, caused by rapid calcite growth. ¹³C enrichments can be accounted for by Rayleigh distillation of the HCO₃⁻ (aq) reservoir during degassing of ¹³C-depleted CO₂.Modern speleothems from Harrison’s Cave are not in O isotopic equilibrium with their corresponding drip waters and are 0.2‰ to 2.3‰ enriched in ¹⁸O relative to equilibrium values. δ¹⁸O variations in modern calcite are likely controlled by kinetically driven changes in the fractionation between HCO₃⁻ (aq) and CaCO₃ from equilibrium conditions to nonequilibrium conditions, consistent with rapid calcite growth. In contrast to δ¹³C, δ¹⁸O values of modern calcite may not be affected by Rayleigh distillation during degassing because CO₂ hydration and hydroxylation reactions will buffer the O isotopic composition of the HCO₃⁻ (aq) reservoir. If the effects of Rayleigh distillation manifest themselves in the O isotopic system, they will result in ¹⁸O enrichment in the HCO₃⁻ (aq) reservoir and ultimately in the precipitated CaCO₃.     

Precipitation kinetics and carbon isotope partitioning of inorganic siderite at 25°C and 1 atm

Siderite was precipitated from NaHCO₃ and Fe(ClO₄)₂ solutions under anaerobic conditions at 25°C and 1 atm total pressure using a modified version of the chemo-stat technique and the free-drift technique. Samples of solution and solid were withdrawn at different time intervals during time course experiments to determine the bulk and isotope composition of the solution and solid, and the morphology and mineralogy of the solid. A series of metastable precursors precipitated and dissolved sequentially, culminating in well-crystallized siderite rhombohedra having an average edge of ∼ 2 μm and a limited size distribution. Siderite precipitation rate ranged from 10^0.23 to 10^2.44 μmol•m⁻²•h⁻¹ for saturation states (with respect to siderite) ranging from near equilibrium to 10^3.53. Calculated carbon isotope fractionation factors (10³lnα) averaged 8.5 ± 0.2 (1σ n = 4) for the siderite-CO_2(g) system and 0.5 ± 0.2 (1σ n = 4) for the siderite-HCO₃⁻_(aq) system.     

Geochemical models of metasomatism in ultramafic systems: serpentinization, rodingitization, and sea floor carbonate chimney precipitation

In a series of water-rock reaction simulations, we assess the processes of serpentinization of harzburgite and related calcium metasomatism resulting in rodingite-type alteration, and seafloor carbonate chimney precipitation. At temperatures from 25 to 300°C (P = 10 to 100 bar), using either fresh water or seawater, serpentinization simulations produce an assemblage commonly observed in natural systems, dominated by serpentine, magnetite, and brucite. The reacted waters in the simulations show similar trends in composition with decreasing water-rock ratios, becoming hyper-alkaline and strongly reducing, with increased dissolved calcium. At 25°C and w/r less than ∼32, conditions are sufficiently reducing to yield H₂ gas, nickel-iron alloy and native copper. Hyperalkalinity results from OH⁻ production by olivine and pyroxene dissolution in the absence of counterbalancing OH⁻ consumption by alteration mineral precipitation except at very high pH; at moderate pH there are no stable calcium minerals and only a small amount of chlorite forms, limited by aluminum, thus allowing Mg²⁺ and Ca²⁺ to accumulate in the aqueous phase in exchange for H⁺. The reducing conditions result from oxidation of ferrous iron in olivine and pyroxene to ferric iron in magnetite. Trace metals are computed to be nearly insoluble below 300°C, except for mercury, for which high pH stabilizes aqueous and gaseous Hg°. In serpentinization by seawater at 300°C, Ag, Au, Pd, and Pt may approach ore-forming concentrations in sulfide complexes. Simulated mixing of the fluid derived from serpentinization with cold seawater produces a mineral assemblage dominated by calcite, similar to recently discovered submarine, ultramafic rock-hosted, carbonate mineral deposits precipitating at hydrothermal vents. Simulated reaction of gabbroic or basaltic rocks with the hyperalkaline calcium- and aluminum-rich fluid produced during serpentinization at 300°C yields rodingite-type mineral assemblages, including grossular, clinozoisite, vesuvianite, prehnite, chlorite, and diopside.     

Physicochemical characterization of the microhabitat of the epibionts associated with Alvinella pompejana, a hydrothermal vent annelid

Alvinella pompejana is a polychaetous annelid that inhabits narrow tubes along the walls of high-temperature hydrothermal vent chimneys. The worm hosts a rich community of epibiotic bacteria that coats its dorsal surface. Although the worm tube microhabitat is a challenging environment to sample, characterizing the thermal and geochemical regime is important for understanding the ecology of the worm and its bacteria, as the worm spends most of its time inside the tube. We characterized the physicochemical conditions of diffuse hydrothermal flow inside inhabited worm tubes using in situ analysis and wet chemical analysis of discrete water samples. Thermistor probes deployed inside worm tubes measured temperatures ranging from 28.6°C to 84.0°C, while temperatures at tube orifices ranged from 7.5°C to 40.0°C. In situ electrochemical analysis of tube fluids revealed undetectable oxygen (<5 μM) and surprisingly low levels of free H₂S (<0.2 μM), with most of the sulfide existing as aqueous FeS molecular clusters. Acid-volatile sulfide measured on discrete samples of tube fluids ranged from 62.9 to 359.3 μM, while free sulfide (H₂S) ranged from undetectable (<0.2 μM) to 46.5 μM. The pH ranged from 5.33 to 6.40, and sulfate ranged from 22.5 mM to 27.5 mM. Nitrate ranged from 13.9 to 20.0 μM, whereas ammonium ranged from 2.5 to 9.7 μM. Total Fe ranged from 72.1 to 730.2 μM. Mn, Zn, Ni, V, P, and Cu were present in micromolar amounts; Pb, Cd, Co, and Ag were present in nanomolar levels. The worm tube fluids contained between 72% to 91% of Mg concentrations typically found in deep seawater. Plots of Mg concentrations vs. other fluid components showed that the tube fluid is geochemically altered from theoretical mixing values. Values of SO₄²⁻ were enriched inside the worm tube fluids, whereas NO₃⁻, Sr, Mn, Fe, Zn, and acid-volatile sulfide were depleted. The geochemistry of the tube microhabitat likely influences the structure of resident microbial communities.     

Stable carbon and nitrogen isotopic compositions of high molecular weight dissolved organic matter from four U.S. estuaries

High molecular weight dissolved organic matter (HMW-DOM) represents an important component of dissolved organic carbon (DOC) in seawater and fresh-waters. In this paper, we report measurements of stable carbon (δ¹³C) isotopic compositions in total lipid, total hydrolyzable amino acid (THAA), total carbohydrate (TCHO) and acid-insoluble “uncharacterized” organic fractions separated from fourteen HMW-DOM samples collected from four U.S. estuaries. In addition, C/N ratio, δ¹³C and stable nitrogen (δ¹⁵N) isotopic compositions were also measured for the bulk HMW-DOM samples. Our results indicate that TCHO and THAA are the dominant organic compound classes, contributing 33-46% and 13-20% of the organic carbon in HMW-DOM while total lipid accounts for only <2% of the organic carbon in the samples. In all samples, a significant fraction (35-49%) of HMW-DOM was included in the acid-insoluble fraction. Distinct differences in isotopic compositions exist among bulk samples, the compound classes and the acid-insoluble fractions. Values of δ¹³C and δ¹⁵N measured for bulk HMW-DOM varied from −22.1 to −30.1‰ and 2.8 to 8.9‰, respectively and varied among the four estuaries studied as well. Among the compound classes, TCHO was more enriched in ¹³C (δ¹³C = −18.5 to −22.8‰) compared with THAA (δ¹³C = −20.0 to −29.6‰) and total lipid (δ¹³C = −25.7 to −30.7‰). The acid-insoluble organic fractions, in general, had depleted ¹³C values (δ¹³C = −23.0 to −34.4‰). Our results indicate that the observed differences in both δ¹³C and δ¹⁵N were mainly due to the differences in sources of organic matter and nitrogen inputs to these estuaries in addition to the microbial processes responsible for isotopic fractionation among the compound classes. Both terrestrial sources and local sewage inputs contribute significantly to the HMW-DOM pool in the estuaries studied and thus had a strong influence on its isotopic signatures.     

Goethite, calcite, and organic matter from Permian and Triassic soils: carbon isotopes and CO2 concentrations

Pedogenic goethites in each of two Early Permian paleosols appear to record mixing of two isotopically distinct CO₂ components—atmospheric CO₂ and CO₂ from in situ oxidation of organic matter. The δ¹³C values measured for the Fe(CO₃)OH component in solid solution in these Permian goethites are −13.5‰ for the Lower Leonardian (∼283 Ma BP) paleosol (MCGoeth) and −13.9‰ for the Upper Leonardian (∼270 Ma BP) paleosol (SAP). These goethites contain the most ¹³C-rich Fe(CO₃)OH measured to date for pedogenic goethites crystallized in soils exhibiting mixing of the two aforementioned CO₂ components. δ¹³C measured for 43 organic matter samples in the Lower Leonardian (Waggoner Ranch Fm.) has an average value of −20.3 ± 1.1‰ (1s). The average value yields a calculated Early Permian atmospheric Pco₂ value of about 1 × PAL, but the scatter in the measured δ¹³C values of organic matter permits a calculated maximum Pco₂ of 11 × PAL (PAL = present atmospheric level). Measured values of the mole fraction of Fe(CO₃)OH in MCGoeth and SAP correspond to soil CO₂ concentrations in the Early Permian paleosol profiles of 54,000 and 50,000 ppmV, respectively. Such high soil CO₂ concentrations are similar to modern soils in warm, wet environments.The average δ¹³C values of pedogenic calcite from 9 paleosol profiles stratigraphically associated with MCGoeth (Waggoner Ranch Fm.) range from −6.5‰ to −4.4‰, with a mean δ¹³C value for all profiles of −5.4‰. Thus, the value of Δ¹³C between the pedogenic calcite data set and MCGoeth is 8.1 (±0.9)‰, which is in reasonable accord with the value of 7.7‰ expected if atmospheric Pco₂ and organic matter δ¹³C values were the same for both paleosol types. Furthermore, the atmospheric Pco₂ calculated for the Early Permian from the average measured carbon isotopic compositions of the paleosol calcite and organic matter is also analytically indistinguishable from 1 × PAL, with a maximum calculated atmospheric Pco₂ (permitted by one standard deviation of the organic matter δ¹³C value) of ∼5 × PAL.If, however, measured average δ¹³C values of the plant organic matter are more positive than the original soil organic matter as a result of diagenetic loss of ¹³C-depleted, labile organic compounds, calculated Permian atmospheric Pco₂ using these ¹³C-enriched organic values would underestimate the actual atmospheric Pco₂ using either goethite or calcite. This is the first stratigraphically constrained, intrabasinal study to compare ancient atmospheric CO₂ concentrations calculated from pedogenic goethite and calcite. These results demonstrate that the two different proxies record the same information about atmospheric CO₂.The Fe(CO₃)OH component in pedogenic goethite from a Triassic paleosol in Utah is significantly enriched in ¹³C relative to Fe(CO₃)OH in goethites from soils in which there are mixtures of two isotopic CO₂ components. Field-relationships and the δ¹³C value (−1.9‰) of the Triassic goethite indicate that this ancient paleosol profile experienced mixing of three isotopically distinct CO₂ components at the time of goethite crystallization. The three components were probably atmospheric CO₂, CO₂ from in situ oxidation of organic matter and CO₂ from in situ dissolution of preexisting calcite. Although mixing of three isotopically distinct CO₂ components, as recorded by Fe(CO₃)OH in goethite, has been described in modern soil, this is the first example from a documented paleosol. Its preservation affirms the need for careful, case-by-case assessment of ancient paleosols to establish that goethite in any particular soil is likely to be a valid proxy of atmospheric Pco₂.