The chlorine isotope composition of Martian meteorites 2. Implications for the early solar system and the formation of Mars

We determined the chlorine isotope composition of 16 Martian meteorites using gas source mass spectrometry on bulk samples and in situ secondary ion microprobe analysis on apatite grains. Measured δ³⁷Cl values range from ?3.8 to +8.6‰. The olivine‐phyric shergottites are the isotopically lightest samples, with δ³⁷Cl mostly ranging from ?4 to ?2‰. Samples with evidence for a crustal component have positive δ³⁷Cl values, with an extreme value of 8.6‰. Most of the basaltic shergottites have intermediate δ³⁷Cl values of ?1 to 0‰, except for Shergotty, which is similar to the olivine‐phyric shergottites. We interpret these data as due to mixing of a two‐component system. The first component is the mantle value of ?4 to ?3‰. This most likely represents the original bulk Martian Cl isotope value. The other endmember is a ³⁷Cl‐enriched crustal component. We speculate that preferential loss of ³⁵Cl to space has resulted in a high δ³⁷Cl value for the Martian surface, similar to what is seen in other volatile systems. The basaltic shergottites are a mixture of the other two endmembers. The low δ³⁷Cl value of primitive Mars is different from Earth and most chondrites, both of which are close to 0‰. We are not aware of any parent‐body process that could lower the δ³⁷Cl value of the Martian mantle to ?4 to ?3‰. Instead, we propose that this low δ³⁷Cl value represents the primordial bulk composition of Mars inherited during accretion. The higher δ³⁷Cl values seen in many chondrites are explained by later incorporation of ³⁷Cl‐enriched HCl‐hydrate.     

Zoning of phosphorus in igneous olivine

We describe P zoning in olivines from terrestrial basalts, andesites, dacites, and komatiites and from a martian meteorite. P₂O₅ contents of olivines vary from below the detection limit (≤0.01 wt%) to 0.2–0.4 wt% over a few microns, with no correlated variations in Fo content. Zoning patterns include P-rich crystal cores with skeletal, hopper, or euhedral shapes; oscillatory zoning; structures suggesting replacement of P-rich zones by P-poor olivine; and sector zoning. Melt inclusions in olivines are usually located near P-rich regions but in direct contact with low-P olivine. Crystallization experiments on basaltic compositions at constant cooling rates (15–30°C/h) reproduce many of these features. We infer that P-rich zones in experimental and natural olivines reflect incorporation of P in excess of equilibrium partitioning during rapid growth, and zoning patterns primarily record crystal-growth-rate variations. Occurrences of high-P phenocryst cores may reflect pulses of rapid crystal growth following delayed nucleation due to undercooling. Most cases of oscillatory zoning in P likely reflect internal factors whereby oscillating growth rates occur without external forcings, but some P zoning in natural olivines may reflect external forcings (e.g., magma mixing events, eruption) that result in variable crystal growth rates and/or P contents in the magma. In experimental and some natural olivines, Al, Cr, and P concentrations are roughly linearly and positively correlated, suggesting coupled substitutions, but in natural phenocrysts, Cr zoning is usually less intense than P zoning, and Al zoning weak to absent. We propose that olivines grow from basic and ultrabasic magmas with correlated zoning in P, Cr, and Al superimposed on normal zoning in Fe/Mg; rapidly diffusing divalent cations homogenize during residence in hot magma; Al and Cr only partially homogenize; and delicate P zoning is preserved because P diffuses very slowly. This interpretation is consistent with the fact that zoning is largely preserved not only in P but also in Al, Cr, and divalent cations in olivines with short residence times at high temperature (e.g., experimentally grown olivines, komatiitic olivines, groundmass olivines, and the rims of olivine phenocrysts grown during eruption). P zoning is widespread in magmatic olivine, revealing details of crystal growth and intra-crystal stratigraphy in what otherwise appear to be relatively featureless crystals. Since it is preserved in early-formed olivines with prolonged residence times in magmas at high temperatures, P zoning has promise as an archive of information about an otherwise largely inaccessible stage of a magma’s history. Study of such features should be a valuable supplement to routine petrographic investigations of basic and ultrabasic rocks, especially because these features can be observed with standard electron microprobe techniques.     

A simple concept for calibrating runoff thresholds in quasi‐distributed variable source area watershed models

Most semi‐distributed watershed water quality models divide the watershed into hydrologic response units (HRU) with no flow among them. This is problematic when watersheds are delineated to include variable source areas (VSAs) because it is the lateral flows from upslope areas to downslope areas that generate VSAs. Although hydrologic modellers have often successfully calibrated these types of models, there can still be considerable uncertainty in model results. In this paper, a topographic‐index‐based method is described and tested to distribute effective soil water holding capacity among HRUs, which can be subsequently adjusted using the watershed baseflow coefficient. The method is tested using a version of the Soil and Water Assessment Tool (SWAT) model that simulates VSA runoff and is applied to two watersheds: a New York State (NYS) watershed, and one in the head waters of the Blue Nile Basin (BNB) in Ethiopia. Daily streamflow predicted using effective soil water storage capacities based only on the topographic index were reassuringly accurate in both the NYS watershed (daily Nash Sutcliffe (E) = 0·73) and in the BNB (E = 0·70). Using the baseflow coefficient to adjust the effective soil water storage capacity only slightly improved streamflow predictions in NYS (E = 0·75) but substantially improved the BNB predictions (E = 0·80). By comparison, the standard SWAT model, which uses the traditional look‐up tables to determine a runoff curve number, performed considerably less accurately in un‐calibrated form (E = 0·51 for NYS and E = 0·45 for BNB), but improved substantially when explicitly calibrated to streamflow measurements (E = 0·76 for NYS and E = 0·67 for the BNB). The calibration method presented here provides a parsimonious, systematic approach to using established models in VSA watersheds that reduces the ambiguity inherent in model calibration. Copyright © 2011 John Wiley & Sons, Ltd.     

Potassium Permanganate Doped Geopolymers for Remedial Applications

This study investigates the use of KMnO₄ doped geopolymers as controlled‐release materials for remedial applications. The geopolymers were prepared by mixing alkali activated Na‐silicate solutions, metakaolin, and various amounts of granular KMnO₄. Samples were heat treated at 75 °C for 48 h. Concentrations of KMnO₄ in samples 1, 2, and 3 were 1.40 × 10^?1, 4.63 × 10^?1, and 6.07 × 10^?1 g/cm³, respectively. 1D column experiments showed that a high MnO₄^? release rate lasted for the first few hours, followed by a gradual decrease of MnO₄^? release. Neither cracks nor surface erosion of the geopolymers were observed throughout the experiments. Sample 1 approached exhaustion at the end of the Day 7. It took about 18 d for exhaustion of KMnO₄ releases in samples 2 and 3. Modeling of the observed KMnO₄ releases suggested diffusion and dissolution‐related fast transport as the most important mechanisms. This latter mechanism involves the creation of a connected secondary porosity in the geopolymers by dissolution of KMnO₄ granules. The contribution of Fickian diffusion to the total release decreased as the KMnO₄ content of the samples increased, and the dissolution mechanism became increasingly important.     

Microhabitat influences on stream insect emergence

Understanding the factors controlling insect emergence from streams has applications to ecological theory regarding cross-boundary flux, along with practical value for monitoring stream function after restoration projects. We hypothesized that stream microhabitat would have effects on emergence that were independent of those mediated by the local stock of benthic macroinvertebrates. We set 50 emergence traps in a third-order stream in northern Minnesota, USA, during two study periods and used structural equation modeling to examine direct and indirect effects of benthic stock and microhabitat features on emergence. Emergence by biomass showed direct positive relationships to substrates of fines and detritus in the first sampling period, and to shallow depth and wood area in the second period. Emergence by abundance had direct positive relationships with benthic stock, CPOM, and fewer macrophytes in the first period, and with benthic stock and periphyton in the second period. Fine substrates may act to concentrate burrowing larvae, whereas CPOM and particularly wood may intercept drifting pre-emergent insects and provide exiting surfaces. Shallow depths may reduce the extent to which resident insects drift downstream (and leave the sample area) while emerging. Periphyton may be an indicator for patches with greater illumination, which itself attracts emergers. Our results suggest emergence is sensitive to environmental conditions at the microhabitat scale, and that stream restoration activities should consider habitat for emerging insects when designing projects.     

Oxygen isotope evidence for subduction and rift-related mantle metasomatism beneath the Colorado Plateau–Rio Grande rift transition

Spinel lherzolite and pyroxenite xenoliths from the Rio Puerco Volcanic Field, New Mexico, were analyzed for oxygen isotope ratios by laser fluorination. In lherzolites, olivine δ¹⁸O values are high (+5.5‰), whereas δ¹⁸O values for pyroxenes are low (cpx=+5.1‰; opx=+5.4‰) compared to average mantle values. Pyroxenite δ¹⁸O values (cpx=+5.0‰; opx=+5.3‰) are similar to those of the lherzolites and are also lower than typical mantle oxygen isotope compositions. Texturally and chemically primary calcite in pyroxenite xenoliths is far from isotopic equilibrium with other phases, with δ¹⁸O values of +21‰. The isotopic characteristics of the pyroxenite xenoliths are consistent with a petrogenetic origin from mixing of lherzolitic mantle with slab-derived silicate and carbonatite melts. The anomalously low δ¹⁸O in the pyroxenes reflects metasomatism by a silicate melt from subducted altered oceanic crust, and high δ¹⁸O calcite is interpreted to have crystallized from a high δ¹⁸O carbonatitic melt derived from subducted ophicarbonate. Similar isotopic signatures of metasomatism are seen throughout the Rio Puerco xenolith suite and at Kilbourne Hole in the southern Rio Grande rift. The discrete metasomatic components likely originated from the subducted Farallon slab but were not mobilized until heating associated with Rio Grande rifting occurred. Oxygen diffusion modeling requires that metasomatism leading to the isotopic disequilibrium between calcite and pyroxene in the pyroxenites occurred immediately prior to entrainment. Melt infiltration into spinel-facies mantle (xenoliths) prior to eruption was thus likely connected to garnet-facies melting that resulted in eruption of the host alkali basalt.