The distribution of helium in oceanic basalt glasses

We have determined the concentrations and isotopic composition of helium in oceanic basaltic glass both by melting and by crushing in vacuo. A significant fraction of the helium is released by crushing, confirming that it resides within the vesicles. Comparison of volume percent vesicles to the fraction of helium contained in the vesicles gives qualitative agreement with experimental gas-melt partitioning studies. Measured concentrations are therefore, a function of original helium content, magmatic history, vesicle size and quantity, and grain size analyzed. Helium released by crushing is isotopically indistinguishable from that contained in the glass. Diffusion rates for helium in basaltic glass (in the temperature range 125–400°C) determined using the method of stepwise heating, yielded an activation energy of 19.9 ± 1 kcal/mole andlnD₀ = ?2.7 ± 0.6 (cgs units). Extrapolation of these results to ocean floor temperatures (0°C) gives a diffusivity of 1.0 ± 0.6 × 10^?17 cm²/s, indicating that diffusion is an insignificant mechanism for helium loss from fresh basaltic glasses. The³He/⁴He ratios are remarkably constant (at 1.10 ± 0.03 × 10^?5) for samples from the Mid-Atlantic Ridge (FAMOUS area and 23°N), the Juan de Fuca Ridge, the Galapagos spreading center, the Mid-Cayman Rise, and the Central Indian Ocean Ridge. This result is interpreted in terms of similar geochemical histories within the source regions for these samples.     

Sulphur isotope equilibrium during sulphur hydrolysis at high temperatures

Studies of the sulphur hydrolysis reaction, 4S + 4H₂O /ag 3H₂S + HSO₄^? + H⁺, were conducted between 200 and 320°C in sealed silica glass tubes. The isotope exchange reaction: H₂¹⁸O + HS¹⁶O₄^? /ag H₂¹⁶O + HS¹⁸O₄^? is so rapid at the low pH (1.5–3) as to be unquenchable. However, the sulphur isotope exchange reaction: H₂³⁴S+ H³²SO₄^? /ag H₂³²S + H³⁴SO₄^? gave t12 values of 0.1, 0.3 and 1.7 days at 320, 260 and 200°C respectively and equilibrium H₂S - HSO₄^? sulphur isotope fractionation values of 20.9, 22.4, 24.8, 26.7 and 29.3‰ at 320, 290, 260, 230 and 200°C respectively. This latter data is represented by: 1000lnα_(HSO4^??H2S) = 5.07 (10⁶T^?2) + 6.33, and has valuable applications in geothermal and ore deposit studies.     

Ion microprobe studies of water in silicate melts: Temperature-dependent water diffusion in obsidian

The temperature dependence of water diffusivity in rhyolite melts over the range 650–950°C and [P_T(H₂O] = 700 bars is evaluated from water concentration-distance profiles measured in glass with an ion microprobe. Diffusivities are exponentially dependent on concentration over this temperature range and vary from about 10^?8 cm²/s at 650°C to about 10^?7 cm²/s at 950°C at 2 wt.% water. Water solubility also varies with temperature at a rate of ?0.14 wt. per 100°C increase. The avtivation energy (E_a) appears to be constant at 19 ± 1kal/mole for 1, 2,and 3 wt.% H₂O. Comparison of these data with results for cation diffusion indicates that this value is a minimum E_a for diffusion of any species in a rhyolite melt.Compensation plots of log₁₀D₀ (the frequency factor) versus E_a indicate that hydrous rhyolite melts follow the same trend as anhydrous basalts. D₀ increases for H₂O and Ca²⁺ [1] as E_a decreases. This suggests that these molecules may diffuse by different mechanisms than do monovalent cations, and that hydration of the melt affects diffusion of Ca²⁺ and H₂O differently than it does monovalent cation diffusion. The results imply that dramatic increases in cation diffusivities by hydration [1] may occur with additions of less than 1 wt.% H₂O.     

Experimental reproduction of textures of chondrules

The textures of chondrules have been reproduced by crystallizing melts of three different compositions at 1 atm with cooling rates ranging from 400 to 20°C/min under 10^?9 to 10^?12 atmP_O2. A porphyritic olivine texture has been formed from a melt of olivine-rich composition (SiO₂ = 45 wt.%), a barred-olivine texture from melt of intermediate composition (SiO₂ = 47 wt.%), and radial-olivine texture from melt of pyroxene-rich composition (SiO₂ = 57 wt.%). The cooling rate for producing barred olivine is most restricted; the rate ranges from 120 to 50°C/min. Other textures can be formed with wider ranges of cooling rate. The results of the experiments indicate that some of the major types of textures of chondrules can be formed with cooling rate of about 100°C/min. With this cooling rate, the texture varies depending on the composition of melt.     

Carbon monoxide on the primitive earth

The reaction of CO + OH^? in aqueous solution to give formate was studied as a carbon monoxide sink on the primitive earth and in the present ocean. The reaction is first order in OH^? and first order in the molar CO concentration. The second order rate constant is given by log k(M^?1hr^?1) = 15.83?4886/T between 25°C and 60°C. Using the solubility of CO in sea water, and assuming a pH of 8 for a primitive ocean of the present size, the halflife of CO in the atmosphere is calculated to be 12 × 10⁶ yr at 0°C and 5.5 × 10⁴ yr at 25°C.Three other CO sinks would have been important in the primitive atmosphere: CO + H₂ → H₂CO driven by various energy sources, CO + OH → CO₂ + H, and the Fischer-Tropsch reaction of CO + H₂ → hydrocarbons, etc. It is concluded that the lifetime of a CO atmosphere would have been very short on the geological time scale although the relative importance of these four CO sinks is difficult to estimate.The CO + OH^? reaction to give formate is a very minor CO sink on the earth at the present time.     

Acute toxicity of copper to sea catfish

Sea catfish (Arius felis) were exposed to aqueous solutions of reagent grade cupric chloride in artificial seawater ($\text{30.0±2.0‰}$, 21–23°C) in four static bioassays. The 24, 48, 72 and 96 h LC₅₀ were calculated and found to be 5.43, 4.17, 3.57 and 2.40 mg l.^?1 copper, respectively. Experimental concentrations of copper producing subtle behavioral changes in this species correspond to less than 0.3% of the 72 h LC₅₀. Based on this comparison with literature values, a new, maximum ‘safe’ concentration for copper in marine waters of 0.01 mg l.^?1 is proposed.     

Low boundary layer response and temperature dependence of nitrogen and phosphorus releases from oxic sediments of an oligotrophic lake

The effects of temperature, diffusive boundary-layer thickness, and sediment composition on fluxes of inorganic N and P were estimated for sediment cores with oxidized surfaces from nearshore waters (2?C10?m) of a montane oligotrophic lake. Fluxes of N and P were not affected by diffusive boundary-layer thickness but were strongly affected by temperature. Below 16?°C, sediments sequestered small amounts of P and released small amounts of N. Above 16?°C, the seasonal maximum water temperature, sediments were substantial sources of N (NH₄ ⁺?CN?=?2?C24?mg?m^?2 d^?1; NO₃ ^??+?NO₂ ^??CN?=?2?C5?mg?m^?2 d^?1) and P (0.1?C0.4?mg?m^?2 d^?1), indicating potential responsiveness of sediment?Cwater nutrient exchange, and of corresponding phytoplankton growth, to synoptic warming.     

Mineralogy and stable isotope geochemistry of hydrothermally altered oceanic rocks

Data for the diffusion of cations in pyroxenes are relevant to a variety of sub-solidus processes including order-disorder and exsolution. Similar data must also be available if the reliability of geobarometers and geothermometers involving pyroxenes is to be assessed. Two types of diffusion experiment have been performed to determine cation diffusion rates in pyroxenes: (1) interdiffusion between single crystals of diopside and polycrystalline sinters enriched in Al and Fe, and (2) interdiffusion between single crystals of diopside and a glass of the same composition which was isotopically enriched in²⁶Mg and⁴³Ca. Following high-temperature annealing for periods up to several hundred hours, analysis of the diffusion couples, using an electron microprobe and an ion microprobe respectively, failed to show any measurable diffusion profiles. From these “null result” experiments the diffusion coefficients (D) for Al and Fe in diopside are estimated to be less than4×10^?14cm²s^?1 at 1200°C, and values ofD for Ca and Mg in diopside are estimated to be less than7 × 10^?14cm²s^?1 at 1250°C. These rates are significantly slower than published tracer-type diffusion data for Ca and Al.A review of studies of order-disorder, microstructural coarsening, and diffusion in pyroxenes suggest that activation energies for cation exchange are typically in excess of 60 kcal mol^?1. Transport rates will be assisted, and activation energies lowered by sample non-stoichiometry, inhomogeneities, high dislocation densities and the presence of water.The collective data for Al, Mg and Ca diffusion in diopside indicate diffusion coefficients? 10^?15cm²s^?1 at 1200°C. A comparison with data for diffusion in garnet, olivine and spinel suggests that pyroxenes may have the highest blocking temperatures.     

Thermal expansion of stishovite

The thermal expansion of stishovite has been determined by an X-ray camera technique in a temperature range of 18 – 600°C at an atmospheric pressure. The thermal-expansion coefficients along the crystallographic a- and c-axes at 300 K are α_a = (6.0 ± 0.6) · 10^?6K^?1 and α_c = (1.4 ± 0.5) · 10^?6K^?1, respectively. The volume coefficient at 300 K is α_ν = (13.5 ± 0.6) · 10^?6K^?1.     

Experimental crystallization of chrome spinel in FAMOUS basalt 527-1-1

FAMOUS basalt 527-1-1 (a high-Mg oceanic pillow basalt) has three generations of spinel which can be distinguished petrographically and chemically. The first generation (Group I) have reaction coronas and are high in Al₂O₃. The second generation (Group II) have no reaction coronas and are high in Cr₂O₃ and the third generation (Group III) are small, late-stage spinels with intermediate Al₂O₃ and Cr₂O₃. Experimental synthesis of spinels from fused rock powder of this basalt was carried out at temperatures of 1175–1270°C and oxygen fugacities of 10^?5.5 to 10^?10 atm at 1 atm pressure. Spinel is the liquidus phase at oxygen fugacities of 10^?8.5 atm and higher but it does not crystallize at any temperature at oxygen fugacities less than 10^?9.5. The composition of our spinels synthesized at 1230–1250°C and 10^?9 atmf_O2 are most similar to the high-Cr spinels (Group II) found in the rock. Spinels synthesized at 1200°C and 10^?8.5 atm_O2 are chemically similar to the Group III spinels in 527-1-1. We did not synthesize spinel at any temperature or oxygen fugacity that are similar to the high-Al (Group I) spinel found in 527-1-1. These results indicate that the high-Cr (Group II) spinel is the liquidus phase in 527-1-1 at low pressure and Group III spinel crystallize below the liquidus (～1200°C) after eruption of the basalt on the sea floor. The high-Al spinel (Group I) could have crystallized at high pressure or from a magma enriched in Al and perhaps Mg compared to 527-1-1.     

Isotopic fractionations during oxygen consumption and carbonate dissolution within the North Atlantic Deep Water

The trajectory of the North Atlantic Deep Water is traced from 65°N to 20°N latitude. Along this track the dissolved O₂ decreases, theδ¹⁸O of the dissolved O₂ increases, and the¹⁴C content of the water decreases. From these observations the rate of in-situ O₂ utilization in the deep water is calculated to be 0.10 μmol kg^?1 yr^?1. As was observed previously in the Pacific, theδ¹⁸O data presented here indicate that the utilization is probably caused by bacterial respiration. Carbon dioxide is being added to the water at the rate of 0.07 μmol kg^?1 yr^?1 from the oxidation of this organic matter. An additional 0.12 μmol kg^?1 yr^?1 of CO₂ is derived from the dissolution of particles of CaCO₃.     

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.     

Elastic modulus and internal friction in enstatite,forsterite and peridotite at seismic frequencies and high temperatures

Spectra of internal friction between 2 and 8 Hz were studied in a single crystal of enstatite, in a polycrystal of synthetic forsterite and in several samples of natural peridotite. Measurements of Q^?1 and μ were performed in vacuum (10^?6 torr), from room temperature up to 1100°C. For these experimental conditions no peak was observed in the polycrystalline undeformed forsterite, but the background attenuation irregularly increased from 5 · 10^?3 to 10^?2.A peak Q^?1 = 7 · 10^?2 appears in a deformed peridotite at 930°C. It is reduced of 60% after 5 h of annealing at 1100°C. But the background attenuation persists. In the single crystal of enstatite, a peak is observed at 760°C (Q^?1 = 6 · 10^?2). A mechanism involving dislocations is suggested as a possible explanation for the peak obtained with the peridotite samples. If this hypothesis is right, the observed effect would be diffusion controlled so that one can expect pressure to translate it towards higher temperature. This mechanism could therefore appear in the upper mantle. Background attenuation could be the result of intergranular thermal losses.     

The influence of oxidation state on the electrical conductivity of olivine

The electrical conductivity of a single crystal of San Carlos olivine (Fo₉₂, 0.16 wt.% Fe₂O₃) has been measured as a function of temperature and oxygen fugacity (fO₂). After heating to 1338°C at fO₂ = 10^?12 atm., the conductivity at 950°C was 10^?5 (ohm-m)^?1, almost 3 orders of magnitude less than that measured in air. This decrease is due to the reduction of Fe³⁺ to Fe²⁺. Further heating to 1500°C at fO₂ = 10^?14 atm., decreased the electrical conductivity at 950°C to 10^?6 (ohm-m)^?1. When recovered at room temperature, the speciment had Fo₉₆ composition and contained small, opaque blebs distributed throughout the crystal. Derivations of temperature profiles for the earth's mantle from conductivity-depth models must take account of the important role played by iron oxidation state in the electrical conductivity of olivine.     

Lithium tracer-diffusion in an alkali-basaltic melt — An ion-microprobe determination

An ion-microprobe-based technique has been used to measure lithium tracer-diffusion coefficients (D_Li) in an alkali-basaltic melt at 1300, 1350 and 1400°C. The results can be expressed in the form:D_Li=7.5 ×10^?2exp(?27,600/RT)cm²S^?1The results show significantly faster diffusion rates than those previously recorded for other monovalent, divalent and trivalent cations in a tholeiitic melt. Consequently, diffusive transport of ions acting over a given time in a basaltic melt can produce a wider range of transport distance values than hitherto supposed. Hence, it is concluded that great care should be exercised when applying diffusion data to petrological problems.     

Apatite/liquid partition coefficients for the rare earth elements and strontium

Sixteen sets of apatite/liquid partition coefficients (D^ap/liq) for the rare earth elements (REE; La, Sm, Dy, Lu) and six values for Sr were experimentally determined in natural systems ranging from basanite to granite. The apatite + melt (glass) assemblages were obtained from starting glasses artificially enriched in REE, Sr and fluorapatite components; these were run under dry and hydrous conditions of 7.5–20 kbar and 950–1120°C in a solid-media, piston-cylinder apparatus. An SEM-equipped electron microprobe was used for subsequent measurement of REE and Sr concentrations in coexisting apatites and quenched glasses. The resulting partition coefficient patterns resemble previously determined apatite phenocryst/groundmass concentration ratios in the following respects: (1) the rare earth patterns are uniformly concave downward (i.e., the middle REE are more compatible in apatite than the light and heavy REE); (2) D_REE^ap/liq is much higher for silicic melts than for basic ones; and (3) strontium (and therefore Eu²⁺) is less concentrated by apatite than are the trivalent REE. The effects of both temperature and melt composition on D_REE^ap/liq are systematic and pronounced. At 950°C, for example, a change in melt SiO₂ content from 50 to 68 wt.% causes the average REE partition coefficient to increase from ～7 to ～30. A 130°C increase in temperature, on the other hand, results in a two-fold decrease in D_REE^ap/liq. Partitioning of Sr is insenstitive to changes in melt composition and temperature, and neither the Sr nor the REE partition coefficients appear to be affected by variations in pressure or H₂O content of the melt.The experimentally determined partition coefficients can be used not only in trace element modelling, but also to distinguish apatite phenocrysts from xenocrysts in rocks. Reported apatite megacryst/host basalt REE concentration ratios [12], for example, are considerably higher than the equilibrium partition coefficients, which suggest that in this particular case the apatite is actually xenocrystic.A reversal experiment incorporated in our study yielded diffusion profiles of REE in apatite, from which we extracted a REEαCa interdiffusion coefficient of 2–4×10^?14 cm²/s at 1120°C. Extrapolated downward to crustal temperatures, this low value suggests that complete REE equilibrium between felsic partial melts and residual apatite is rarely established.     

Thermal diffusivity of rhyolitic glasses and melts: effects of temperature, crystals and dissolved water

Thermal diffusivity (D) was measured using laser-flash analysis on pristine and remelted obsidian samples from Mono Craters, California. These high-silica rhyolites contain between 0.013 and 1.10?wt% H₂O and 0 to 2?vol% crystallites. At room temperature, D _glass varies from 0.63 to 0.68?mm²?s^?1, with more crystalline samples having higher D. As T increases, D _glass decreases, approaching a constant value of ??0.55?mm²?s^?1 near 700?K. The glass data are fit with a simple model as an exponential function of temperature and a linear function of crystallinity. Dissolved water contents up to 1.1?wt% have no statistically significant effect on the thermal diffusivity of the glass. Upon crossing the glass transition, D decreases rapidly near ??1,000?K for the hydrous melts and ??1,200?K for anhydrous melts. Rhyolitic melts have a D _melt of ??0.51?mm²?s^?1. Thermal conductivity (k?=?D·??·C _P) of rhyolitic glass and melt increases slightly with T because heat capacity (C _P) increases with T more strongly than density (??) and D decrease. The thermal conductivity of rhyolitic melts is ??1.5?W?m^?1?K^?1, and should vary little over the likely range of magmatic temperatures and water contents. These values of D and k are similar to those of major crustal rock types and granitic protoliths at magmatic temperatures, suggesting that changes in thermal properties accompanying partial melting of the crust should be relatively minor. Numerical models of shallow rhyolite intrusions indicate that the key difference in thermal history between bodies that quench to obsidian, and those that crystallize, results from the release of latent heat of crystallization. Latent heat release enables bodies that crystallize to remain at high temperatures for much longer times and cool more slowly than glassy bodies. The time to solidification is similar in both cases, however, because solidification requires cooling through the glass transition in the first case, and cooling only to the solidus in the second.     

Study of the Contributions of Non‐Specific and Specific Interactions during Fluoxetine Adsorption onto Activated Carbons

The adsorption of fluoxetine onto activated carbons (ACs) prepared from almond tree pruning by steam and CO₂ activation under different temperature conditions (650–950°C), was studied. In both series increasing the temperature caused an increase in the BET apparent surface area, yielding ACs with S_BET up to 870 and 710 m² g^?1 after steam and CO₂ activation, respectively. Also, a slight widening of the porosity was found in both cases. In order to modify the functionality of the ACs, two of them were impregnated with triethylenediamine (TEDA) prior to the adsorption process, which caused a decrease in the AC apparent surface mainly due to micropore blockage. The fluoxetine adsorption isotherms at 25°C showed maximum adsorption capacities between 110 and 224 mg g^?1. The adsorption isotherms were analyzed using Langmuir and Freundlich models. Although the impregnation reduced the pore volume, it did not cause a decrease in the fluoxetine maximum adsorption capacity, but a modification in the adsorption mechanism was observed.     

Experimental petrology of sample 77135

The matrix of 77135 would not be a liquid at less than 1280°C, 1 atm pressure. The petrography and lack of evidence of crystallization in the 1280-1150°C interval suggest that the matrix is either a devitrified, shock-melted and supercooled glass, or a devitrified, depressurised liquid whose liquidus temperature had been depressed by the presence of a small amount of water at pressures attainable in the upper part of the lunar crust. Devitrification fronts would have advanced faster than 1 mm min^?1 in 77135 glass at 1050°C under lunar surface conditions.     

The238U spontaneous fission decay constant re-determined by fission tracks

The decay constant(λ_f²³⁸) for the spontaneous fission of²³⁸U was re-determined by means of a man-made uranium glass of known age (126 yr). The spontaneous U fission tracks that had accumulated since the date of manufacture were counted on internal faces of the glass with an error of less than 1.7%. No thermal annealing of the spontaneous tracks was observed. The U content was determined by induced fission tracks. The value obtained forλ_f²³⁸ is(8.57 ± 0.42) × 10^?17yr^?1. Main sources of error are the date of glass melting and the determination of the thermal neutron dose.