Oxygen isotopic compositions and origins of calcium‐aluminum‐rich inclusions and chondrules

Abstract— Primary minerals in calcium‐aluminum‐rich inclusions (CAIs), Al‐rich and ferromagnesian chondrules in each chondrite group have δ¹⁸O values that typically range from ?50 to +5%0. Neglecting effects due to minor mass fractionations, the oxygen isotopic data for each chondrite group and for micrometeorites define lines on the three‐isotope plot with slopes of 1.01 ± 0.06 and intercepts of ?2 ± 1. This suggests that the same kind of nebular process produced the ¹⁶O variations among chondrules and CAIs in all groups. Chemical and isotopic properties of some CAIs and chondrules strongly suggest that they formed from solar nebula condensates. This is incompatible with the existing two‐component model for oxygen isotopes in which chondrules and CAIs were derived from heated and melted ¹⁶O‐rich presolar dust that exchanged oxygen with ¹⁶O‐poor nebular gas. Some FUN CAIs (inclusions with isotope anomalies due to fractionation and unknown nuclear effects) have chemical and isotopic compositions indicating they are evaporative residues of presolar material, which is incompatible with ¹⁶O fractionation during mass‐independent gas phase reactions in the solar nebula. There is only one plausible reason why solar nebula condensates and evaporative residues of presolar materials are both enriched in ¹⁶O. Condensation must have occurred in a nebular region where the oxygen was largely derived from evaporated ¹⁶O‐rich dust. A simple model suggests that dust was enriched (or gas was depleted) relative to cosmic proportions by factors of ～10 to >50 prior to condensation for most CAIs and factors of 1–5 for chondrule precursor material. We infer that dust‐gas fractionation prior to evaporation and condensation was more important in establishing the oxygen isotopic composition of CAIs and chondrules than any subsequent exchange with nebular gases. Dust‐gas fractionation may have occurred near the inner edge of the disk where nebular gases accreted into the protosun and Shu and colleagues suggest that CAIs formed.     

Large‐ion lithophile element fractionation during the early differentiation of Mars and the composition of the martian primitive mantle

Abstract— Basaltic shergottites display a systematic decrease in K/Th, K/U, and K/La ratios with increasing K content. These trends are interpreted as mixing lines between relatively young martian magmas derived from highly depleted mantle sources and an ancient large‐ion lithophile (LIL) element‐enriched crustal component. One implication of this is that a substantial fractionation of these ratios occurs during the early crustal differentiation on Mars. Isotopic evidence from SNC meteorites and compositional data from Pathfinder and orbital gamma ray spectroscopy suggest that in excess of 50% of the LIL element complement of Mars resides in the crustal reservoir. If so, the primitive mantle of Mars is significantly more volatile‐depleted (i.e., lower K/Th, K/U, K/La) than previously thought but probably (though not necessarily) still less volatile‐depleted than the primitive mantle of the Earth. The La/Th ratios of virtually all SNC meteorites are subchondritic, including those with the most severe LREE‐depletion. Extrapolation of the basaltic shergottite trend suggests that both the depleted mantle end member and the enriched crustal end member have subchondritic La/Th ratios. This is in contrast with the Earth where basalts from LIL element‐depleted sources such as MORB have superchondritic La/Th ratios, complementary to the subchondritic ratios of the continental crust. Accordingly, assuming that the refractory elements are in chondritic proportions for the Mars primitive mantle, an additional major geochemical reservoir must exist on Mars that may not yet have been sampled.     

Desert methane: Implications for life detection on Mars

Methane, a potential biosignature, has recently been detected in the martian atmosphere. This Note focuses on field investigations/operational simulations and laboratory studies which resulted in successful detection of methane within arid terrestrial soils, as distinct from the usual methanogen environment, but in at least partial analogy to martian conditions.     

Development of the mixed conifer forest in northern New Mexico and its relationship to Holocene environmental change

Chihuahueños Bog (2925 m) in the Jemez Mountains of northern New Mexico contains one of the few records of late-glacial and postglacial development of the mixed conifer forest in southwestern North America. The Chihuahueños Bog record extends to over 15,000 cal yr BP. An Artemisia steppe, then an open Picea woodland grew around a small pond until ca. 11,700 cal yr BP when Pinus ponderosa became established. C/N ratios, δ¹³C and δ¹⁵N values indicate both terrestrial and aquatic organic matter was incorporated into the sediment. Higher percentages of aquatic algae and elevated C/N ratios indicate higher lake levels at the opening of the Holocene, but a wetland developed subsequently as climate warmed. From ca. 8500 to 6400 cal yr BP the pond desiccated in what must have been the driest period of the Holocene there. C/N ratios declined to their lowest Holocene levels, indicating intense decomposition in the sediment. Wetter conditions returned after 6400 cal yr BP, with conversion of the site to a sedge bog as groundwater levels rose. Higher charcoal influx rates after 6400 cal yr BP probably result from greater biomass production rates. Only minor shifts in the overstory species occurred during the Holocene, suggesting that mixed conifer forest dominated throughout the record.     

Kinetics of Cd sorption, desorption and fixation by calcite: A long-term radiotracer study

Time-dependent sorption and desorption of Cd on calcite was studied over 210 days utilizing ¹⁰⁹Cd as a tracer to distinguish between ‘labile’ and ‘non-labile’ forms of sorbed Cd. Stabilizing the calcite suspensions for 12 months under atmospheric P_CO2 and controlled temperature was necessary to reliably follow Cd dynamics following initial sorption. Results revealed time-dependant Cd sorption and marked desorption hysteresis by calcite under environmentally relevant conditions. Data obtained were fitted to a first-order kinetic model and a concentric shell diffusion model. Both models described the progressive transfer of Cd²⁺ to a less reactive form within calcite and subsequent desorption of Cd subject to different initial contact times. The kinetic model provided a better fit to the combined sorption and desorption data (R² = 0.992). It differentiates between two ‘pools’ of sorbed Cd²⁺ on calcite, ‘labile’ and ‘non-labile’, in which labile sorbed Cd is in immediate equilibrium with the free Cd²⁺ ion activity in solution whereas non-labile Cd is kinetically restricted. For the diffusion model (R² = 0.959), the rate constants describing Cd dynamics in calcite produced a half-life for Cd desorption of ∼175 d, for release to a ‘zero-sink’ solution. Results from this study allow comment on the likely mechanisms occurring at the calcite surface following long-term Cd sorption.     

Reaction mechanism of uranyl in the presence of zero-valent iron nanoparticles

The current study provides an investigation of abiotic reduction of an oversaturated uranyl solution driven by iron nanoparticle oxidation. The reactivity of nano-scale zero-valent iron (ZVI) under mildly oxic conditions (1.2% O₂ and 0.0017% CO₂) was studied in 1000 ppm uranyl solution in the pH range 3-7, at reaction times from 10 min to 4 h. Reductive precipitation of UO₂ was observed as the main process responsible for the removal of uranium from solution with the kinetics of reaction becoming increasingly favourable at higher pH. Despite working with an oversaturated uranium solution, the precipitation of UO₂ occurred in preference to precipitation of UO₃·2H₂O (metaschoepite) at reaction times between 1 and 4 h and for uranyl solutions initially set up at pH ?5. Characterisation of both solid and solution phases was performed using X-ray photoelectron spectroscopy (XPS), focused ion beam (FIB) imaging, X-ray diffraction (XRD) and inductively coupled plasma atomic emission spectroscopy (ICP-AES).     

Pervasive wetland flooding in the glacial drift prairie of North Dakota (USA)

This article describes a unique flood hazard, produced by the dramatic expansion of wetlands in Nelson County, located within the North American Prairie Pothole Region of North Dakota, USA. There has been an unprecedented increase in the number, average size, and permanence of prairie wetlands, and a significant increase in the size of a closed lake (Stump Lake) due to a decade-long wet spell that began in 1993 following a prolonged drying trend. Base-line land cover information from the 1992 USGS National Land Cover Characterization dataset, and a Landsat TM scene acquired 9 July 2001 are used to assess the growth of the closed lake and wetland pond surface areas, and to analyze the type and area of various land cover classes inundated between 1992 and 2001. The open water profile in Nelson County changed from one marked by relatively comparable coverage of closed lake and wetland pond areas in 1992, to one in which wetland open water accounted for the vast majority of total open water in 2001. The bulk of the wetland pond area expansion occurred by displacing existing wetland vegetation and agricultural cropland. Producers responded to the flood hazard by filing Federal Crop Insurance Corporation (FCIC) claims and enrolling cropland in the Conservation Reserve Program (CRP), a federal land retirement program. Land taken out of agricultural production has had an enormous impact upon the agricultural sector that forms the economic base of the rural economy. In 2001 the land taken out of production due to CRP enrollment and preventive planting claims represented nearly 42% of Nelson County’s 205.2 K ha base agricultural land. The patterns obtained from this detailed study of Nelson County are likely to be the representative of the more publicized flood disaster occurring within the Devils Lake Basin of North Dakota.     

Variations in exospheric density at heights near 1100km, derived from satellite orbits

In an earlier paper, values of exospheric density were obtained from the orbit of Echo 2 for the years 1964–1965. The results indicated a semi-annual variation in density by a factor of between 2 and 3, considerably larger than predicted by existing atmospheric models.

These studies have now been extended to the beginning of 1967, using both Echo 2 and Calsphere 1, to show how the density is responding to increasing solar activity. Variations in density during 1964 have been analysed in more detail. The long-term variation associated with the solar cycle and the short-term variations associated with magnetic and solar disturbances agree with the variations expected on the basis of current models. The semi-annual variation is persisting to higher levels of solar activity, and although its amplitude is diminishing the factor of variation was still 1.6 in 1966.     

Accumulation and effects of organotin compounds in oysters and mussels: Correlation with serum biochemical and cytological factors and tissue burdens

Oysters and mussels exposed to a concentration of 0·7 ppb (μg/liter) tributyltin from painted panels in flowing seawater accumulated tin in the digestive glands to comparable levels. The mussels experienced approximately 50% mortality during the 60-day test period, but the oysters suffered virtually no deaths. There was no evidence from either bivalve of elevated numbers of hemocytes during the test period and no evidence for cellular disruption as detected by increased levels of serum lysosomal hydrolases. Serum protein of exposed mussels relative to controls increased with time of exposure to the toxicant, while oyster serum protein, normally 10 x higher than in mussels, did not. No evidence was found for elevated stress proteins (heat shock proteins) or metallothioneins in the serum hemocytes of either bivalve. Responses by these animals to fatal or near fatal doses of TBT were thus very different from responses to copper that we have reported elsewhere.^1,2