The ortho- to para- ratio of H2 in the starburst of NGC 253

We present measurements of several near-infrared emission lines from the nearby galaxy NGC 253. We have been able to measure four H₂ lines across the circumnuclear starburst, from which we estimate the ortho- to para- ratio of excited H₂ to be ∼2. This indicates that the bulk of the H₂ emission arises from photodissociation regions (PDRs), rather than from shocks. This is the case across the entire region of active star formation.
As the H₂ emission arises from PDRs, it is likely that the ratio of H₂ to Brγ (the bright hydrogen recombination line) is a measure of the relative geometry of O and B stars and PDRs. Towards the nucleus of NGC 253 the geometry is deduced to be tightly clustered O and B stars in a few giant H  II regions that are encompassed by PDRs. Away from the nuclear region, the geometry becomes that of PDRs bathed in a relatively diffuse ultraviolet radiation field.
The rotation curves of 1–0 S(1) and Brγ suggest that the ionized gas is tracing a kinetic system different from that of the molecular gas in NGC 253, particularly away from the nucleus.     

A finite element approach to the simulation of hydraulic fractures with lag

We presented a finite‐element‐based algorithm to simulate plane‐strain, straight hydraulic fractures in an impermeable elastic medium. The algorithm accounts for the nonlinear coupling between the fluid pressure and the crack opening and separately tracks the evolution of the crack tip and the fluid front. It therefore allows the existence of a fluid lag. The fluid front is advanced explicitly in time, but an implicit strategy is needed for the crack tip to guarantee the satisfaction of Griffith's criterion at each time step. We enforced the coupling between the fluid and the rock by simultaneously solving for the pressure field in the fluid and the crack opening at each time step. We provided verification of our algorithm by performing sample simulations and comparing them with two known similarity solutions. Copyright © 2012 John Wiley & Sons, Ltd.     

Experimental analysis of arsenic precipitation during microbial sulfate and iron reduction in model aquifer sediment reactors

Microbial SO₄²⁻ reduction limits accumulation of aqueous As in reducing aquifers where the sulfide that is produced forms minerals that sequester As. We examined the potential for As partitioning into As- and Fe-sulfide minerals in anaerobic, semi-continuous flow bioreactors inoculated with 0.5% (g mL⁻¹) fine-grained alluvial aquifer sediment. A fluid residence time of three weeks was maintained over a ca. 300-d incubation period by replacing one-third of the aqueous phase volume of the reactors with fresh medium every seven days. The medium had a composition comparable to natural As-contaminated groundwater with slightly basic pH (7.3) and 7.5 μM aqueous As(V) and also contained 0.8 mM acetate to stimulate microbial activity. Medium was delivered to a reactor system with and without 10 mmol L⁻¹ synthetic goethite (α-FeOOH). In both reactors, influent As(V) was almost completely reduced to As(III). Pure As-sulfide minerals did not form in the Fe-limited reactor. Realgar (As₄S₄) and As₂S₃(am) were undersaturated throughout the experiment. Orpiment (As₂S₃) was saturated while sulfide content was low (∼50 to 150 μM), but precipitation was likely limited by slow kinetics. Reaction-path modeling suggests that, even if these minerals had formed, the dissolved As content of the reactor would have remained at hazardous levels. Mackinawite (Fe_1 + xS; x ? 0.07) formed readily in the Fe-bearing reactor and held dissolved sulfide at levels below saturation for orpiment and realgar. The mackinawite sequestered little As (<0.1 wt.%), however, and aqueous As accumulated to levels above the influent concentration as microbial Fe(III) reduction consumed goethite and mobilized adsorbed As. A relatively small amount of pyrite (FeS₂) and greigite (Fe₃S₄) formed in the Fe-bearing reactor when we injected a polysulfide solution (Na₂S₄) to a final concentration of 0.5 mM after 216, 230, 279, and 286 days. The pyrite, and to a lesser extent the greigite, that formed did sequester As from solution, containing 0.84 and 0.23 wt.% As on average, respectively. Our results suggest that As precipitation during Fe-sulfide formation in nature occurs mainly in conjunction with pyrite formation. Our findings imply that the effectiveness of stimulating microbial SO₄²⁻ reduction to remediate As contamination may be limited by the rate and extent of pyrite formation and the solubility of As-sulfides.     

Early solar system processes recorded in the matrices of two highly pristine CR3 carbonaceous chondrites, MET 00426 and QUE 99177

The mineralogy and bulk compositions of the matrices of the CR chondrites MET 00426 and QUE 99177 have been studied using a combination of SEM, EPMA, and TEM techniques. The matrices of these two chondrites are texturally, chemically, and mineralogically similar and are characterized by significant FeO-enrichments with respect to other CR chondrite matrices, nearly flat refractory lithophile patterns, variable volatile element patterns, and a simple mineral assemblage dominated by amorphous silicate material and Fe,Ni sulfides. Fine-grained, crystalline silicate phases such as olivine and pyroxene appear to be extremely rare in the matrices of both meteorites. Instead, the mineralogy of matrices and fine-grained rims of both meteorites consists of abundant amorphous FeO-rich silicate material, containing nanoparticles of Fe,Ni sulfides (troilite, pyrrhotite, and pentlandite). Secondary alteration minerals that are characteristic of other CR chondrites (e.g., Renazzo and Al Rais), such as phyllosilicates, magnetite, and calcite are also rare. The texture and mineralogy of the matrices of MET 00426 and QUE 99177 share many features with matrices in the primitive carbonaceous chondrites ALH A77307 (CO3.0) and Acfer 094 (unique). These observations show that MET 00426 and QUE 99177 are very low petrologic type 3 chondrites that have escaped the effects of aqueous alteration, unlike other CR chondrites, which are typically classified as petrologic type 2. We suggest that these meteorites represent additional samples of highly primitive, but extremely rare carbonaceous chondrites of petrologic type 3.00, according to the classification scheme of Grossman and Brearley (2005). The highly pristine nature of MET 00426 and QUE 99177 provides important additional insights into the origins of fine-grained materials in carbonaceous chondrites. Based on our new observations, we infer that the amorphous silicate material and nanosulfide particles that dominate the matrices of these meteorites formed in the solar nebula by rapid condensation of material following high-temperature events, such as those that formed chondrules.     

The potential origins and palaeoenvironmental implications of high temporal resolution δO heterogeneity in coral skeletons

δ¹⁸O was determined at high spatial resolution (beam diameter ∼30 μm) by secondary ion mass spectrometry (SIMS) across 1-2 year sections of 2 modern Porites lobata coral skeletons from Hawaii. We observe large (>2‰) cyclical δ¹⁸O variations that typically cover skeletal distances equivalent to periods of ∼20-30 days. These variations do not reflect seawater temperature or composition and we conclude that skeletal δ¹⁸O is principally controlled by other processes. Calcification site pH in one coral record was estimated from previous SIMS measurements of skeletal δ¹¹B. We model predicted skeletal δ¹⁸O as a function of calcification site pH, DIC residence time at the site and DIC source (reflecting the inputs of seawater and molecular CO₂ to the site). We assume that oxygen isotopic equilibration proceeds at the rates observed in seawater and that only the aqueous carbonate ion is incorporated into the precipitating aragonite. We reproduce successfully the observed skeletal δ¹⁸O range by assuming that DIC is rapidly utilised at the calcification site (within 1 h) and that ∼80% of the skeletal carbonate is derived from seawater. If carbonic anhydrase catalyses the reversible hydration of CO₂ at the calcification site, then oxygen isotopic equilibration times may be substantially reduced and a larger proportion of the skeletal carbonate could be derived from molecular CO₂. Seasonal skeletal δ¹⁸O variations are most pronounced in the skeleton deposited from late autumn to winter (and coincide with the high density skeletal bands) and are dampened in skeleton deposited from spring to summer. We observed no annual pattern in sea surface temperature or photosynthetically active radiation variability which could potentially correlate with the coral δ¹⁸O. At present we are unable to resolve an environmental cue to drive seasonal patterns of short term skeletal δ¹⁸O heterogeneity.