Sorption of noble gases by solids,with reference to meteorites. I. Magnetite and carbon

To simulate trapping of meteoritic noble gases by solids, 18 samples of Fe₃O₄ were synthesized in a noble gas atmosphere at 350–720 K by the reactions: 3Fe + 4H₂O → Fe₃O₄ + 4H₂ (Ne, Ar, Kr, Xe) 3Fe + 4CO → Fe₃O₃ + 4C + carbides (Xe only) Phases were separated by selective solvents (HgCl₂, HCl). Noble gas contents were analyzed by mass spectrometry, or, in runs where 36 d Xe¹²⁷ tracer was used, by γ-counting. Surface areas, as measured by the BET method, ranged from 1 to 400 m²/g. Isotopic fractionations were below the detection limit of 0.5%/m.u.Sorption of Xe on Fe₃O₄ and C obeys Henry's Law between $\text{1 × 10}{}^{\mathrm{?8}}$ and $\text{4 × 10}{}^{\mathrm{?5}}$ atm, but shows only a slight temperature dependence between 650 and 720 K ($\text{ΔH}{}_{\mathrm{sol}}\text{= ?4 ± 2}\text{kcal/mole}$). The mean distribution coefficient K_Xe is $\text{0.28 ± 0.09}$ cc STP/g atm for Fe₃O₄ and only a factor of $\text{1.2 ± 0.4}$ greater for C; such similarity for two cogenetic phases was predicted by Lewis et al. (1977). Stepped heating and etching experiments show that 20–50% of the total Xe is physically adsorbed and about 20% is trapped in the solid. The rest is chemisorbed with $\text{ΔH}{}_{\mathrm{s}}\text{? ?13}\text{kcal/mole}$. The desorption or exchange half-time for the last two components is >10² yr at room temperature.Etching experiments showed a possible analogy to “Phase $\text{Q}$” in meteorites. A typical carbon + carbide sample, when etched with HNO₃, lost 47% of its Xe but only 0.9% of its mass, corresponding to a ~0.6 Å layer. Though this etchable, surficial gas component was more thermolabile than $\text{Q}$ (release $\text{T}$ below 1000°C, compared to 1200–1600°C), another experiment shows that the proportion of chemisorbed Xe increases upon moderate heating (1 hr at 450°C). Apparently adsorbed gases can become “fixed” to the crystal, by processes not involving volume diffusion (recrystallization, chemical reaction, migration to traps, etc.). Such mechanisms may have acted in the solar nebula, to strengthen the binding of adsorbed gases.Adsorbed atmospheric noble gases are present in all samples, and dominate whenever the noble gas partial pressure in the atmosphere is greater than that in the synthesis. Many of the results of Lancet and Anders (1973) seem to have been dominated by such an atmospheric component; others are suspect for other reasons, whereas still others seem reliable. When the doubtful samples of Lancet and Anders are eliminated or corrected, the fractionation pattern—as in our samples—no longer peaks at Ar, but rises monotonically from Ne to Xe. No clear evidence remains for the strong temperature dependence claimed by these authors.     

Sorption of noble gases by solids,with reference to meteorites. III. Sulfides,spinels, and other substances; on the origin of planetary gases

To simulate trapping of noble gases by meteorites, we reacted 15 FeCr or FeCrNi alloy samples with CO, H₂O or H₂S at 350–720 K, in the presence of noble gases. The reaction products, including (Fe,Cr)₂O₃, FeCr₂S₄, FeS, C, and Fe₃C, were analyzed by mass spectrometry, usually after chemical separation by selective solvents. Three carbon samples were prepared by catalytic decomposition of CO or by dehydration of carbohydrates with H₂SO₄.The spinel and carbon samples were similar to those of earlier studies (Yang et al., 1982 and Yang and Anders, 1982), with only minor effects attributable to the presence of Ni. All samples sorted substantial amounts of noble gases, with distribution coefficients of 10^?1–10^?2 cm³ STP/g atm for Xe. On the basis of release temperature three gas components were distinguished: a generally dominant physisorbed component (20–80% of total), and two more strongly bound, chemisorbed and trapped components. Judging from the elemental pattern, the adsorbed components were acquired at the highest noble gas partial pressure encountered by the sample—atmosphere or synthesis vessel.Sulfides, particularly daubréelite, showed three distinctive trends relative to chromite or magnetite: the high-T component was larger, 30–70% of the total; $\text{Ne}\text{Xe}$ ratios were higher, by up to 10², possibly due to preferential diffusion of Ne during synthesis. In one synthesis, at relatively high P, the gases were sorbed with only minimal elemental fractionation, presumably by occlusion.Most of the features of primordial noble gases can be explained in terms of the data and concepts presented in the three papers of this series. The elemental fractionation pattern of Ar, Kr, Xe in meteorites, terrestrial rocks, and planets resembles the adsorption pattern on the solids studied: carbon, spinels, Sulfides, etc. The variation in $\text{Ne}\text{Ar}$ ratio may be explained by preferential diffusion of Ne. The high release temperature of meteoritic noble gases may be explained by transformation of physisorbed to chemisorbed gas, as observed in some experiments. The ready loss of meteoritic heavy gases on surficial oxidation (“Phase Q”) is consistent with adsorption, as is the high abundance. Extrapolation of the limited laboratory data suggests that the observed amounts of noble gases could have been adsorbed from a solar gas at 160–170 K and 10^?6–10^?5 atm, i.e. in the early contraction stages of the solar nebula. The principal unsolved problem is the origin of isotopically anomalous, apparently mass-fractionated noble gases in the Earth's atmosphere and in meteoritic carbon and chromite.     

Are C1 chondrites chemically fractionated? a trace element study

Six C1 chondrite samples and a C2 xenolith from the Plainview H5 chondrite were analyzed by radiochemical neutron activation for the elements Ag, Au, Bi, Br, Cd, Ce, Cs, Eu, Ge, In, Ir, Lu, Nd, Ni, Os, Pd, Pt, Rb, Re, Sb, Se, Sn, Tb, Te, Tl, Yb, and Zn. The data were combined with 9 earlier analyses from this laboratory and examined for evidence of chemical fractionation in C1 chondrites.A number of elements (Br, Rb, Cs, Au, Re, Os, Ni, Pd, Sb, Bi, In, Te) show small but correlated variations. Those of the first 8 probably reflect hydrothermal alteration in the meteorite parent body, whereas those of Sb, Bi, In, and Te may at least in part involve nebular processes. Br and Au show systematic abundance differences from meteorite to meteorite, which suggests hydrothermal transport on a kilometer scale. The remaining elements vary from sample to sample, suggesting transport on a centimeter scale.There is no conclusive evidence for nebular fractionation affecting C1 's. Though C1 chondrites have lower $\text{Zr}\text{Hf}$ and $\text{Ir}\text{Re}$ ratios than do other chondrite classes, these ratios vary in other classes, suggesting that those classes rather than C1's are fractionated. Three fractionation-prone REE—Ce, Eu, and Yb have essentially the same relative abundances in C1's and all other chondrite classes, and hence apparently are not fractionated in C1's. We did not confirm the large Tb and Yb variations in C1's reported by other workers.We present revised mean C1 abundances for 35 elements, based on the new data and a critical selection of literature data. Changes are generally less than 10%, except for Br, Rb, Ag, Sb, Te, Au, and the REE.The Plainview C2 xenolith has normal trace element abundances, except for 3 elements falling appreciably above the C2 range: Rb, Cs, and Bi. Hydrothermal alteration may be the reason for all 3, though nebular fractionation remains a possibility for Bi.     

Rock bursting phenomena in a superficial rock mass in southern central Sweden

SummaryRock Bursting Phenomena in a Superficial Rock Mass in Southern Central Sweden Rock bursting phenomena have been observed in connection with excavation of two shallow sited rock tunnels in the Forsmark area in southern, central Sweden. The tunnels are excavated in gneiss granite and the rock cover varies between 5–15 m. The stress release occurred locally in the tunnels which indicates significant variations in rock stresses.In situ measurements of the triaxial stress situation carried out in the area show values of the principal stresses in the horizontal plane of a magnitude in excess of 20 MPa in the superficial rock mass. The rock stress measurements indicate a clear correspondence of the directions of the highest compressive stress and the rock foliation. There is also a clear correspondence between the directions of a vertical and a horizontal joint set and the highest compressive stress. The three-dimensional stress tensor indicates that the horizontal fractures are exposed to the smallest closure pressure, i. e. the vertical stress, which set should therefore be most open. The horizontal joint set in the superficial rock mass has a significantly higher value of aperture than the vertical sets which may be a consequence of the stress situation in the rock mass. The rock bursting is not attributed to a breakage of the rock matrix, but merely to a propagation of already existing small fractures and potential fractures. The stress situation in the Forsmark area may be regarded as an uniaxial stress field in the horizontal plane.With 12 Figures     

Respiration of Recently-Fixed Plant Carbon Dominates Mid-Winter Ecosystem CO2 Production in Sub-Arctic Heath Tundra

Arctic ecosystems could provide a substantial positive feedback to global climate change if warming stimulates below-ground CO₂ release by enhancing decomposition of bulk soil organic matter reserves.Ecosystem respiration during winter is important in this context because CO₂ release from snow-covered tundra soils is a substantial component of annual net carbon (C) balance, and because global climate models predict that the most rapid rises in regional air temperature will occur in the Arctic during winter. In this manipulative field study, the relative contributions of plant and bulk soil organic matter C pools to ecosystem CO₂ production in mid-winter were investigated. We measured CO₂ efflux rates in Swedish sub-arctic heath tundra from control plots and from plots that had been clipped in the previous growing season to disrupt plant activity. Respiration derived from recently-fixed plant C (i.e., plant respiration, and respiration associated with rhizosphere exudates and decomposition of fresh litter) was the principal source of CO₂ efflux, while respiration associated with decomposition of bulk soil organic matter was low, and appeared relatively insensitive to temperature. These results suggest that warmer mid-winter temperatures in the Arctic may have a much greater impact on the cycling of recently-fixed, plant-associated C pools than on the depletion of tundra bulk soil C reserves, and consequently that there is a low potential for significant initial feedbacks from arctic ecosystems to climate change during mid-winter.     

Measured And Simulated Latent And Sensible Heat Fluxes At Two Marine Sites In The Baltic Sea

In this study, turbulent heat flux data from two sites within the Baltic Sea are compared with estimates from two models. The main focus is on the latent heat flux. The measuring sites are located on small islands close to the islands of Bornholm and Gotland. Both sites have a wide wind direction sector with undisturbed over-water fetch. Mean parameters and direct fluxes were measured on masts during May to December 1998.The two models used in this study are the regional-scale atmospheric model HIRLAM and the ocean model PROBE-Baltic. It is shown that both models overestimate the sensible and latent heat fluxes. The overestimation can, to a large extent, be explained by errors in the air-water temperature and humidity differences. From comparing observed and modelled data, the estimated 8-month mean errors in temperature and humidity are up to 1 °C and 1 g kg^-1, respectively. The mean errors in the sensible and latent heat fluxes for the same period are approximately 15 and 30 W m^-2, respectively.Bulk transfer coefficients used for calculating heat and humidity fluxes at the surface were shown to agree rather well with the measurements, at least for the unstable data. For stable stratification, the scatter in data is generally large, and it appears that the bulk formulation chosen overestimates turbulent heat fluxes.     

Hydrogeologic studies for nuclear-waste disposal in Sweden

Safety Report 1997 (SR 97) of the Swedish Nuclear Fuel and Waste Management Company is a comprehensive performance assessment of three hypothetical radioactive waste repositories in Sweden. It includes hydrogeologic studies (data compilation, parameter synthesis, and groundwater flow modeling) to determine groundwater flow and the associated uncertainties for the three sites. This report reviews and compares the hydrogeologic characterization programs, the site characteristics, and the groundwater flow models used in the SR 97 performance assessment. Although differences in site-characterization programs tend to mask differences in site characteristics, the sites do have notable differences that affect the results of the performance assessment. The effects of model uncertainties evaluated by the variant cases appear to be smaller than the variability of results for the base case (best estimate of site conditions) of each site. Electronic Publication     

Some physical and chemical properties of lakes in north-eastern Norway

Summary Chemical and physical properties in 12 lakes in the north-easternmost part of Norway are studied. Geologically the lakes are situated on the pre-cambrian “Baltic shield”, with metamorphic and intrusive rocks that are not easily soluble. Vertical series of temperature, pH, O₂ and x₁₈ together with colour measurements and transparency indicate that the lakes are temperate and fundamentally oligotrophic, some with a dystrophic character. Some individual differences are discussed, with special reference to the surroundings, flow-through rate and morphometry. In accordance with the geology of the area the amount of electrolytes is small. Major ions (Ca, Mg, Na, K, HCO₃, SO₄ and Cl) are analysed. The greatest differences in the composition of these ions in the lakes are shown to be due mainly to the varying proximity to the sea and to geological differences. Rain is shown to be the most important factor in supplying major ions toat least some of the lakes. Individual variations are discussed, and comparisons are made with the ionic composition of water in other districts.

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Zusammenfassung An 12 im n?rdlichesten Teil von Norwegen, auf dem pr?kambrischen Baltischen Schild gelegenen Seen werden die chemischen und physikalischen Eigenschaften studiert. Das Einzugsgebiet besteht aus schwerl?slichem, metamorphem und intrusivem Gestein. Die vertikale Verteilung von Temperatur, pH, O₂ und x₁₈ samt Farbmessungen und Transparenz zeigt, dass die Seen dem temperierten Typus angeh?ren und im wesentlichen oligotroph sind, einige von dystrophem Charakter. Einige individuelle Unterschiede werden er?rtert mit besonderer Berücksichtigung der Umgebung, der Durchflutungszeit und der Morphometrie. In übereinstimmung mit der geologischen Beschaffenheit der Umgebung ist der Elektrolytgehalt neigdrig. Die dominierenden Ionen (Ca, Mg, Na, K, HCO₃, SO₄ und Cl) werden analysiert. Es wird nachgewiesen, dass die gr?ssten Unterschiede in der Zusammensetzung dieser Ionen in den Seen auf die verschiedene Entfernung vom Meer und auf geologische Unterschiede zurückzuführen sind. Für einige der Seen wird nachgewiesen, dass der Regen als wichtigster Faktor für ihre Versorgung mit Ionen anzusehen ist. Es werden individuelle Unterschiede er?rtert und Vergleiche mit der ionalen Zusammensetzung von Gew?ssern anderer Gegenden gezogen.

     

Analysis of some aromatic hydrocarbons in a benzene-soluble bitumen from Green River shale

The hydrocarbon content of an aromatic fraction, isolated from the bitumen of Green River shale, was studied by mass spectrometry, infra-red spectrometry, gas chromatography and a dehydrogenation technique. The hydrocarbon types and their distribution in this aromatic fraction, as determined by mass spectrometry, include the following: C_nH_2n?6(10%), C_nH_{2n?8 (31 %)}, C_nH_2n?10(18%), C_nH_2n?12(12%), C_nH_2n?14(8%) and a series of alkenylbenzenes (20%). The carbon-number range, empirical formulae and quantity of each compound in the major types are reported. Mass spectra of several compounds and homologous mixtures of compounds isolated from the aromatic fraction are also given.