Sources and distribution of organic matter in northern Patagonia fjords,Chile (∼44–47°S): A multi-tracer approach for carbon cycling assessment

We investigated the provenance of organic matter in the inner fjord area of northern Patagonia, Chile (～44–47°S), by studying the elemental (organic carbon, total nitrogen), isotopic (δ¹³C, δ¹⁵N), and biomarker (n-alkanoic acids from vascular plant waxes) composition of surface sediments as well as local marine and terrestrial organic matter. Average end-member values of N/C, δ¹³C, and δ¹⁵N from organic matter were 0.127±0.010, ?19.8±0.3‰, and 9.9±0.5‰ for autochthonous (marine) sources and 0.040±0.018, ?29.3±2.1‰, and 0.2±3.0‰ for allochthonous (terrestrial) sources. Using a mixing equation based on these two end-members, we calculated the relative contribution of marine and terrestrial organic carbon from the open ocean to the heads of fjords close to river outlets. The input of marine-derived organic carbon varied widely and accounted for 13–96% (average 61%) of the organic carbon pool of surface sediments. Integrated regional calculations for the inner fjord system of northern Patagonia covered in this study, which encompasses an area of ～4280 km², suggest that carbon accumulation may account for between 2.3 and 7.8×10⁴ ton C yr^?1. This represents a storage capacity of marine-derived carbon between 1.8 and 6.2×10⁴ ton yr^?1, which corresponds to an assimilation rate of CO₂ by marine photosynthesis between 0.06 and 0.23×10⁶ ton yr^?1. This rate suggests that the entire fjord system of Patagonia, which covers an area of ～240,000 km², may represent a potentially important region for the global burial of marine organic matter and the sequestration of atmospheric CO₂.     

Cave air ventilation and CO2 outgassing by radon-222 modeling: How fast do caves breathe?

In general, the rate and timing of calcite precipitation is in part affected by variations in cave air CO₂ concentrations. Knowledge of cave ventilation processes is required to quantify the effect variations in CO₂ concentrations have on speleothem deposition rates and thus paleoclimate records. In this study we use radon-222 (²²²Rn) as a proxy of ventilation to estimate CO₂ outgassing from the cave to the atmosphere, which can be used to infer relative speleothem deposition rates. Hollow Ridge Cave, a wild cave preserve in Marianna, Florida, is instrumented inside and out with multiple micro-meteorological sensor stations that record continuous physical and air chemistry time-series data. Our time series datasets indicate diurnal and seasonal variations in cave air ²²²Rn and CO₂ concentrations, punctuated by events that provide clues to ventilation and drip water degassing mechanisms. Average cave air ²²²Rn and CO₂ concentrations vary seasonally between winter (²²²Rn = 50 dpm L^? 1, where 1 dpm L^? 1 = 60 Bq m^? 3; CO₂ = 360 ppmv) and summer (²²²Rn = 1400 dpm L^? 1; CO₂ = 3900 ppmv). Large amplitude diurnal variations are observed during late summer and autumn (²²²Rn = 6 to 581 dpm L^? 1; CO₂ = 360 to 2500 ppmv).We employ a simple first-order ²²²Rn mass balance model to estimate cave air exchange rates with the outside atmosphere. Ventilation occurs via density driven flow and by winds across the entrances which create a ‘venturi’ effect. The most rapid ventilation occurs 25 m inside the cave near the entrance: 45 h^? 1 (1.33 min turnover time). Farther inside (175 m) exchange is slower and maximum ventilation rates are 3 h^? 1 (22 min turnover time). We estimate net CO₂ flux from the epikarst to the cave atmosphere using a CO₂ mass balance model tuned with the ²²²Rn model. Net CO₂ flux from the epikarst is highest in summer (72 mmol m^? 2 day^? 1) and lowest in late autumn and winter (12 mmol m^? 2 day^? 1). Modeled ventilation and net CO₂ fluxes are used to estimate net CO₂ outgassing from the cave to the atmosphere. Average net CO₂ outgassing is positive (net loss from the cave) and is highest in late summer and early autumn (about 4 mol h^? 1) and lowest in winter (about 0.5 mol h^? 1). Modeling of ventilation, net CO₂ flux from the epikarst, and CO₂ outgassing to the atmosphere from cave monitoring time-series can help better constrain paleoclimatic interpretations of speleothem geochemical records.     

A reassessment of current volcanic emissions from the Central American arc with specific examples from Nicaragua

The Central American volcanic arc supplies a significant proportion of the persistent annual global sulphur dioxide emissions from volcanoes. In November/December 2003, we completed a survey of the arc section from Mombacho to San Cristóbal in Nicaragua recording individual mean fluxes of 800, 530 and 220 Mg day^− 1 in the plumes from San Cristóbal, Telica and Masaya, respectively. An assessment of fluxes published since 1997 along the entire Central America arc yields a mean total arc flux of SO₂ of 4360 Mg day^− 1 or 8–16% of the annual estimated global volcanic SO₂ flux to the troposphere. New field data shows that Masaya volcano continues to show stable HCl/SO₂ and HF/SO₂ ratios, suggesting a sustained flux of these components of ∼ 220 and 30 Mg day^− 1, respectively (1997 to 2004). Masaya's plume composition also appears to have been stable, between 2001 and 2003, with respect to all the particulate species measured, with significant fluxes of SO₄²⁻ (4 Mg day^− 1), Na⁺ (0.9–1.3 Mg day^− 1) and K⁺ (0.7 Mg day^− 1). Extrapolating the Masaya plume species ratios to the entire Central American arc gives mean HCl and HF fluxes of 1300 and 170 Mg day^− 1 and a particulate sulphate flux of 40 Mg day^− 1 for 1997 to 2004, although without further understanding of the degassing processes and sources at depth of these different volatiles, these arc-scale estimates should be treated with caution. Combining our arc scale mean SO₂ flux with published measurements of volcanic gas compositions with respect to CO₂ and H₂O allows us to estimate mean CO₂ fluxes of 4400–9600 Mg day^− 1 and H₂O fluxes of 70,000–78,000 Mg day^− 1 for the arc. Preliminary comparisons of these estimates of outgassing rates with published volatile input fluxes into the Central American subduction zone, suggest that Cl is more efficiently recycled through the subduction zone than CO₂. The results for H₂O are inconclusive.     

UV camera measurements of fumarole field degassing (La Fossa crater,Vulcano Island)

The UV camera is becoming an important new tool in the armory of volcano geochemists to derive high time resolution SO₂ flux measurements. Furthermore, the high camera spatial resolution is particularly useful for exploring multiple-source SO₂ gas emissions, for instance the composite fumarolic systems topping most quiescent volcanoes. Here, we report on the first SO₂ flux measurements from individual fumaroles of the fumarolic field of La Fossa crater (Vulcano Island, Aeolian Island), which we performed using a UV camera in two field campaigns: in November 12, 2009 and February 4, 2010. We derived ~ 0.5 Hz SO₂ flux time-series finding fluxes from individual fumaroles, ranging from 2 to 8.7 t d^?1, with a total emission from the entire system of ~ 20 t d^?1 and ~ 13 t d^?1, in November 2009 and February 2010 respectively. These data were augmented with molar H₂S/SO₂, CO₂/SO₂ and H₂O/SO₂ ratios, measured using a portable MultiGAS analyzer, for the individual fumaroles. Using the SO₂ flux data in tandem with the molar ratios, we calculated the flux of volcanic species from individual fumaroles, and the crater as a whole: CO₂ (684 t d^?1 and 293 t d^?1), H₂S (8 t d^?1 and 7.5 t d^?1) and H₂O (580 t d^?1 and 225 t d^?1).     

Mantle-derived carbon in Hercynian granites. Stable isotopes signatures and C/He associations in the thermomineral waters,N-Portugal

Na–HCO₃–CO₂-rich thermomineral waters issue in the N of Portugal, within the Galicia-Trás-os-Montes region, linked to a major NNE-trending fault, the so-called Penacova-Régua-Verin megalineament. Along this tectonic structure different occurrences of CO₂-rich thermomineral waters are found: Chaves hot waters (67 °C) and also several cold (16.1 °C) CO₂-rich waters. The δ²H and δ¹⁸O values of the thermomineral waters are similar to those of the local meteoric waters. The chemical composition of both hot and cold mineral waters suggests that water–rock reactions are mainly controlled by the amount of dissolved CO₂ (g) rather than by the water temperature. Stable carbon isotope data indicate an external CO₂ inorganic origin for the gas. δ¹³C_CO2 values ranging between ? 7.2‰ and ? 5.1‰ are consistent with a two-component mixture between crustal and mantle-derived CO₂. Such an assumption is supported by the ³He/⁴He ratios measured in the gas phase, are between 0.89 and 2.68 times the atmospheric ratio (Ra). These ratios which are higher than that those expected for a pure crustal origin (≈ 0.02 Ra), indicating that 10 to 30% of the He has originated from the upper mantle. Release of deep-seated fluids having a mantle-derived component in a region without recent volcanic activity indicates that extensive neo-tectonic structures originating during the Alpine Orogeny are still active (i.e., the Chaves Depression).     

Volatile and trace elements in basaltic glasses from Samoa: Implications for water distribution in the mantle

We report volatile (H₂O, CO₂, F, S, Cl) and trace element data for submarine alkalic basalt glasses from the three youngest Samoan volcanoes, Ta'u, Malumalu and Vailulu'u. Most samples are visibly sulfide saturated, so have likely lost some S during fractionation. Cl / K ratios (0.04–0.15) extend to higher values than pristine MORBs, but are suspected to be partly due to source differences since Cl / K roughly varies as a function of ⁸⁷Sr / ⁸⁶Sr. There are no resolvable differences in the relative enrichment of F among sources, and compatibility of F during mantle melting is established to be nearly identical to Nd. Shallow degassing has affected CO₂ in all samples, and H₂O only in the most shallowly erupted samples from Vailulu'u. Absolute water contents are high for Samoa (0.63–1.50 wt.%), but relative enrichment of water compared to equally incompatible trace elements (Ce, La) is low and falls entirely below normal MORB values. H₂O / Ce (58–157) and H₂O / La (120–350) correlate inversely with ⁸⁷Sr / ⁸⁶Sr compositions (0.7045–0.7089). This leads us to believe that, because of very fast diffusion of hydrogen in mantle minerals, recycled lithospheric material with high initial water and trace element content will lose water to the drier ambient mantle during storage within the inner Earth. The net result is the counter-intuitive appearance of greater dehydration with greater mantle enrichment. We expect that subducted slabs will experience a two-stage dehydration history, first within subduction zones and then in the ambient mantle during long-term convective mixing.     

Carbon isotopic compositions of organic matter across continental Cretaceous–Tertiary (K–T) boundary sections: Implications for paleoenvironment after the K–T impact event

To assess the environmental perturbation induced by the impact event that marks the Cretaceous–Tertiary (K–T) boundary, concentrations and isotopic compositions of bulk organic carbon were determined in sedimentary rocks that span the terrestrial K–T boundary at Dogie Creek, Montana, and Brownie Butte, Wyoming in the Western Interior of the United States. The boundary clays at both sites are not bounded by coals. Although coals consist mainly of organic matter derived from plant tissue, siliceous sedimentary rocks, such as shale and clay, may contain organic matter derived from microbiota as well as plants. Coals record δ¹³C values of plant-derived organic matter, reflecting the δ¹³C value of atmospheric CO₂, whereas siliceous sedimentary rocks record the δ¹³C values of organic matter derived from plants and microbiota. The microbiota δ¹³C value reflects not only the δ¹³C value of atmospheric CO₂, but also biological productivity. Therefore, the siliceous rocks from these sites yields information that differs from that obtained previously from coal beds.Across the freshwater K–T boundary at Brownie Butte, the δ¹³C values decrease by 2.6‰ (from − 26.15‰ below the boundary clay to − 28.78‰ above the boundary clay), similar to the trend in carbonate at marine K–T sites. This means that the organic δ¹³C values reflect the variation of δ¹³C of atmospheric CO₂, which is in equilibrium with carbon isotopes at the ocean surface. Although a decrease in δ¹³C values is observed across the K–T boundary at Dogie Creek (from − 25.32‰ below the boundary clay to − 26.11‰ above the boundary clay), the degree of δ¹³C-decrease at Dogie Creek is smaller than that at Brownie Butte and that for marine carbonate.About 2‰ decrease in δ¹³C of atmospheric CO₂ was expected from the δ¹³C variation of marine carbonate at the K–T boundary. This δ¹³C-decrease of atmospheric CO₂ should affect the δ¹³C values of organic matter derived from plant tissue. As such a decrease in δ¹³C value was not observed at Dogie Creek, a process that compensates the δ¹³C-decrease of atmospheric CO₂ should be involved. For example, the enhanced contribution of ¹³C-enriched organic matter derived from algae in a high-productivity environment could be responsible. The δ¹³C values of algal organic matter become higher than, and thus distinguishable from, those of plant organic matter in situations with high productivity, where dissolved HCO₃⁻ becomes an important carbon source, as well as dissolved CO₂. As the δ¹³C-decrease of atmospheric CO₂ reflected a reduction of marine productivity, the compensation of the δ¹³C decrease by the enhanced activity of the terrestrial microbiota means that the microbiota at freshwater environment recovered more rapidly than those in the marine environment.A distinct positive δ¹³C excursion of 2‰ in the K–T boundary clays is superimposed on the overall decreasing trend at Dogie Creek; this coincides with an increase in the content of organic carbon. We conclude that the K–T boundary clays include ¹³C-enriched organic matter derived from highly productive algae. Such a high biological productivity was induced by phenomena resulting from the K–T impact, such as nitrogen fertilization and/or eutrophication induced by enhanced sulfide formation. The high productivity recorded in the K–T boundary clays means that the freshwater environments (in contrast to marine environments) recovered rapidly enough to almost immediately (within 10 yr) respond to the impact-related environmental perturbations.     

Coupled silicon–oxygen isotope fractionation traces Archaean silicification

Silica alteration zones and cherts are a conspicuous feature of Archaean greenstone belts worldwide and provide evidence of extensive mobilisation of silica in the marine environment of the early Earth. In order to understand the process(es) of silicification we measured the silicon and oxygen isotope composition of sections of variably silicified basalts and overlying bedded cherts from the Theespruit, Hooggenoeg and Kromberg Formations of the Barberton Greenstone Belt, South Africa.The δ³⁰Si and δ¹⁸O values of bulk rock increase with increasing amount of silicification from unsilicified basalts (?0.64‰ < δ³⁰Si < ?0.01‰ and + 8.6‰ < δ¹⁸O < + 11.9‰) to silicified basalts (δ³⁰Si and δ¹⁸O values as high as + 0.81‰ and + 15.6‰, respectively). Cherts generally have positive isotope ratios (+ 0.21‰ < δ³⁰Si < + 1.05‰ and + 10.9 < δ¹⁸O < + 17.1), except two cherts, which have negative δ³⁰Si values, but high δ¹⁸O (up to + 19.5‰).The pronounced positive correlations between δ³⁰Si, δ¹⁸O and SiO₂ imply that the isotope variation is driven by the silicification process which coevally introduced both ¹⁸O and ³⁰Si into the basalts. The oxygen isotope variation in the basalts from about 8.6‰ to 15.6‰ is likely to represent temperature-dependent isotope fractionation during alteration. Our proposed model for the observed silicon isotope variation relies on a temperature-controlled basalt dissolution vs. silica deposition process.     

Deep pooling of low degree melts and volatile fluxes at the 85°E segment of the Gakkel Ridge: Evidence from olivine-hosted melt inclusions and glasses

We present new analyses of volatile, major, and trace elements for a suite of glasses and melt inclusions from the 85°E segment of the ultra-slow spreading Gakkel Ridge. Samples from this segment include limu o pele and glass shards, proposed to result from CO₂-driven explosive activity. The major element and volatile compositions of the melt inclusions are more variable and consistently more primitive than the glass data. CO₂ contents in the melt inclusions extend to higher values (167–1596 ppm) than in the co-existing glasses (187–227 ppm), indicating that the melt inclusions were trapped at greater depths. These melt inclusions record the highest CO₂ melt concentrations observed for a ridge environment. Based on a vapor saturation model, we estimate that the melt inclusions were trapped between seafloor depths (～ 4 km) and ～ 9 km below the seafloor. However, the glasses are all in equilibrium with their eruption depths, which is inconsistent with the rapid magma ascent rates expected for explosive activity. Melting conditions inferred from thermobarometry suggest relatively deep (25–40 km) and cold (1240°–1325 °C) melting conditions, consistent with a thermal structure calculated for the Gakkel Ridge. The water contents and trace element compositions of the melt inclusions and glasses are remarkably homogeneous; this is an unexpected result for ultra-slow spreading ridges, where magma mixing is generally thought to be less efficient based on the assumption that steady-state crustal magma chambers are absent in these environments. All melts can be described by a single liquid line of descent originating from a pooled melt composition that is consistent with the aggregate melt calculated from a geodynamic model for the Gakkel Ridge. These data suggest a model in which deep, low degree melts are efficiently pooled in the upper mantle (9–20 km depth), after which crystallization commences and continues during ascent and eruption. Based on our melting model and the assumption that CO₂ is perfectly incompatible, we show that the highest CO₂ concentrations of the melt inclusions (～ 1600 ppm) are consistent with the calculated CO₂ concentrations of primary undegassed melts. The highest measured CO₂/Nb ratio (443) of Gakkel Ridge melt inclusions predicts a mantle CO₂ content of 134 ppm and would result in a global ridge flux of 2.0 × 10¹² mol CO₂/yr.     

Balancing the global oceanic neodymium budget: Evaluating the role of groundwater

The distinctly different, ε_Nd(0) values of the Atlantic, Indian, and Pacific Oceans requires that the residence time of Nd in the ocean (i.e., τ_Nd) be on the order of, or less than, the ocean mixing time of ∼ 500–1500 yr. However, estimates of τ_Nd, based on river influxes, range from 4000 to 15,000 yr, thus exceeding the ocean mixing time. In order to reconcile the oceanic Nd budget and lower the residence time by roughly a factor of 10, an additional, as yet unidentified, and hence “missing Nd flux” to the ocean is necessary. Dissolution of materials deposited on continental margins has previously been proposed as a source of the missing flux. In this contribution, submarine groundwater discharge (SGD) is examined as a possible source of the missing Nd flux. Neodymium concentrations (n = 730) and ε_Nd(0) values (n = 58) for groundwaters were obtained from the literature in order to establish representative groundwater values. Mean groundwater Nd concentrations and ε_Nd(0) values were used along with recent estimates of the terrestrial (freshwater) component of SGD (6% of river discharge on a global basis) to test whether groundwater discharge to the coastal oceans could account for the missing flux. Employing mean Nd concentrations of the compiled data base (i.e., 31.8 nmol/kg for all 730 analyses and 11.3 nmol/kg for 141 groundwater samples from a coastal aquifer), the global, terrestrial-derived SGD flux of Nd is estimated to range between 2.9 × 10⁷ and 8.1 × 10⁷ mol/yr. These estimates are of the same order of magnitude, and within a factor of 2, of the missing Nd flux (i.e., 5.4 × 10⁷ mol/yr). Applying the SGD Nd flux estimates, the global average ε_Nd(0) of SGD is predicted to be − 9.1, which is similar to our estimate for the missing Nd flux (− 9.2), and in agreement with the mean (± S.D.) ε_Nd(0) measured in groundwaters (i.e., ε_Nd(0) = −8.9 ± 4.2). The similarities in the estimated SGD Nd flux and corresponding ε_Nd(0) values to the magnitude and isotope composition of the missing Nd flux are compelling, and suggest that discharge of groundwater to the oceans could account for the missing Nd flux. Future investigations should focus on quantifying the Nd concentrations and isotope compositions of groundwater from coastal aquifers from a variety of coastal settings, as well as the important geochemical reactions that effect Nd concentrations in subterranean estuaries in order to better constrain contributions of SGD to the oceanic Nd budget.     

Quantification of the gas mass emitted during single explosions on Stromboli with the SO2 imaging camera

We performed measurements using an SO₂ imaging camera of the SO₂ gas mass emitted during five discrete explosive events on Stromboli volcano on 3 October 2006. The SO₂ gas mass released during discrete explosions was 15–40 kg per explosion, producing 3–8% of the total daily SO₂ gas emission, demonstrating that in terms of gas flux Strombolian explosions are a second-order phenomenon compared with quiescent degassing. Using the typical gas composition measured with OP-FTIR allows us to determine the total gas mass released during an explosion as 360–960 kg with a volume of 1500–4100 m³ at 1 bar. At the probable source pressure of gas slug formation of 75 MPa this gas amount would occupy a volume equivalent to a sphere with a radius of 0.8–1 m, comparable with estimates of Stromboli's conduit geometry.     

Magnesium isotopes constraints on the origin of Mg-rich olivines from the Allende chondrite: Nebular versus planetary?

High precision Mg isotope measurements by multi-collector ion microprobe show that refractory olivines from the Allende chondrite, either olivines isolated in the matrix (2 samples studied) or olivines in type I chondrules (6 samples studied), have variable δ²⁶Mg* enrichments and deficits (calculated in permil as the ²⁶Mg deviation from the instrumental mass fractionation line) relative to the Earth. Most average δ²⁶Mg* (noted δ²⁶Mg*_av) values (between 10 and 20 analyses per chondrule) are negative but the total range is from ?0.029 (± 0.010) ‰ (2 sigma errors) to + 0.011 (± 0.011) ‰ with an exception of one olivine at + 0.043 (± 0.023) ‰. These variations in δ²⁶Mg*_av reflect the formation of the olivines from reservoirs enriched in various amounts of ²⁶Mg by the decay of short-lived ²⁶Al (T_1/2 = 0.73 Ma). Similarly, 30 analyses of olivines from the Eagle Station pallasite show a δ²⁶Mg*_av value of ?0.033 ± 0.008‰, as negative as some olivines from Allende chondrules and the Solar system initial δ²⁶Mg* value of ?0.038 ± 0.004‰ (defined at the time of formation of type B Ca–Al-rich inclusions – CAIs – when ²⁶Al/²⁷Al = 5.23 × 10^?5, Jacobsen et al., 2008).Because olivines are Al-poor and because their Mg isotopic compositions are not reset during the chondrule forming events, their δ²⁶Mg*_av can be used to calculate model crystallization ages relative to various theoretical Mg isotope growth curves. The two end-member scenarios considered are (i) a “nebular” growth in which the Al/Mg ratio remains chondritic and (ii) a “planetary” growth in which a significant increase of the Al/Mg ratio can be due to, for instance, olivine magmatic fractionation. The low δ²⁶Mg*_av value of olivines from the Eagle Station pallasite demonstrate that metal-silicate differentiation occurred as early as ~ 0. 15_- 0. 23^+ 0. 29 Ma after CAIs in either of the growth scenarios. Similarly the variable δ²⁶Mg*_av values of refractory olivines can be understood if they were formed in planetesimals which started to differentiate as early as the Eagle Station parent body. Accretion of these planetesimals must have been coeval to the formation of CAIs and their disruption could explain why their fragments (Mg-rich olivines) were distributed in the chondrule forming regions of the disk.     

Century-long record of Mo isotopic composition in sediments of a seasonally anoxic estuary (Chesapeake Bay)

A double-spike method was used to obtain Mo isotope data for sediments and waters of the seasonally anoxic Chesapeake Bay, and its primary tributary, the Susquehanna River. The dissolved Mo distribution in the estuary is non-conservative, reflecting minor Mo loss to the sediments, although removal of Mo to the sediments does not have a large influence on the isotopic composition of the water column. The δ⁹⁸Mo of dissolved Mo in most of the estuary is dominated by seawater. Six samples with salinity > 15 have an average δ⁹⁸Mo = + 2.17‰ (± 0.12), which agrees well with a δ⁹⁸Mo value for the CASS-4 seawater standard of + 2.23‰. A single sample of Susquehanna River water has a δ⁹⁸Mo of + 1.02‰, consistent with recent findings of positive δ⁹⁸Mo in rivers worldwide. Susquehanna river sediments, in contrast, have δ⁹⁸Mo ～ ? 0.1‰. The difference between the river water and sediment values implies that isotopic fractionation occurs within the river basin. The δ⁹⁸Mo values for estuarine sediments are offset from values in the overlying water. Most samples deposited before 1925 have δ⁹⁸Mo less than 0‰, similar to the Susquehanna sediments. Subsequently, there is an increase in the variability of δ⁹⁸Mo, with values ranging up to + 0.8‰. The transition to increased variability coincides with the onset of authigenic Mo deposition, which was previously attributed to escalating summertime anoxia. Authigenic Mo concentrations correlate poorly with δ⁹⁸Mo in core samples, suggesting that independent mechanisms influence the two parameters. Authigenic Mo concentrations may be controlled by shifting pore water H₂S levels, while δ⁹⁸Mo may be primarily affected by annual variations in Mn refluxing.     

Cooling-induced fractionation of mantle Li isotopes from the ultraslow-spreading Gakkel Ridge

Li isotopic compositions of magmatic rocks have gained considerable attention recently as probes of mantle-scale processes. However, the concentrations and isotopic composition of Li in mantle minerals from mid-ocean ridges remain relatively unconstrained. This is largely because of the general presence of seawater alteration in abyssal peridotites. Lithium elemental and isotopic compositions for mineral separates of coexisting olivine, clinopyroxene, orthopyroxene and bulk rocks of serpentine-free Gakkel Ridge peridotites were investigated. Bulk rocks have Li contents of 1.6 to 2.7 ppm and δ⁷Li values of 3 to 5‰, which fall within the range of reported normal pristine “MORB mantle” values. Lithium concentrations vary in the order cpx (2.1–4.7 ppm) > opx (0.9–1.7 ppm) ≥ olivine (0.4–0.9 ppm), the opposite found in “equilibrated” mantle peridotite xenoliths (Seitz and Woodland, 2000). The Li isotopic compositions indicate a systematic mineral variation with δ⁷Li_olivine (7.14‰–15.09‰) > δ⁷Li_opx (1.81‰–3.66‰) > δ⁷Li_cpx (?2.43‰ ? ?0.39‰). The δ⁷Li values of cpx are negatively correlated with their Li concentrations with the lightest value for the most enriched cpx grains. There is a first order negative linear correlation between Δ_{olivine–cpx} (δ⁷Li_olivine ? δ⁷Li_cpx) and ^ol/cpxD (Li_olivine/Li_cpx).Numerical simulations indicate that the observed systematic inter-mineral variations of Li concentrations and isotopic compositions could be explained by a cooling driven diffusive redistribution between minerals in a closed system if there is a temperature dependent partitioning of Li between olivine and clinopyroxene. The studied Gakkel Ridge abyssal peridotites may alternatively have cooled under a variable cooling rate with a rapid cooling before the Li system was closed, which is less likely given the tectonic setting. Our calculations confirm that Li systematics in minerals, especially in coexisting mineral phases could potentially be used as a mantle geospeedometer, even for slowly cooled mantle rocks.     

Significant changes in water pCO2 caused by turbulence from waterfalls

Inland waters are sites of intense carbon processing, stocking and transport. We examined the influence of waterfall-turbulence on CO₂ partial pressures (pCO₂) before and after waterfalls in a tropical river. The results indicated a 51.4% decrease of pCO₂ from up (1375 ± 320 ppm) to downriver (655 ± 58 ppm), suggesting an unaccounted degassing promoted by waterfall-turbulence. This process needs to be better understood in order to more accurately determine the role of freshwater environments in the global carbon balance.     

Oxygen isotope constraints on the origin and differentiation of the Moon

We report new high-precision laser fluorination three-isotope oxygen data for lunar materials. Terrestrial silicates with a range of δ¹⁸O values (− 0.5 to 22.9‰) were analyzed to independently determine the slope of the terrestrial fractionation line (TFL; λ = 0.5259 ± 0.0008; 95% confidence level). This new TFL determination allows direct comparison of lunar oxygen isotope systematics with those of Earth. Values of Δ¹⁷O for Apollo 12, 15, and 17 basalts and Luna 24 soil samples average 0.01‰ and are indistinguishable from the TFL. The δ¹⁸O values of high- and low-Ti lunar basalts are distinct. Average whole-rock δ¹⁸O values for low-Ti lunar basalts from the Apollo 12 (5.72 ± 0.06‰) and Apollo 15 landing sites (5.65 ± 0.12‰) are identical within error and are markedly higher than Apollo 17 high-Ti basalts (5.46 ± 0.11‰). Evolved low-Ti LaPaz mare-basalt meteorite δ¹⁸O values (5.67 ± 0.05‰) are in close agreement with more primitive low-Ti Apollo 12 and 15 mare basalts. Modeling of lunar mare-basalt source composition indicates that the high- and low-Ti mare-basalt mantle reservoirs were in oxygen isotope equilibrium and that variations in δ¹⁸O do not result from fractional crystallization. Instead, these differences are consistent with mineralogically heterogeneous mantle sources for mare basalts, and with lunar magma ocean differentiation models that result in a thick feldspathic crust, an olivine–pyroxene-rich mantle, and late-stage ilmenite-rich zones that were convectively mixed into deeper portions of the lunar mantle. Higher average δ¹⁸O (WR) values of low-Ti basalts compared to terrestrial mid ocean ridge basalts (Δ=0.18‰) suggest a possible oxygen isotopic difference between the terrestrial and lunar mantles. However, calculations of the δ¹⁸O of lunar mantle olivine in this study are only 0.05‰ higher than terrestrial mantle olivine. These observations may have important implications for understanding the formation of the Earth–Moon system.     

The Late Eocene 187Os / 188Os excursion: Chemostratigraphy,cosmic dust flux and the Early Oligocene glaciation

High resolution records (ca. 100 kyr) of Os isotope composition (¹⁸⁷Os / ¹⁸⁸Os) in bulk sediments from two tropical Pacific sites (ODP Sites 1218 and 1219) capture the complete Late Eocene ¹⁸⁷Os / ¹⁸⁸Os excursion and confirm that the Late Eocene ¹⁸⁷Os / ¹⁸⁸Os minimum, earlier reported by Ravizza and Peucker-Ehrenbrink [Earth Planet. Sci. Lett. 210 (2003) 151–165], is a global feature. Using the astronomically tuned age models available for these sites, it is suggested that the Late Eocene ¹⁸⁷Os / ¹⁸⁸Os minimum can be placed at 34.5 ± 0.1 Ma in the marine records. In addition, two other distinct features of the ¹⁸⁷Os / ¹⁸⁸Os excursion that are correlatable among sections are proposed as chemostratigraphic markers which can serve as age control points with a precision of ca. ± 0.1 Myr. We propose a speculative hypothesis that higher cosmic dust flux in the Late Eocene may have contributed to global cooling and Early Oligocene glaciation (Oi-1) by supplying bio-essential trace elements to the oceans and thereby resulting in higher ocean productivity, enhanced burial of organic carbon and draw down of atmospheric CO₂. To determine if the hypothesis that enhanced cosmic dust flux in the Late Eocene was a cause for the ¹⁸⁷Os / ¹⁸⁸Os excursion can be tested by using the paired bulk sediment and leachate Os isotope composition; ¹⁸⁷Os / ¹⁸⁸Os were also measured in sediment leachates. Results of analyses of leachates are inconsistent between the south Atlantic and the Pacific sites, and therefore do not yield a robust test of this hypothesis. Comparison of ¹⁸⁷Os / ¹⁸⁸Os records with high resolution benthic foraminiferal δ¹⁸O records across the Eocene–Oligocene transition suggests that ¹⁸⁷Os flux to the oceans decreased during cooling and ice growth leading to the Oi-1 glaciation, whereas subsequent decay of ice-sheets and deglacial weathering drove seawater ¹⁸⁷Os / ¹⁸⁸Os to higher values. Although the precise timing and magnitude of these changes in weathering fluxes and their effects on the marine ¹⁸⁷Os / ¹⁸⁸Os records are obscured by recovery from the Late Eocene ¹⁸⁷Os / ¹⁸⁸Os excursion, evidence of the global influence of glaciation on supply of Os to the ocean is robust as it has now been documented in both Pacific and Atlantic records.     

Carbon-isotope record of the Early Jurassic (Toarcian) Oceanic Anoxic Event from fossil wood and marine carbonate (Lusitanian Basin,Portugal)

The Toarcian Oceanic Anoxic Event (OAE) in the Early Jurassic (∼ 183 Ma ago) was characterized by widespread near-synchronous deposition of organic-rich shales in marine settings, as well as perturbations to several isotopic systems. Characteristically, two positive carbon-isotope excursions in a range of materials are separated by an abrupt negative shift. Carbon-isotope profiles from Toarcian fossil wood collected in England and Denmark have previously been shown to exhibit this large drop (∼ − 7‰) in δ¹³C values, interpreted as due to an injection of isotopically light CO₂ into the ocean–atmosphere system. However, the global nature of this excursion has been challenged on the basis of carbon-isotope data from nektonic marine molluscs (belemnites), which exhibit heavier than expected carbon-isotope values. Here we present new data, principally from fossil wood and bulk carbonate collected at centimetre scale from a hemipelagic section at Peniche, coastal Portugal. This section is low in organic carbon (average TOC = ∼ 0.5%), and the samples should not have suffered significant diagenetic contamination by organic carbon of marine origin. The carbon-isotope profile based on wood shows two positive excursions separated by a large and abrupt negative excursion, which parallels exactly the profile based on bulk carbonate samples from the same section, albeit with approximately twice the amplitude (∼ − 8‰ in wood versus ∼ − 3.5‰ in carbonate). These data indicate that the negative carbon-isotope excursion affected the atmosphere and, by implication, the global ocean as well. The difference in amplitude between terrestrial organic and marine carbonate curves can be explained by greater water availability in the terrestrial environment during the negative excursion, for which there is independent evidence from marine osmium-isotope records and, plausibly, changes in atmospheric CO₂ content, for which independent evidence is also available. The Peniche succession is also notable for the occurrence of re-deposited sediments: their lowest occurrence coincides with the base of the negative excursion and their highest occurrence coincides with its top. Thus, slope instability and sediment supply could have been strongly linked to the global environmental perturbation, an association that may misleadingly simulate the effects of sea-level fall.     

A nitrogen fixation estimate for the Baltic Sea based on continuous pCO2 measurements on a cargo ship and total nitrogen data

Organic matter production and nitrogen fixation in the central Baltic Sea were studied on the basis of high-resolution CO₂ partial pressure data that were obtained from an automated measurement system deployed on a cargo ship. The net organic carbon (OC) production was calculated from a surface water CO₂ mass balance and used to estimate the nitrogen uptake by organic matter during the period March to August 2005. It was shown that the net OC production continued despite the exhaustion of dissolved inorganic nitrogen (DIN) after the spring bloom in April. The nitrogen demand for this production was calculated on the basis of the C/N ratio of organic matter. It was of the same order of magnitude than the winter DIN concentration that fuelled the spring bloom. Since the atmospheric DIN deposition was negligible and no indications of alternative DIN sources were found, it was assumed that N₂ fixation had taken place despite the low temperatures (4–8 °C) in April/May. This “cold fixation” amounted to 74 mmol m^?2 whereas a value of 99 mmol m^?2 was obtained for the summer N₂ fixation during June/July. Due to the contribution of the April/May N₂ fixation, a total annual rate (173±35 mmol m^?2) was obtained for 2005 which is considerably higher than presently accepted estimates. These findings were confirmed by a nitrogen budget based on long-term data (1993–2006) for total nitrogen and total phosphorus concentrations. Furthermore, these data revealed a 30% increase in N₂ fixation during the years 1994–2006.     

Isotopic fractionation of zinc in tektites

Tektites are terrestrial natural glasses produced during a hypervelocity impact of an extraterrestrial projectile onto the Earth's surface. The similarity between the chemical and isotopic compositions of tektites and terrestrial upper continental crust implies that the tektites formed by fusion of such target rock. Tektites are among the driest rocks on Earth. Although volatilization at high temperature may have caused this extreme dryness, the exact mechanism of the water loss and the behavior of other volatile species during tektite formation are still debated. Volatilization can fractionate isotopes, therefore, comparing the isotope composition of volatile elements in tektites with that of their source rocks may help to understand the physical conditions during tektite formation.For this study, we have measured the Zn isotopic composition of 20 tektites from four different strewn fields. Almost all samples are enriched in heavy isotopes of Zn compared to the upper continental crust. On average, the different groups of tektites are isotopically distinct (listed from the isotopically lightest to the heaviest): Muong-Nong type indochinites (δ^66/64Zn = 0.61 ± 0.30‰); North American bediasites (δ^66/64Zn = 1.61 ± 0.49‰); Ivory Coast tektites (δ^66/64Zn = 1.66 ± 0.18‰); the Australasian tektites (others than the Muong Nong-type indochinites) (δ^66/64Zn = 1.84 ± 0.42‰); and Central European moldavites (δ^66/64Zn = 2.04 ± 0.19‰). These results are contrasted with a narrow range of δ^66/64Zn = 0–0.7‰ for a diverse spectrum of upper continental crust materials.The elemental abundance of Zn is negatively correlated with δ^66/64Zn, which may reflect that isotopic fractionation occurred by evaporation during the heating event upon tektite formation. Simple Rayleigh distillation predicts isotopic fractionations much larger than what is actually observed, therefore, such a model cannot account for the observed Zn isotope fractionation in tektites. We have developed a more realistic model of evaporation of Zn from a molten sphere: during its hypervelocity trajectory, the molten surface of the tektite will be entrained by viscous coupling with air that will then induce a velocity field inside the molten sphere. This velocity field induces significant radial chemical mixing within the tektite that accelerates the evaporation process. Our model, albeit parameter dependent, shows that both the isotopic composition and the chemical abundances measured in tektites can be produced by evaporation in a diffusion-limited regime.