Mathematical modeling of PCB bioaccumulation in Perna viridis

In the present work, we built a mathematical model of polychlorinated biphenyl (PCB) bioaccumulation in Perna viridis, namely, a one-compartment model with a time dependent incorporation rate R (μg g⁻¹ lipid per ppb water per day), with positive substrate cooperativity as the underlying physical mechanism. The temporal change of the PCB concentration Q (μg g⁻¹ lipid) in the soft tissues of the mussel depends on the competition of the input rate RW and the output rate kQ, where W is the concentration of PCB in water (ppb water) and k is the elimination rate (per day). From our experimental data, k=0.181±0.017 d⁻¹. The critical concentration in water W_c for positive substrate cooperativity was found to be 2.4 ppb. Below W_c, R is a constant. For a water concentration of 0.5 ppb Aroclor 1254, R=24.0±2.4 μg g⁻¹ lipid ppb⁻¹ d⁻¹. Above W_c, positive substrate cooperativity comes into effect and R becomes a function of time and dependent on the concentration Q in a form R=γQ/(Q+δ). This is the case for a water concentration of 5 ppb Aroclor 1254, where γ=15.1 μg g⁻¹ lipid ppb⁻¹ d¹ and δ≈200 μg g⁻¹ lipid. From this model, the uptake is exponentially increasing when the PCB concentration in the mussel is small compared to 200 μg g⁻¹ lipid, and hyperbolically increasing when the concentration is large compared to 200 μg g⁻¹ lipid, which are consistent with the experimental data. The model is useful for understanding the true processes taking place during the bioaccumulation and for risk assessment with higher confidence. Future experimental data which challenge the present model are anticipated and in fact desirable for improvement and perfection of the model.     

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.     

The fate of B, Cl and Li in the subducted oceanic mantle and in the antigorite breakdown fluids

We present an inventory of B, Cl and Li concentrations in (a) key minerals from a set of ultramafic samples featuring the main evolutionary stages encountered by the subducted oceanic mantle, and in (b) fluid inclusions produced during high-pressure breakdown of antigorite serpentinite. Samples correspond to (i) nonsubducted serpentinites (Northern Apennine and Alpine ophiolites), (ii) high-pressure olivine-bearing antigorite serpentinites (Western Alps and Betic Cordillera), (iii) high-pressure olivine-orthopyroxene rocks recording the subduction breakdown of antigorite serpentinites (Betic Cordillera). Two main dehydration episodes are recorded by the sample suite: partial serpentinite dewatering during formation of metamorphic olivine, followed by full breakdown of antigorite serpentine to olivine+orthopyroxene+fluid. Ion probe and laser ablation ICP-MS (LA ICP-MS) analyses of Cl, B and Li in the rock-forming minerals indicate that the hydrous mantle is an important carrier of light elements. The estimated bulk-rock B and Cl concentrations progressively decrease from oceanic serpentinites (46.7 ppm B and 729 ppm Cl) to antigorite serpentinites (20 ppm B and 221 ppm Cl) to olivine-orthopyroxene rocks (9.4 ppm B and 45 ppm Cl). This suggests release of oceanic Cl and B in subduction fluids, apparently without inputs from external sources. Lithium is less abundant in oceanic serpentinites (1.3 ppm) and the initial concentrations are still preserved in high-pressure antigorite serpentinites. Higher Li contents in olivine, Ti-clinohumite of the olivine-orthopyroxene rocks (4.9 ppm bulk rock Li), as well as in the coexisting fluid inclusions, suggest that their budget may not be uniquely related to recycling of oceanic Li, but may require input from external sources.Laser ablation ICP-MS analyses of fluid inclusions in the olivine-orthopyroxene rocks enabled an estimate of the Li and B concentrations in the antigorite breakdown fluid. The inclusion compositions were quantified using a range of salinity values (0.4-2 wt.% NaCl_equiv) as internal standards, yielding maximum average ^fluid/rockD_B∼5 and ^fluid/rockD_Li∼3.5. We also performed model calculations to estimate the B and Cl loss during the two dehydration episodes of serpentinite subduction. The first event is characterized by high fluid/rock partition coefficients for Cl (∼100) and B (∼60) and by formation of a fluid with salinity of 4-8 wt.% NaCl_equiv. The antigorite breakdown produces less saline fluids (0.4-2 wt.% NaCl_equiv) and is characterized by lower partition coefficients for Cl (25-60) and B (12-30). Our calculations indicate that the salinity of the subduction fluids decreases with increasing depths. ^fluid/rockD_B/^fluid/rockD_Cl<1 (∼0.5) indicates that Cl preferentially partitions into the evolved fluids relative to B and that the B/Cl of fluids progressively increases with increasing depths and temperatures.Despite light element release in fluids, appreciable B, Cl and Li are still retained in chlorite, olivine and Ti-clinohumite beyond the antigorite stability field. This permits a bulk storage of about 10 ppm B, 45 ppm Cl and 5 ppm Li, i.e., concentrations much higher than in mantle reservoirs. Chlorite is the Cl repository and its stability controls the Cl and H₂O budget beyond the antigorite stability; B and Li are bound in olivine and clinohumite. The subducted oceanic mantle thus retains light elements beyond the depths of arc magma sources, potentially introducing anomalies in the upper mantle.     

Lithium isotope variations in Tonga–Kermadec arc–Lau back‐arc lavas and Deep Sea Drilling Project (DSDP) Site 204 sediments

Lithium isotopes have been identified as a promising tracer of subducted materials in arc lavas due to the observable variations in related reservoirs such as subducting sediments and altered oceanic crust. The Tonga–Kermadec arc–Lau back‐arc provides an end‐member of subduction zones with the coldest thermal structure on Earth. Reported here are Li isotope data for 14 lavas from the arc front and 7 back‐arc lavas as well as 12 pelagic and volcaniclastic sediments along a profile through the sedimentary sequence at DSDP Site 204. The arc and back‐arc lavas range from basalts to dacites in composition with SiO₂ = 48.3–65.3 wt% over which Li concentrations increase from 2 ppm to 16 ppm. Li/Y ratios range from 0.08 to 0.77 and from 0.24 to 0.65 in the arc and back‐arc lavas, respectively. The majority of the lavas have δ⁷Li that ranges from 2.5 ‰ to 5.0 ‰ with an average of (3.6 ±0.7) ‰, similar to that reported from other arcs and there is no distinction between the arc front and back‐arc lavas. The pelagic sediments have variable Li concentrations (33–133 ppm) and δ⁷Li that ranges from 1.2 ‰ to 10.2 ‰ while the volcaniclastic sediments have an even greater range of Li concentrations (3.6–165 ppm) and generally higher δ⁷Li values (8–14 ‰). However, δ⁷Li in the lavas does not correlate with commonly used trace element ratio or isotope signatures indicative of slab‐derived fluids or the sediments. This is probably because the range of δ⁷Li in the lavas and sediments overlap. Calculated sediment mass‐balance models require significantly more sediment than previous estimates based on Th–Nd–Be isotopes. This may indicate that a sizeable proportion of the total Li budget in the lavas is provided by Li‐enriched fluids from the subducting sediments and/or altered oceanic crust.     

Interaction of Solar-Flare-Accelerated Nuclei with the Solar Photosphere and the Isotopic Composition of the Solar Wind

The nuclear interactions of solar-flare-accelerated protons and ions with the solar atmosphere and the deeper layers of the Sun lead to the formation of several stable and radioactive isotopes. This article examines the GEANT4 depth profiles of ²H, ³H, ³He, ⁶Li, ⁷Li, ¹⁰Be, and ¹⁴C. When accelerated particles pass through a layer of 0.1–2 g cm^–2, ⁶Li, ⁷Li, ¹⁰Be, and ¹⁴C isotopes form in sufficient amounts to explain their anomalous abundances in lunar soil samples. It is assumed that they escape into interplanetary space with coronal mass ejections immediately after the flare.     

Lead concentration and isotopic composition in five peridotite inclusions of probable mantle origin

The lead content of five whole-rock peridotite inclusions (four lherzolites and one harzburgite) in alkali basalt ranges from 82 to 570 ppb (parts per billion). Approximately 30–60 ppb of this amount can be accounted for by analyzed major silicate minerals (olivine ≤ 10 ppb; enstatite 5–28 ppb; chrome diopside ～400 ppb). Through a series of acid leaching experiments, the remainder of the lead is shown to be quite labile and to reside in either glassy or microcrystalline veinlets or accessory mineral phases, such as apatite and mica. The lead isotopic composition of the peridotites (²⁰⁶Pb/²⁰⁴Pb= 18.01–18.90;²⁰⁷Pb/²⁰⁴Pb= 15.52–15.61;²⁰⁸Pb/²⁰⁴Pb= 37.80–38.86) lies within the range of values defined by many modern volcanic rocks and, in particular, is essentially coextensive with the abyssal tholeiite field. In all but one instance, isotopic differences were found between the peridotite and its host alkali basalt. Two of the peridotites clearly demonstrated internal isotopic heterogeneity between leachable and residual fractions that could not simply be due to contamination by the host basalt. However, there is no evidence that these ultramafic rocks form some layer in the mantle with isotopic characteristics fundamentally different from those of the magma sources of volcanic rocks.     

Fumaroles in ice caves on the summit of Mount Rainier—preliminary stable isotope, gas, and geochemical studies

The edifice of Mount Rainier, an active stratovolcano, has episodically collapsed leading to major debris flows. The largest debris flows are related to argillically altered rock which leave areas of the edifice prone to failure. The argillic alteration results from the neutralization of acidic magmatic gases that condense in a meteoric water hydrothermal system fed by the melting of a thick mantle of glacial ice. Two craters atop a 2000-year-old cone on the summit of the volcano contain the world's largest volcanic ice-cave system. In the spring of 1997 two active fumaroles (T=62°C) in the caves were sampled for stable isotopic, gas, and geochemical studies.Stable isotope data on fumarole condensates show significant excess deuterium with calculated δD and δ¹⁸O values (−234 and −33.2‰, respectively) for the vapor that are consistent with an origin as secondary steam from a shallow water table which has been heated by underlying magmatic–hydrothermal steam. Between 1982 and 1997, δD of the fumarole vapor may have decreased by 30‰.The compositions of fumarole gases vary in time and space but typically consist of air components slightly modified by their solubilities in water and additions of CO₂ and CH₄. The elevated CO₂ contents (δ¹³C_CO2=−11.8±0.7‰), with spikes of over 10,000 ppm, require the episodic addition of magmatic components into the underlying hydrothermal system. Although only traces of H₂S were detected in the fumaroles, most notably in a sample which had an air δ¹³C_CO2 signature (−8.8‰), incrustations around a dormant vent containing small amounts of acid sulfate minerals (natroalunite, minamiite, and woodhouseite) indicate higher H₂S (or possibly SO₂) concentrations in past fumarolic gases.Condensate samples from fumaroles are very dilute, slightly acidic, and enriched in elements observed in the much higher temperature fumaroles at Mount St. Helens (K and Na up to the ppm level; metals such as Al, Pb, Zn Fe and Mn up to the ppb level and volatiles such as Cl, S, and F up to the ppb level).The data indicate that the hydrothermal system in the edifice at Mount Rainier consists of meteoric water reservoirs, which receive gas and steam from an underlying magmatic system. At present the magmatic system is largely flooded by the meteoric water system. However, magmatic components have episodically vented at the surface as witnessed by the mineralogy of incrustations around inactive vents and gas compositions in the active fumaroles. The composition of fumarole gases during magmatic degassing is distinct and, if sustained, could be lethal. The extent to which hydrothermal alteration is currently occurring at depth, and its possible influence on future edifice collapse, may be determined with the aid of on site analyses of fumarole gases and seismic monitoring in the ice caves.     

Tracking the lithium isotopic evolution of the mantle using carbonatites

Carbonatites are mantle-derived, intraplate magmas that provide a means of documenting isotopic variations of the Earth's mantle through time. To investigate the secular Li isotopic evolution of the mantle and to test whether Li isotopes document systematic recycling of material processed at or near the Earth's surface into the mantle, we analyzed the Li isotopic compositions of carbonatites and spatially associated mafic silicate rocks. The Li isotopic compositions of Archean (2.7 Ga) to Recent carbonatites (δ⁷Li = 4.1 ± 1.3 (n = 23, 1σ)) overlap the range typical for modern mantle-derived rocks, and do not change with time, despite ongoing crustal recycling. Thus, the average Li isotopic composition of recycled crustal components has not deviated greatly from the mantle value (~ + 4) and/or Li diffusion is sufficiently fast to attenuate significant heterogeneities over timescales of 10⁸ years. Modeling of Li diffusion at mantle temperatures suggests that limited δ⁷Li variation in the mantle through time reflects the more effective homogenization of Li in the mantle compared to radiogenic isotope systems. The real (but limited) variations in δ⁷Li that exist in modern mantle-derived magmas as well as carbonatites studied here may reflect isotopic fractionation associated with shallow-level processes, such as crustal assimilation and diffusive isotopic fractionation in magmatic systems, with some of the scatter possibly related to low-temperature alteration.     

Patterns of dissolved organic matter in subarctic peatlands

Samples of water from poor to very rich fens in the Schefferville region of subarctic Quebec revealed strong spatial and temporal variations in dissolved organic carbon (DOC), ranging from 2 to 40 mg 1^?1. Concentrations of DOC tend to increase during the summer and decrease in the autumn, at most sites, which probably reflects increased plant tissue decomposition and higher rates of evapotranspiration. Principal components analysis revealed that DOC is strongly associated with Fe, NO^?₃-N and NO^?₂-N, but essentially independent of other chemical properties of the peat water, such as pH, Ca, Mg, K, P, and NH⁺₄-N. Based on observed concentrations of DOC and estimates of summer runoff (June to September), export of DOC from four peatlands ranges from 1·1 to 4·9 gCm^?2, with the lowest values for peatlands underlain by dolomite. Molecular weight fractionation of four samples revealed significant differences in the dissolved organic matter (DOM), with the largest fractions (GF/C to 10 000 nmw) being dominant in the more acid samples. The ratio of absorbance at 400 and 600 nm wavelengths (E₄:E₆) has been used as a simple indicator of differences in DOM type, ranging from 3 to 15. There is a strong seasonal pattern of increasing E₄:E₆ ratio during the summer at many sites, though this ratio is essentially independent of other chemical properties of peat waters.     

Evidence for244Pu fission tracks in hibonites from Murchison carbonaceous chondrite

We have developed a technique for revealing nuclear tracks in the mineral hibonite (CaAl₁₂O₁₉), found in the refractory inclusions from carbonaceous chondrites. The tracks in hibonitesfrom Murchison carbonaous chondrite are dominated by fission tracks from²⁴⁴Pu (constituting more than 90% of the total). The measured uranium contents in these crystals range from 1.2 to 62 ppb. We deduce that the average value for the²⁴⁴Pu/²³⁸U ratio in most of the Murchison hibonites at the time of track retention is0.022 ± 0.011.     

Oxysulfates of copper, sodium, and potassium in the lava flows of the 2012–2013 Tolbachik Fissure Eruption

Samples from the surface of lava flows discharged by the 2012–2013 Tolbachik Fissure Eruption were found to contain oxysulfates of copper, sodium, and potassium: K₂Cu₃O(SO₄)₂ (fedotovite), NaKCu₂O(SO₄)₂, and Na₃K₅Cu₈O₄(SO₄)₈. The last two phases have no naturally occurring or synthetic analogues that we are aware of. They form flattened crystals of prismatic to long-prismatic habits. The crystals of Na₃K₅Cu₈O₄(SO₄)₈ have a chemical composition corresponding to the empirical formula Na_2.22K_5.47Cu_8.02S_8.05O₃₆. An X-ray analysis of this compound showed that it has a monoclinic symmetry, P2/c, a = 13.909(4), b = 4.977(1), c = 23.525(6) Å, β = 90.021(5)°, V = 1628.3(7) ų. The crystal structure was determined by direct techniques and refined to yield R ₁ for 3955 reflexes//web// with F ² > 4σF. The compound NaKCu₂O(SO₄)₂ also belongs to the monoclinic system, P2/c, a = 14.111(4), b = 4.946(1), c = 23.673(6) Å, β = 92.052(6)°, V = 1651.1(8) ų. The structure was determined by direct techniques to yield a tentative structural model that has been refined up to R ₁ = 0.135 for 4088 reflexes with F ² > 4σF. The crystal structure of Na₃K₅Cu₈O₄(SO₄)₈ is based on chains of [O₂Cu₄]⁴⁺ consisting of rib-coupled oxy-centered tetrahedrons of (OCu₄)⁶⁺. The chains are surrounded by sulfate radicals, resulting in columns of {[O₂Cu₄](SO₄)₄}^4? aligned along the b axis. The interchain space contains completely ordered positions of Na⁺ and K⁺ cations. The principle underlying the connection of NaKCu₂O(SO₄)₂ columns in the crystal structure of {[O₂Cu₄](SO₄)₄}^4? is different, in view of the relation Na:K = 1 as contrasted with 3:5 for the compound Na₃K₅Cu₈O₄(SO₄)₈. The presence of oxy-centered tetrahedrons in the structure of these new compounds furnishes an indirect hint at the importance of polynuclear copper-oxygen radicals with centering oxygen atoms as forms of transport of copper by volcanic gases.     

Author index volume 40

Tracer diffusion coefficients for Li in glasses of albite, orthoclase, and obsidian composition have been determined by a method involving deposition of a thin source on polished glass wafers, anneal under controlled temperature conditions (300–900°C), and ion-microprobe determination of the concentration profile. All results conform to an Arrhenius-type relationship,D = D₀exp(?Q/RT), whereQ is 23, 17, and 22 kcal mol^?1;D₀ is 0.2, 0.003, and 0.03 cm²s^?1 for albite and orthoclase glasses, and obsidian respectively. Lithium is thus a fast diffusing ion and behaves similarly to sodium in the same glasses. A mechanism involving jumps of the diffusing ions through oxygen hexagonal rings is suggested by consideration of ionic radii ratio of alkali (H, Li, Na, K, Rb, and Cs) ions to the oxygen anions.     

Sorption of Eu<Superscript>3+</Superscript>onto nano-size silica-water interfaces

The sorption of Eu species onto nano-size silica-water interfaces is investigated at pH range of 1―8.5 and the initial Eu concentrations (C_Eu) of 2×10⁻⁵, 2×10⁻⁴ and 2×10⁻³ M using fluorescence spectroscopy. The sorption rate of Eu is initially low, but significantly increases at pH > 4. For the initial C_Eu of 2×10⁻⁵, 2×10⁻⁴ and 2×10⁻³ M, the dissolved Eu species are completely sorbed onto silica-water interfaces at pH = 4.75, −5.8 and 6.6, respectively, with the respective sorption densities of −1.58×10⁻⁸, 1.58×10⁻⁷ and 1.58×10⁻⁶ mol/m². The sorbed Eu species at pH < 6 is aquo Eu³⁺, which is sorbed onto silica-water interfaces as an outer-sphere complex at pH < 5, but may be sorbed as an inner-sphere bidentate complex at 5 < pH < 6, due to the decrease of the N_H2O to −6 at pH = 6. At pH = 6 – 8, Eu(OH)²⁺, Eu(CO₃)⁺and Eu(CO₃)₂ ⁻ form in the solutions, and Eu(CO₃)⁺is dominant at pH = −7.5. These ions may be sorbed onto silica-water interfaces as inner-sphere bidentate complexes or multi-nuclear pre-cipitates.     

The influence of plants on atmospheric carbon monoxide and dinitrogen oxide

It is shown by laboratory experiments and extensivein-situ measurements that higher plants (Vicia faba, Platanus acerifolia, Fagus silvatica, andPinus silvestris) produce carbon monoxide. The measurements were carried out under natural conditions with respect to the concentrations of O₂ and H₂O, and temperature. The CO₂- and CO-mixing ratios were varied in the ranges 350 to 530 ppm and 3–270 ppb, respectively. The CO-production rates were found to be light dependent with an average value per cm² of leaf area of 3×10^–13 g/sec for a radiation intensity of 5×10⁴ erg/cm² sec. The production rates are independent of the CO₂- and CO-mixing ratios employed in the test atmosphere. Considering the production rate of 3×10^–13 g/cm² sec to be representative for global conditions the total CO-production by plants is estimated to be 0.5–1.0×10¹⁴ g/year. In contrast to carbon monoxide atmospheric dinitrogen oxide is not influenced by plants in the same manner.     

A lithium isotopic study of sub-greenschist to greenschist facies metamorphism in an accretionary prism,New Zealand

To investigate the behavior of Li during low-grade metamorphism and fluid flux in an accretionary prism we measured the Li concentrations ([Li]) and isotopic compositions (δ⁷Li) of sub-greenschist and greenschist-facies Otago Schist composites, as well as cross-cutting quartz veins, which are interpreted to have precipitated from slab-derived fluids. The average [Li] of sub-greenschist facies composites (41 ± 13 μg/g, 2σ) is statistically distinct (97% confidence level, student t test) to that of greenschist facies composites (34 ± 9 μg/g, 2σ), which have experienced mass addition of silica in the form of quartz veins having [Li] between 0.4–2.3 μg/g. A linear regression of the correlation between [Li] and calculated mass additions suggests that the depletion of [Li] in greenschist facies composites is due to both dilution from the addition of the quartz veins, as well as metamorphic dehydration. The [Li] of both groups of composites correlates with their CIA (Chemical Index of Alteration) values (50–58), which are low, consistent with the inferred graywacke protolith of the Otago Schist. The δ⁷Li of sub-greenschist and greenschist facies composites are remarkably constant, with an average δ⁷Li of 0.2 ± 1.7 (2σ) and ?0.5 ± 1.9 (2σ), respectively, and comparable to that of the average upper continental crust. Thus, metamorphism has had no discernable effect on δ⁷Li in these samples. The Li isotopic signature of the schists is similar to that seen in pelitic sedimentary rocks and likely reflects the δ⁷Li of the protoliths. The surprisingly light δ⁷Li of the quartz veins (?2.8 to ?1.4) likely records kinetic fractionation associated with Li ingress into the veins from surrounding wallrock.An isotopic equilibrium fluid flow model indicates that: 1) if the [Li] of slab-derived fluids is less than a few μg/g, the δ⁷Li of the overlying lithologies (i.e., the schists) is not significantly influenced by the fluid flux, regardless of the δ⁷Li of the fluids, 2) the slab-derived fluids will have heavy δ⁷Li of > + 10 after reacting with the prism sediments during their ascent, and 3) the [Li] of the slab-derived fluids is likely in the range of 0 < [Li] ≤ 41(μg/g). Thus, isotopically heavy slab-derived fluids that traverse sediments in accretionary prisms may leave little trace in the rocks and their surface compositional characteristics will reflect the net result of their interaction with the sediments of the prism.     

Lithium and lithium isotope profiles through the upper oceanic crust: a study of seawater-basalt exchange at ODP Sites 504B and 896A

Ocean Drilling Program (ODP) Hole 504B near the Costa Rica Rift is the deepest hole drilled in the ocean crust, penetrating a volcanic section, a transition zone and a sheeted dike complex. The distribution of Li and its isotopes through this 1.8-km section of oceanic crust reflects the varying conditions of seawater alteration with depth. The upper volcanic rocks, altered at low temperatures, are enriched in Li (5.6-27.3 ppm) and have heavier isotopic compositions (δ⁷Li=6.6-20.8‰) relative to fresh mid-ocean ridge basalt (MORB) due to uptake of seawater Li into alteration clays. The Li content and isotopic compositions of the deeper volcanic rocks are similar to MORB, reflecting restricted seawater circulation in this section. The transition zone is a region of mixing of seawater with upwelling hydrothermal fluids and sulfide mineralization. Li enrichment in this zone is accompanied by relatively light isotopic compositions (−0.8-2.1‰) which signify influence of basalt-derived Li during mineralization and alteration. Li decreases with depth to 0.6 ppm in the sheeted dike complex as a result of increasing hydrothermal extraction in the high-temperature reaction zone. Rocks in the dike complex have variable isotopic values that range from −1.7 to 7.9‰, depending on the extent of hydrothermal recrystallization and off-axis low-temperature alteration. Hydrothermally altered rocks are isotopically light because ⁶Li is preferentially retained in greenschist and amphibolite facies minerals. The δ⁷Li values of the highly altered rocks of the dike complex are complementary to those of high-temperature mid-ocean ridge vent fluids and compatible to equilibrium control by the alteration mineral assemblage. The inventory of Li in basement rocks permits a reevaluation of the role of oceanic crust in the budget of Li in the ocean. On balance, the upper 1.8 km of oceanic crusts remains a sink for oceanic Li. The observations at 504B and an estimated flux from the underlying 0.5 km of gabbro suggest that the global hydrothermal flux is at most 8×10⁹ mol/yr, compatible with geophysical thermal models. This work defines the distribution of Li and its isotopes in the upper ocean crust and provides a basis to interpret the contribution of subducted lithosphere to arc magmas and cycling of crustal material in the deep mantle.     

Helium and carbon isotopes in fluorites: implications for mantle carbon contribution in an ancient subduction zone

The concentrations of helium and carbon in fluorite associated with Cretaceous to Neogene (90–13 Ma) granitic magmatism in the Japanese arc have been measured. Concentrations of Li, U, Th and Gd were measured to correct for secondary generated ³He. The CO₂/³He of fluorites are almost uniform (1.5×10¹⁰–4×10¹⁰) and in fair agreement with the range of present island arc volcanic gases. The calculated mantle C contribution in the Mesozoic subduction zone appear to have been identical to the present one (7–19%) indicating that the C flux from the mantle in supra-subduction zone environments has remained fairly constant during the past 70 million years.     

Major Ion and Trace Metal Geochemistry of an Acidic Septic-System Plume in Silt

Four years of detailed ground-water monitoring at a newly installed, seasonal-use, domestic septic system located on poorly buffered (CaCO₃ equivalent content ≤ 1.6 wt.%) lacustrine silt, has revealed the development of an acidic ground-water plume. Acid, generated by the partial oxidation of effluent NH₄⁺ dissolved organic carbon (DOC), and possibly sulfide minerals present in the sediment, has resulted in a distal plume core zone with pH values in the range of 4.4 to 5.0. The acidic zone, where NH₄⁺ does, however, persist (> 2 mg/1, as N) and where DOC remains elevated (6–13 mg/1), is associated with high average concentrations of the trace metals Fe (4.7 mg/1), Al (1.9 mg/1), and Mn (3.6 mg/1). Attenuation of nitrogen along the plume core flowpath is indicated by a decrease in the N/ Cl⁻ ratio from an effluent value of 1.7, to a plume value of only 0.5 after 4 m of subsurface flow. Increased SO₄²⁻ levels observed in the zone of N depletion suggest that attenuation can be at least partly attributed to reduction of plume NO₃⁻ by oxidation of reduced S present in the sediment. PO₄³⁻ has not migrated significantly beyond the infiltration bed gravel layer, demonstrating that PO₄³⁻ mobility is limited in these sediments (retardation factor > 10).     

Magnesioferrite from the Cretaceous-Tertiary boundary,Caravaca, Spain

Magnesioferrite grading toward magnetite has been identified as a very small but meaningful constituent of the basal iron-rich portion of the Cretaceous-Tertiary (K-T) boundary clay at the Barranco del Gredero section, Caravaca, Spain. This spinel-type phase and others of the spinel group, found in K-T boundary clays at many widely separated sites, have been proposed as representing unaltered remnants of ejecta deposited from an earth-girdling dust cloud formed from the impact of an asteroid or other large bolide at the end of the Cretaceous period. The magnesioferrite occurs as euhedral, frequently skeletal, micron-sized octahedral crystals. The magnesioferrite contains29 ± 11 ppb Ir, which accounts for only part of the Ir anomaly at this K-T boundary layer(52 ± 1 ppb Ir). Major element analyses of the magnesioferrite show variable compositions. Some minor solid solution exists toward hercynite-spinel and chromite-magnesiochromite. A trevorite-nichromite (NiFe₂O₄-NiCr₂O₄) component is also present. The analyses are very similar to those reported for sites at Furlo and Petriccio, Umbria, Italy.On the basis of the morphology and general composition of the magnesioferrite grains, rapid crystallization at high temperature is indicated, most likely directly from a vapor phase and in an environment of moderate oxygen fugacity. Elemental similarity with metallic alloy injected into rocks beneath two known impact craters suggests that part of the magnesioferrite may be derived from the vaporized chondritic bolide itself, or from the mantle; there is no supporting evidence for its derivation from crustal target rocks.     

Hydrostatic theory of the Earth and its mechanical implications

A second-order hydrostatic theory is developed on the assumption that the trace of the Earth's inertia tensor, its mass and mean radius are invariant under any process causing deviations from the hydrostatic state.The hydrostatic flattening and the zonal coefficients of the hydrostatic gravitational field are obtained as ?^?1 = 299.638, J₂ = 1072.618 × 10^?6 and J₄ = ?2.992 × 10^?6, respectively.The internal theory using the preliminary reference earth model (PREM) of Dziewonski and Anderson (1981) yields ?^?1 = 299.627, J₂ = 1072.701 × 10^?6 and J₄ = ?2.992 × 10^?6. The agreement between these and the hydrostatic values indicate that PREM is suitable as a reference model as it represents the spheroidal density distribution in a state of zero non-hydrostatic stress while satisfying the fundamental geodetic observations of the invariant quantities.The small discrepancy between the hydrostatic flattening and the value deduced from PREM suggests that the density is underestimated at large depths and/or it is slightly overestimated in shallow regions of the Earth.The discrepancies between the hydrostatic and observed quantities persist after the removal of the accountable effects of isostatically compensated topography, permanent tidal deformation and the present mass anomalies associated with the Late-Pleistocene deglaciation. These ‘corrected’ discrepancies point to a triaxial non-hydrostatic figure which cannot be explained by the delayed response of the Earth to tidal deceleration.