Low solubility of He and Ar in carbonatitic liquids: Implications for decoupling noble gas and lithophile isotope systems

In order to asses the importance of carbonatitic liquids in transporting noble gases in the mantle, the solubilities of He and Ar in carbonatitic liquids were estimated from analyses of calcium-potassium carbonate glasses that had been synthesized at 1 bar and temperatures between 850 and 950 °C under He or Ar enriched atmospheres. Despite poor reproducibility related to difficulties synthesizing carbonatite glass, we have been able to estimate He and Ar solubilities in carbonatite liquids to be 1 × 10⁻⁸ and 2 × 10⁻⁹ mol g⁻¹ at 1 bar respectively (with ?50% uncertainty). Despite the significant uncertainties on these estimates, it is clear that the noble gases are not massively soluble in carbonatite liquids (within error, these solubilities are identical to their equivalent solubilities in tholeiitic melts). Assuming the results of these low pressure experiments can be applied to mantle conditions, it seems unlikely that carbonatite metasomatism per se transports noble gases within the mantle. It is nevertheless possible that partitioning of lithophile trace elements (including the important radioelements, U, K and Th) and noble gases between a carbonatitic melt and a silicate melt could effectively decouple lithophile and noble gas isotope systematics because the carbonatitic melt expressedly does not transport noble gases, yet is known to efficiently transport incompatible trace elements.     

Inter-comparison of cosmogenic in-situ He, Ne and Cl at low latitude along an altitude transect on the SE slope of Kilimanjaro volcano (3°S, Tanzania)

Because the intensity and energy spectrum of the cosmic ray flux are affected by atmospheric depth and geomagnetic-field strength, cosmogenic nuclide production rates increase considerably with altitude and to a lesser degree with latitude. The scaling methods used to account for spatial variability in production rates assume that all cosmogenic nuclides have the same altitude dependence. In this study we evaluate whether the production rates of cosmogenic ³⁶Cl, ³He and ²¹Ne change differently with altitude, which is plausible due to the different threshold energies of their production reactions. If so, nuclide-specific scaling factors would be required.Concentrations of the three cosmogenic nuclides were determined in mafic phenocrysts over an altitude transect between 1000 and 4300 m at Kilimanjaro volcano (3°S). Altitude dependence of relative production rates was assessed in two ways: by determination of concentration ratios and by calculation of apparent exposure age ratios for all nuclide pairs. The latter accounts for characteristics of ³⁶Cl that the stable nuclides ³He and ²¹Ne do not possess (radioactive decay, high sensitivity to mineral composition and significant contributions from production reactions other than spallation). All ratios overlap within error over the entire transect, and altitudinal variation in relative production rates is not therefore evident. This suggests that nuclide-specific scaling factors are not required for the studied nuclides at this low-latitude location. However, because previous studies have documented anomalous altitude-dependent variations in ³He production at mid-latitude sites, the effect of latitude on cross-calibrations should be further evaluated.We determined cosmogenic ²¹Ne/³He concentration ratios of 0.1864 ± 0.0085 in pyroxenes and 0.377 ± 0.018 in olivines, agreeing with those reported in previous studies.Despite the absence of independently determined ages for the studied lava surfaces, the consistency in the dataset should enable progress to be made in the determination of the production rates of all three nuclides as soon as the production rate of one of the nuclides has been accurately defined.To our knowledge this is the first time that ³⁶Cl has been measured in pyroxene. The Cl extraction method was validated by measuring ³⁶Cl in co-existing plagioclase phenocrysts in one of the samples.     

Road density as a proxy for population density in regional-scale risk modeling

This paper examines the use of road network data as a proxy for interpreting population density, which is of use in regional-scale qualitative risk assessment for natural hazards. Comparison of available road network and population data at various scales in Ontario and Quebec yields a best-fit relationship of D _P  = 28 D _R ² . Analysis of available high-resolution topographic data for the Caribbean island nation of Saint Lucia suggests similar power law trends, with expected population density in Saint Lucia roughly half that of Canada for the same road density. Together, these findings suggest that D _P  ~ 10–30 D _R ² may represent a useful range broadly applicable for a wide variety of geographic, climactic and socioeconomic settings. The Canadian relationship has been used to generate a population density model for the lowlands of eastern Ontario and southern Quebec, and this model has been compared with the spatial distribution of seismic hazard to develop a qualitative seismic risk map. The seismic risk map, presented primarily for illustrative purposes, shows elevated seismic risk in urban centers in the study area, and along a predominantly rural area east of Quebec City on both shores of the Saint Lawrence River.     

Carbon, oxygen, and strontium isotope geochemistry of carbonate rocks of the upper Miocene Kudankulam Formation, southern India: Implications for paleoenvironment and diagenesis

The carbon, oxygen, and strontium isotope compositions of carbonate rocks from the upper Miocene Kudankulam Formation, southern India, were measured to understand palaeoenvironment and carbonate diagenesis of this formation. Both carbon and oxygen isotope ratios of various carbonate phases including whole rocks, ooids, molluscan mold-fill and sparry pore-fill calcite cements are depleted in ¹⁸O and ¹³C compared to those of contemporaneous seawater, indicating that the Kudankulam carbonates underwent extensive meteoric diagenesis. Based on δ¹³C and δ¹⁸O values for sparry calcite cements (pore-fill and molluscan mold-fill) formed in the meteoric diagenetic realm (δ¹³C from −7.8‰ to −6.0‰ and −9.0‰ to −7.0‰; δ¹⁸O from −9.2‰ to −6.5‰ and −9.4‰ to −2.6‰, respectively), it is interpreted that the diagenetic system was open and was proximal to the vadose water recharge zone. The negative δ¹⁸O values of various carbonate components (about −9.4‰ to −4.1‰ for whole rocks; about −8.4‰ to −2.6‰ for ooids) suggest that during the late Miocene the paleoclimate of the study area was humid, unlike today, probably due to the intense Indian monsoon system. The carbon isotope compositions (−7.9‰ to −3.6‰ for whole rocks; −4.9‰ to −1.5‰ for ooids) are consistent with the interpretation that the paleo-ecosystem comprised a significant proportion of C₄ type plants, supporting a scenario of expansion of C₄ plants during the late Miocene in the Indian subcontinent as far south as the southern tip of India. The ⁸⁷Sr/⁸⁶Sr ratios of the Kudankulam carbonates (0.70920 to 0.72130) are much greater than those of the contemporaneous or modern seawater (between 0.7089 and 0.7091) and show a general decrease up-sequence. Such high Sr isotope ratios indicate significant radiogenic ⁸⁷Sr influx to the system from the Archean rocks exposed in the drainage area, implying that the deep-seated Archean rocks were already exposed in southern India by the late Miocene.     

Laser Ablation (193 nm), Purification and Determination of Very Low Concentrations of Solar Wind Nitrogen Implanted in Targets from the GENESIS Spacecraft

The GENESIS space mission recovered ions emitted by the Sun during a 27 month period. In order to extract, purify and determine the very low quantities of solar nitrogen implanted in the GENESIS targets, a new installation was developed and constructed at the CRPG (Nancy, France). It permitted the simultaneous determination of nitrogen and noble gases extracted from the target by laser ablation. The extraction procedure used a 193 nm excimer laser that allowed for surface contamination in the outer 5 nm to be removed, followed by a step that removed 50 nm of the target material, extracting the solar nitrogen and noble gases implanted in the target. Following purification using Ti and Zr getters for noble gases and a Cu-CuO oxidation cycle for N₂, the extracted gases were analysed by static mode (pumps closed) mass spectrometry using electron multiplier and Faraday cup detectors. The nitrogen blanks from the purification section and the static line (30 minutes) were only 0.46 picomole and 0.47 picomole, respectively.     

The influence of crystallography and kinetics on phengite breakdown reactions in a low-pressure metamorphic aureole

A natural example of phengite that had undergone partial thermal decomposition at a pressure of about 0.5 kbar and a temperature of about 680° C in a contact aureole was exmined in the transmission electron microscope (TEM). Partially pseudomorphed phengites were found to consist of combinations of phengite, biotite, K-feldspar, mullite, sillimanite, spinel and cordierite. Different areas within individual, partially pseudomorphed, phengite grains show various degrees of reaction and different reaction products; the cores are the least reacted and the margins have reacted most. In the cores the assemblage Al-, Mg-enriched phengite+biotite +K-feldspar+mullite±spinel has formed, whereas the assemblage K-feldspar+mullite+sillimanite+spinel +biotite+cordierite has formed at the edges. According to our thermodynamic calculations, the breakdown of phengite should have produced cordierite+spinel +corundum+K-feldspar in regions isolated from the influx of SiO₂ and cordierite+andalusite+quartz+K-feldspar in regions near the edge of the grains that were essentially saturated with SiO₂. Chemical equilibrium was not achieved in any part of the partially pseudomorphed phengites on a micron scale or larger. Breakdown theoretically should have been complete by about 550° C; the reaction temperature was overstepped by at least 130° C for 20–25 years. The variations in the degree and type of reaction are probably due partly to the availability of suitable nucleation sites in different regions, partly to the need to remove H₂O from reaction sites and partly to the influence of SiO₂, which diffused into the grains during metamorphism. The presence of SiO₂ lowers the equilibrium temperatures. Thus there is a higher driving force for breakdown near the grain boundaries than in the cores. Most of the products show an orientation relationship with the parent phengite and have consistent habit planes; they have their closest-packed planes and closest-packed directions parallel to one another and to those of phengite. Such relationships minimize the strain and surface energies at nucleation and favour most rapid nucleation and growth of the reaction products. The great structural similarity of biotite to phengite resulted in its having the highest rate of nucleation and growth of any product and it occurred in all areas of the phengite pseudomorphs studied. Mullite and sillimanite were produced metastably. Mullite has more rapid nucleation kinetics than other aluminosilicates because it is structurally disordered. Sillimanite formed rather than andalusite in regions of the partially pseudomorphed phengites where the reaction reached an advanced stage, because the reaction from phengite to andalusite requires an energetically unfavourable change in aluminium co-ordination state.     

Acute toxicity of the water-soluble fraction of Cook Inlet crude oil to the Manila clam

Recognition of the inherent complexities of oil bioassays prompted the development of several apparatuses designed to deliver uniform solutions of the water-soluble components of crude oil and capable of system equilibration for both static and continuous-flow bioassays without the loss of the more volatile compounds and without the formation of emulsions. Clams from a relatively contaminated area exhibited greater resistance to the water-soluble fraction of Cook Inlet crude oil than specimens from a more pristine area. Behaviour was altered below lethal levels suggesting the possibility of using behavioural modifications as a concommitant criterion of toxicity with mortality. An increase in mortality with a longer exposure period and a significant rate of latent mortalities following the end of the 96-h exposure period suggest that future bioassays with bivalves should be determined over a longer exposure period.     

A Rb-Sr isotopic study of weathering in the Mertondale granite,Western Australia

Fresh samples of the Mertondale granite give a Rb-Sr age of 2580 ± 16 m.y. (λRb⁸⁷ = 1.39 × 10^?11 yr^?1), representing the time of emplacement. Very little change in age is detected with progressive alteration of the granite, apparently associated with weathering, even when it is converted to a kaolinite-quartz assemblage. Preservation of the whole-rock age was unexpected, as the region has been subjected to Tertiary lateritisation to which the alteration of the granite would normally be attributed. We conclude that either the apparent weathering of the granite must be re-interpreted as a late-stage hydrothermal kaolinisation, or that the weathering occurred in the Archaean within about 15 m.y. of the granite's crystallisation.     

Chemical and isotopic evidence for secondary alteration of natural gases in the Hetianhe Field, Bachu Uplift of the Tarim Basin

H₂S and CO₂ are found in elevated concentrations in the reservoirs near the Carboniferous–Ordovician unconformity in the Hetianhe Field of the Tarim Basin, NW China. Chemical and isotopic analyses have been performed on produced gases, formation waters and reservoir rocks to determine the origin of CO₂ and H₂S and to explain the heterogeneous distribution of isotopic and geochemical characteristics of petroleum fluids. It is unlikely that H₂S and CO₂ had a mantle component since associated helium has an isotope ratio totally uncharacteristic of this source. Instead, H₂S and CO₂ are probably the result of sulphate reduction of the light hydrocarbon gases (LHG). Increasing H₂S concentrations and CO₂/(CO₂+ΣC_1–4) values to the west of the Hetianhe Field occur commensurately with increasingly heavy hydrocarbon gas δ¹³C values. However, thermochemical sulphate reduction is unlikely because the temperatures of the reservoirs are too low, no H₂S or rare pyrite was detected in deeper reservoirs (where more TSR should have occurred) and inferred δ³⁴S values of H₂S (from late-stage pyrite in the Carboniferous and Ordovician reservoirs) are as low as −24.9‰. Such low δ³⁴S values discount the decomposition of organic matter as a major source of H₂S and CO₂. Bacterial sulphate reduction of the light hydrocarbon gases in the reservoir, possibly coupled indirectly with the consumption of organic acids and anions is most likely. The result is the preferential oxidation of ¹²C-rich alkanes (due to the kinetic isotope effect) and decreasing concentration of organic acids and anions. Modern formation water stable isotope data reveal that it is possible that sulphate-reducing bacteria were introduced into the reservoir by an influx of meteoric water from the west by way of an inversion-related unconformity. This may account for the apparently stronger influence of bacterial sulphate reduction to the west of the Hetianhe Field, and the consequent greatest decrease of the δ¹³C-CO₂ values and the greatest increase in δ¹³C values of the alkane gases.     

Cross formational flow in the Paris Basin

Cross formational flow of water has occurred across several hundred metres of Liassic mudstone from the Triassic Chaunoy Formation sandstone to the Middle Jurassic Dogger Formation carbonate in the Paris Basin, France. This has been demonstrated by chemical and isotopic data from rocks and formation waters, sampled on a basin scale, from the Dogger and Chaunoy formations. Present-day and palaeoformation waters in the Dogger record input of exotic water in terms of salinity and carbon and strontium isotopes. The exotic water was highly saline and contained isotopically light carbon and ⁸⁷Sr-enriched strontium in comparison to the indigenous Dogger Formation water. The source of the exotic water can only have been the Chaunoy Formation. Salinity and isotope data show that present-day Dogger Formation water contains 10–15% invasion Chaunoy water. Modelling strontium isotope ratio and concentration data from mineral cements shows that over the duration of Dogger cementation, Dogger palaeoformation waters were replaced by 1–5% Chaunoy water. Cross formational flow of water must have occurred by convective mass flow, rather than diffusion, in order to preserve the characteristics of water input from the Chaunoy. Flow probably occurred via the major Hercynian fault and fracture systems that run through the centre of the Paris Basin. Upward flow in this setting is most likely in a compressional tectonic regime, the situation during much of the Tertiary in the Paris Basin. Thermodynamic modelling indicates that cross formational flow from the Chaunoy has probably caused carbonate cementation in the Dogger.