Cumberland Falls chondritic inclusions: Mineralogy/petrology of a forsterite chondrite suite

As previously found for a chondritic inclusion of unknown affinity, mineralogic and petrologic properties of 9 inclusions in the Cumberland Falls enstatitc achondrite are primitive members of the forsterite (F) chondrite group, hitherto defined by 4 meteorites of similar redox state. The inclusions define a primitive suite with properties indicating 8 as F3 and one of even lower petrologic type. The abundant minerals include: low-Ca pyroxene, olivine, plagioclase, kamacite, taenite, schreibersite, troilite, ferroan alabandite and daubreelite. Diopside, oldhamite and a Ti-rich sulfide are present in one or two inclusions. Petrologic textures and jadeitic pyroxene, hitherto unidentified in meteorites, indicate substantial degree of shock. The inclusions acquired their chemical characteristics during nebular condensation and accretion over a broad redox range (metal-silicate trends in them verify Prior's Rules): their parent body later impacted the enstatite meteorite parent body. During impact, the inclusions were shocked and incorporated with enstatite achondrite host as a breccia that would become Cumberland Falls.     

Chemical studies of L chondrites—II. Shock-induced trace element mobilization

Previous studies of chondrites heated in the laboratory for extended periods under conditions approximating those in shock-heated collisional debris indicate that Au, Co, Se, Ga, Rb, Cs, Te, Bi, In, Ag, Zn, Tl and Cd progress in mobility. We report data for these 13 trace elements in 14 L4–6 chondrites of established shock history and discuss these and 13 additional chondrites studied earlier. Trace element contents vary with petrologic type, $\text{S}\text{Fe}$ sub-group and shock history, the last dominating strongly. Absolute abundances and interelement relationships for the 6 or 7 most mobile elements vary with degree of shock-loading (i.e. residual temperatures) established from mineralogic/petrologic study. A tertiary process, shock-heating, previously known to have affected radiogenic ⁴⁰Ar and/or ⁴He in meteorites but not other elements, apparently was at least as effective as other open-system processes (secondary [parent body] and primary [nebular and/or accretionary] episodes) in establishing mobile trace element contents of L chondrites and probably others. If conditions during early genetic episodes are to be deduced from compositional information, shocked meteorites should be avoided or effects of later processes should be compensated for.     

Determination of food web support and trophic position of the mummichog,Fundulus heteroclitus, in New Jersey smooth cordgrass (Spartina alterniflora), common reed (Phragmites australis), and restored salt marshes

The invasion ofPhragmites australis into tidal marshes formerly dominated bySpartina alterniflora has resulted in considerable interest in the consequences of this invasion for the ecological functions of marsh habitat. We examined the provision of trophic support for a resident marsh fish,Fundulus heteroclitus, in marshes dominated byP. australis, byS. alterniflora, and in restored marshes, using multiple stable isotope analysis. We first evaluated our ability to distinguish among potential primary producers using the multiple stable isotope approach. Within a tidal creek system we found significant marsh and elevation effects on microalgal isotope values, and sufficient variability and overlap in primary producer isotope values to create some difficulty in identifying unique end members. The food webs supportingF. heteroclitus production were examined using dual isotope plots. At both sites, the δ¹³C values ofF. heteroclitus were clustered over values for benthic microalgae (BMI) and approximately midway between δ¹³C values ofSpartina andPhragmites. Based on comparisons of fish and primary producer δ¹³C, δ¹⁵N, and δ³⁴S values, and consideration ofF. heteroclitus feeding habits, we conclude that BMI were a significant component of the food web supportingF. heteroclitus in these brackish marshes, especially recently-hatched fish occupying pools on the marsh surface. A 2‰ difference in δ¹³C betweenFundulus occupying nearly adjacentSpartina andPhragmites marshes may be indicative of relatively less reliance on BMI and greater reliance onPhragmites production inPhragmites-dominated marshes, a conclusion consistent with the reduced BMI biomass found inPhragmites marshes. The mean δ¹³C value ofF. heteroclitus from restored marshes was intermediate between values of fish from naturally occurringSpartina marshes and areas invaded byPhragmites. We also examined the isotopic evidence for ontogenetic changes in the trophic position of larval and juvenileF. heteroclitus. We found significant positive relationships betweenF. heteroclitus δ¹⁵N values and total length, reflective of an increase in trophic position as fish grow.F. heteroclitus δ¹⁵N values indicate that these fish are feeding approximately two trophic levels above primary producers.     

The oxidation state of europium as an indicator of oxygen fugacity

The distribution of Eu between plagioclase feldspar and magmatic liquid has been determined experimentally for basaltic and andesitic systems as a function of temperature and oxygen fugacity at one atmosphere total pressure. Using the approach of Philpotts the ratios $\text{Eu}{}^{\mathrm{2+}}\text{Eu}{}^{\mathrm{3+}}$ in plagioclase and coexisting magmatic liquid have been calculated. These ratios appear to be simply related to oxygen fugacity for the bulk compositions studied here. Using published trace element distribution data for natural rocks oxygen fugacities may be calculated from these experimental results. For terrestrial basalts calculated oxygen fugacities average 10^?7 with little dispersion from this value. Andesites average 10^?8.1 with considerable dispersion, while dacites and rhyodacites average 10^?9.1, also with considerable dispersion. Oxygen fugacities for lunar ferrobasalts cluster tightly around 10^?12.7. Data on achondritic meteorites are limited, but calculations indicate oxygen fugacities of two-to-five orders of magnitude lower than lunar ferrobasalts.     

Solubility and near-equilibrium dissolution rates of quartz in dilute NaCl solutions at 398-473 K under alkaline conditions

The dissolution-precipitation of quartz controls porosity and permeability in many lithologies and may be the best studied mineral-water reaction. However, the rate of quartz-water reaction is relatively well characterized far from equilibrium but relatively unexplored near equilibrium. We present kinetic data for quartz as equilibrium is approached from undersaturation and more limited data on the approach from supersaturated conditions in 0.1 molal NaCl + NaOH + NaSiO(OH)₃ solutions with pH 8.2-9.7 at 398, 423, 448, and 473 K. We employed a potentiometric technique that allows precise determination of solution speciation within 2 kJ mol⁻¹ of equilibrium without the need for to perturb the system through physical sampling and chemical analysis. Slightly higher equilibrium solubilities between 423 and 473 K were found than reported in recent compilations. Apparent activation energies of 29 and 37 kJ mol⁻¹ are inferred for rates of dissolution at two surface sites with different values of connectedness: dissolution at Q¹ or Q² silicon sites, respectively. The dissolution mechanism varies with ΔG such that reactions at both sites control dissolution up until a critical free energy value above which only reactions at Q¹ sites are important. When our near-equilibrium dissolution rates are extrapolated far from equilibrium, they agree within propagated uncertainty at 398 K with a recently published model by Bickmore et al. (2008). However, our extrapolated rates become progressively slower than model predictions with increasing temperature. Furthermore, we see no dependence of the postulated Q¹ reaction rate on pH, and a poorly-constrained pH dependence of the postulated Q² rate. Our slow extrapolated rates are presumably related to the increasing contribution of dissolution at Q³ sites far from equilibrium. The use of the potentiometric technique for rate measurement will yield both rate data and insights into the mechanisms of dissolution over a range of chemical affinity. Such measurements are needed to model the evolution of many natural systems quantitatively.     

Geochemically induced shifts in catabolic energy yields explain past ecological changes of diffuse vents in the East Pacific Rise 9°50'N area

The East Pacific Rise (EPR) at 9°50'N hosts a hydrothermal vent field (Bio9) where the change in fluid chemistry is believed to have caused the demise of a tubeworm colony. We test this hypothesis and expand on it by providing a thermodynamic perspective in calculating free energies for a range of catabolic reactions from published compositional data. The energy calculations show that there was excess H₂S in the fluids and that oxygen was the limiting reactant from 1991 to 1997. Energy levels are generally high, although they declined in that time span. In 1997, sulfide availability decreased substantially and H₂S was the limiting reactant. Energy availability dropped by a factor of 10 to 20 from what it had been between 1991 and 1995. The perishing of the tubeworm colonies began in 1995 and coincided with the timing of energy decrease for sulfide oxidizers. In the same time interval, energy availability for iron oxidizers increased by a factor of 6 to 8, and, in 1997, there was 25 times more energy per transferred electron in iron oxidation than in sulfide oxidation. This change coincides with a massive spread of red staining (putative colonization by Fe-oxidizing bacteria) between 1995 and 1997. For a different cluster of vents from the EPR 9°50'N area (Tube Worm Pillar), thermodynamic modeling is used to examine changes in subseafloor catabolic metabolism between 1992 and 2000. These reactions are deduced from deviations in diffuse fluid compositions from conservative behavior of redox-sensitive species. We show that hydrogen is significantly reduced relative to values expected from conservative mixing. While H₂ concentrations of the hydrothermal endmember fluids were constant between 1992 and 1995, the affinities for hydrogenotrophic reactions in the diffuse fluids decreased by a factor of 15 and then remained constant between 1995 and 2000. Previously, these fluids have been shown to support subseafloor methanogenesis. Our calculation results corroborate these findings and indicate that the 1992-1995 period was one of active growth of hydrogenotrophic communities, while the system was more or less at steady state between 1995 and 2000.     

Stream Restoration Performance and Its Contribution to the Chesapeake Bay TMDL: Challenges Posed by Climate Change in Urban Areas

In large part driven by total maximum daily load (TMDL) mandates, the restoration community in the Chesapeake Bay region has been implementing novel best management practices (BMPs) and stream restoration designs in urban areas, such as regenerative stream/stormwater conveyance (RSC) structures and stream-wetland complexes (SWCs). However, the nutrient and sediment reduction efficiencies of these novel designs are virtually unknown, and the possibility of increasing riverine flow in the Chesapeake Bay watershed associated with climate change this century necessitates an evaluation of their performance to develop and utilize those that optimize reductions in nutrient and sediment fluxes. We compare pre- and post-construction loads (total nitrogen (TN), total phosphorus (TP), and total suspended solids (TSS)) from RSCs (i.e., upland BMPs) and a SWC (i.e., stream restoration) constructed at the outflow of a highly developed watershed in the Coastal Plain physiographic province of Maryland. The largest of the two RSCs performed best in relation to expected nutrient and sediment reductions because of superior water retention capability. By the length of river reach restored, the SWC attained from 79 to 88% of its N reduction TMDL goal, but only 19 to 23 and 2.7 to 3.1% for TP and TSS, respectively; by watershed area, % attainments of TMDL goals were much lower. Results indicate that SWCs have the potential to curtail N loading from developed catchments, but additional water quality benefits may be limited. Climate change projections indicate that there will be an increased frequency of larger-volume storms that will result in an increase in stormflow runoff from urban areas, and increased pollutant loads will likely curtail potential gains made by efforts to achieve TMDL goals. Given the large-scale implementation of BMPs currently underway to accommodate the Chesapeake Bay TMDL, the restoration community needs to adopt a concerted strategy of building climate resilience into many types of urban BMPs to help attain and maintain loads at TMDL levels in anticipation of a progressively wetter climate throughout this century.     

Measurement and interpretation of molecular-level forces of interaction between the siderophore azotobactin and mineral surfaces

The forces of interaction were measured between the siderophore azotobactin and the minerals goethite (α-FeOOH) and diaspore (α-AlOOH) in aqueous solution using force microscopy. Azotobactin, a pyoverdin-type siderophore, was covalently linked to a hydrazide terminated atomic force microscope tip using a standard active ester protein coupling technique. Upon contact with each mineral surface, the adhesion force between azotobactin and goethite was two to three times the value observed for the isostructural Al-equivalent diaspore. The affinity for the solid iron oxide surface reflected in the force measurements correlates with the specificity of azotobactin for aqueous ferric iron. Further, the adhesion force between azotobactin and goethite significantly decreases (4 nN to 2 nN) when small amounts of soluble iron (0.1 μM FeCl₃ · 6H₂O) are added to the system at pH 3.5 suggesting a significant specific interaction between the chelating reactive center of azotobactin and the mineral surface. Changes in the force signature with pH and ionic strength were fairly predictable when considering mineral solubility, the charge character of the mineral surfaces, the molecular structure of azotobactin, and the intervening solution. For example, azotobactin-goethite adhesion values were consistently smaller at pH 3.5 relative to the forces at pH 7. At the lower pH, the large number of protons and the increase in the mineral solubility provides additional electron acceptors (e.g., H⁺ and Fe³⁺(aq)) that are free to compete for the basic oxygen chelating sites in the azotobactin structure. It is believed that this competition disrupts siderophore affinity for the surface resulting in decreased adhesion values.     

Collagen fingerprinting for the species identification of archaeological amphibian remains

Amphibians are well known as being one of the main groups of animals today most threatened by environmental changes but they are also some of the least well understood of all terrestrial vertebrates. This gap in knowledge is much greater as we look further back into the relatively recent past, despite representing an invaluable resources in archaeological and palaeontological assemblages that are more indicative of palaeoclimate conditions than most other vertebrate taxa. This in part stems from their remains being typically much less studied, partly due to the less common forms of expertise required for identifications based on skeletal morphology – the most frequently observed tissue that remains in ancient assemblages. Here we apply a method of biomolecular species identification by collagen peptide mass fingerprinting to the British Late Pleistocene assemblage of Pin Hole Cave (Creswell Crags, UK) as well as a range of relevant extant taxa for comparison. Our results demonstrate the ability to separate at the species level with all modern taxa investigated, allowing for the identification of these archaeological remains to the amphibian taxa known to exist in Late Pleistocene Britain. Analyses of the Pin Hole assemblage found a dominance of the two species previously known from the site (common frogs and toads: Rana temporaria and Bufo bufo, respectively) and also a small number of the rarer natterjack toad (Epidalea calamita) not previously identified in the Creswell Crags region but known from other sites in the UK; additionally, one specimen appeared to yield the fingerprint of the moor frog (R. arvalis), now extinct in the UK. As such, collagen fingerprinting is here shown to widen the known palaeobiodiversity of taxa, and highlights the further potential to enhance our understanding of climate change in the past.     

International Association of Geoanalysts' Protocol for the Certification of Geological and Environmental Reference Materials: A Supplement

The International Association of Geoanalysts (IAG) published a protocol for the certification of reference materials in close accord with the International Organisation for Standardisation (ISO) guidelines (Kane et al. 2003). This article supplements that protocol, providing additional discussion of best approaches for pre-selecting laboratories for participation in certification projects. This discussion also makes a distinction between inter-laboratory certifications, where n = 15 is the general standard, and expert laboratory certifications, where a much smaller number of laboratories will be deemed qualified to provide data of the quality needed for certification.