The effect of cation substitutions on the physical properties of trioctahedra micas.

Thesis (M.S.)--Massachusetts Institute of Technology, Dept. of Earth and Planetary Sciences, 1971.All plates numbered by preceding leaf. Vita.Bibliography: leaves 65-69.M.S

Geochemical and mineralogical evidence that Rodinian assembly was unique

The mineralogy and geochemistry associated with Rodinian assembly (~1.3–0.9 Ga) are significantly different from those of other supercontinents. Compared to other supercontinents, relatively more Nb-bearing minerals, Y-bearing minerals, and zircons formed during Rodinian assembly, with corresponding enrichments of Nb, Y, and Zr concentrations in igneous rocks. By contrast, minerals bearing many other elements (e.g., Ni, Co, Au, Se, and platinum group elements) are significantly less abundant, without corresponding depletion of Ni and Co concentrations in igneous rocks. Here we suggest that the Nb, Y, and Zr enrichments in igneous rocks and relatively more occurrences of corresponding Nb-bearing minerals, Y-bearing minerals, and zircons result from significant non-arc magmatism during the mid-Proterozoic, while fewer occurrences of many other minerals suggest enhanced erosion of Rodinian volcanic arcs and orogens. The prolonged, extrovert assembly of Rodinia from thickened mid-Proterozoic continental crust via two-sided subduction can account for both the prevalence of non-arc magmatism and the enhanced erosion

Chemical Evidence for Cell Wall Lignification and the Evolution of Tracheids in Early Devonian Plants

Anatomically preserved land plant fossils from the Lower Devonian Rhynie Chert contain conducting tissues with cells that range from dark-colored, elongated cells without secondary wall thickenings to tracheids similar to those of extant tracheophytes. A suite of tissue-specific microanalytical techniques was used to assess lignification in fossils of Aglaophyton, Rhynia, and Asteroxylon. Isotope ratio mass spectrometry provides millimeter-scale resolution of carbon isotopic abundances, whereas soft X-ray carbon (1s) spectromicroscopy provides micrometer-scale resolution of the preservation of organic molecular functionality. The isotopic and organic chemistry of Rhynie Chert plants indicates that the earliest vascular thickenings were probably unlignified and that cell wall lignification may have first appeared in the outer cortex. Only in more derived plants, it seems, was lignin deposited in conducting cells to produce the true tracheids seen today in vascular plants.Organismic and Evolutionary Biolog

Where are the paediatricians? An international survey to understand the global paediatric workforce

Objective: Our primary objective was to examine the global paediatric workforce and to better understand geographic differences in the number of paediatricians globally. Secondary objectives were to describe paediatric workforce expectations, who provides children with preventative care and when children transition out of paediatric care. Design: Survey of identified paediatric leaders in each country. Setting: Paediatric association leaders worldwide. Main outcome measures: Paediatrician numbers, provision of primary care for children, age of transition to adult care. Results: Responses were obtained from 121 countries (73% of countries approached). The number of paediatricians per 100 000 children ranged from a median of 0.5 (IQR 0.3–1.4) in low-income countries to 72 (IQR 4–118) in high-income countries. Africa and South-East Asia reported the lowest paediatrician density (median of 0.8 paediatricians per 100 000 children, IQR 0.4–2.6 and median of 4, IQR 3–9, respectively) and fewest paediatricians entering the workforce. 82% of countries reported transition to adult care by age 18% and 39% by age 15. Most countries (91%) but only 64% of low-income countries reported provision of paediatric preventative care (p\u3c0.001, Cochran-Armitage trend test). Systems of primary care provision varied widely. A majority of countries (63%) anticipated increases in their paediatric workforce in the next decade. Conclusions: Paediatrician density mirrors known inequities in health provider distribution. Fewer paediatricians are entering the workforce in areas with already low paediatrician density, which may exacerbate disparities in child health outcomes. In some regions, children transition to adult care during adolescence, with implications for healthcare training and delivery. Paediatrician roles are heterogeneous worldwide, and country-specific strategies should be used to address inequity in child health provisio

Abundant phosphorus expected for possible life in Enceladus’s ocean

Saturn’s moon Enceladus has a potentially habitable subsurface water ocean that contains canonical building blocks of life (organic and inorganic carbon, ammonia, possibly hydrogen sulfide) and chemical energy (disequilibria for methanogenesis). However, its habitability could be strongly affected by the unknown availability of phosphorus (P). Here, we perform thermodynamic and kinetic modeling that simulates P geochemistry based on recent insights into the geochemistry of the ocean–seafloor system on Enceladus. We find that aqueous P should predominantly exist as orthophosphate (e.g., HPO42−), and total dissolved inorganic P could reach 10−7 to 10−2 mol/kg H2O, generally increasing with lower pH and higher dissolved CO2, but also depending upon dissolved ammonia and silica. Levels are much higher than <10−10 mol/kg H2O from previous estimates and close to or higher than ∼10−6 mol/kg H2O in modern Earth seawater. The high P concentration is primarily ascribed to a high (bi)carbonate concentration, which decreases the concentrations of multivalent cations via carbonate mineral formation, allowing phosphate to accumulate. Kinetic modeling of phosphate mineral dissolution suggests that geologically rapid release of P from seafloor weathering of a chondritic rocky core could supply millimoles of total dissolved P per kilogram of H2O within 105 y, much less than the likely age of Enceladus’s ocean (108 to 109 y). These results provide further evidence of habitable ocean conditions and show that any oceanic life would not be inhibited by low P availability

Catalytic peptide hydrolysis by mineral surface: Implications for prebiotic chemistry

Abstract The abiotic polymerization of amino acids may have been important for the origin of life, as peptides may have been components of the first self-replicating systems. Though amino acid concentrations in the primitive oceans may have been too dilute for significant oligomerization to occur, mineral surface adsorption may have provided a concentration mechanism. As unactivated amino acid polymerization is thermodynamically unfavorable and kinetically slow in aqueous solution, we studied mainly the reverse reaction of polymer degradation to measure the impact of mineral surface catalysis on peptide bonds. Aqueous glycine (G), diglycine (GG), diketopiperazine (DKP), and triglycine (GGG) were reacted with minerals (calcite, hematite, montmorillonite, pyrite, rutile, or amorphous silica) in the presence of 0.05 M, pH 8.1, KHCO 3 buffer and 0.1 M NaCl as background electrolyte in a thermostatted oven at 25, 50 or 70°C. Below 70°C, reaction kinetics were too sluggish to detect catalytic activity over amenable laboratory time-scales. Minerals were not found to have measurable effects on the degradation or elongation of G, GG or DKP at 70°C in solution. At 70°C pyrite was the most catalytic mineral with detectible effects on the degradation of GGG, although several others also displayed catalytic behavior. GGG degraded $1.5-4 times faster in the presence of pyrite than in control reactions, depending on the ratio of solution concentration to mineral surface area. The rate of pyrite catalysis of GGG hydrolysis was found to be saturable, suggesting the presence of discrete catalytic sites on the mineral surface. The mineral-catalyzed degradation of GGG appears to occur via a GGG ? DKP + G mechanism, rather than via GGG ? GG + G, as in solution-phase reactions. These results are compatible with many previous findings and suggest that minerals may have assisted in peptide synthesis in certain geological settings, specifically by speeding the approach to equilibrium in environments where amino acids were already highly concentrated, but that minerals may not significantly alter the expected solution-phase equilibria. Thus the abiotic synthesis of long peptides may have required activating agents, dry heating at higher temperatures, or some form of phase separation

UV Irradiation and Near Infrared Characterization of Laboratory Mars Soil Analog Samples

The search for molecular biosignatures at the surface of Mars is complicated by an intense irradiation in the mid- and near-ultraviolet (UV) spectral range for several reasons: (i) many astrobiologically relevant molecules are electronically excited by efficient absorption of UV radiation and rapidly undergo photochemical reactions; (ii) even though the penetration depth of UV radiation is limited, aeolian erosion continually exposes fresh material to radiation; and (iii) UV irradiation generates strong oxidants such as perchlorates that can penetrate deep into soils and cause subsurface oxidative degradation of organics. As a consequence, it is crucial to investigate the effects of UV radiation on organic molecules embedded in mineral matrices mimicking the martian soil, in order to validate hypotheses about the nature of the organic compounds detected so far at the surface of Mars by the NASA Mars Science Laboratory’s (MSL) Curiosity rover, as well as organics that will be possibly found by the next rover missions Mars 2020 (NASA) and ExoMars 2022 (ESA-Roscosmos). In addition, studying the alteration of possible molecular biosignatures in the martian environment will help to redefine the molecular targets for life detection missions and devise suitable detection methods. Here we report the results of mid- and near-UV irradiation experiments of Mars soil analog samples obtained adsorbing relevant organic molecules on a clay mineral that is quite common on Mars, i.e. montmorillonite, doped with 1 wt% of magnesium perchlorate. Specifically, we chose to investigate the photostability of a plausible precursor of the chlorohydrocarbons detected on Mars by the Curiosity rover, namely phthalic acid, along with the biomarkers of extant life L-phenylalanine and L-glutamic acid, which are proteomic amino acids, and adenosine 5’-monophosphate, which is a nucleic acid component. We monitored the degradation of these molecules adsorbed on montmorillonite through in situ spectroscopic analysis, investigating the reflectance properties of the samples in the Near InfraRed (NIR) spectral region. Such spectroscopic characterization of molecular alteration products provides support for two upcoming robotic missions to Mars that will employ NIR spectroscopy to look for molecular biosignatures, through the instruments SuperCam on board Mars 2020, ISEM, Ma_Miss and MicrOmega on board ExoMars 2022

Surface Water Microbial Community Response to the Biocide 2,2-Dibromo-3-Nitrilopropionamide, Used in Unconventional Oil and Gas Extraction.

Production of unconventional oil and gas continues to rise, but the effects of high-density hydraulic fracturing (HF) activity near aquatic ecosystems are not fully understood. A commonly used biocide in HF, 2,2-dibromo-3-nitrilopropionamide (DBNPA), was studied in microcosms of HF-impacted (HF+) versus HF-unimpacted (HF-) surface water streams to (i) compare the microbial community response, (ii) investigate DBNPA degradation products based on past HF exposure, and (iii) compare the microbial community response differences and similarities between the HF biocides DBNPA and glutaraldehyde. The microbial community responded to DBNPA differently in HF-impacted versus HF-unimpacted microcosms in terms of the number of 16S rRNA gene copies quantified, alpha and beta diversity, and differential abundance analyses of microbial community composition through time. The differences in microbial community changes affected degradation dynamics. HF-impacted microbial communities were more sensitive to DBNPA, causing the biocide and by-products of the degradation to persist for longer than in HF-unimpacted microcosms. A total of 17 DBNPA by-products were detected, many of them not widely known as DBNPA by-products. Many of the brominated by-products detected that are believed to be uncharacterized may pose environmental and health impacts. Similar taxa were able to tolerate glutaraldehyde and DBNPA; however, DBNPA was not as effective for microbial control, as indicated by a smaller overall decrease of 16S rRNA gene copies/ml after exposure to the biocide, and a more diverse set of taxa was able to tolerate it. These findings suggest that past HF activity in streams can affect the microbial community response to environmental perturbation such as that caused by the biocide DBNPA.IMPORTANCE Unconventional oil and gas activity can affect pH, total organic carbon, and microbial communities in surface water, altering their ability to respond to new environmental and/or anthropogenic perturbations. These findings demonstrate that 2,2-dibromo-3-nitrilopropionamide (DBNPA), a common hydraulic fracturing (HF) biocide, affects microbial communities differently as a consequence of past HF exposure, persisting longer in HF-impacted (HF+) waters. These findings also demonstrate that DBNPA has low efficacy in environmental microbial communities regardless of HF impact. These findings are of interest, as understanding microbial responses is key for formulating remediation strategies in unconventional oil and gas (UOG)-impacted environments. Moreover, some DBNPA degradation by-products are even more toxic and recalcitrant than DBNPA itself, and this work identifies novel brominated degradation by-products formed