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PurposeWhy some people are motivated to become leaders is important both conceptually and practically. Motivation to lead compels people to seek out leadership roles and is a distinct predictor of leader role occupancy. The goal of our research is to determine contextual (socioeconomic status and parenting quality), interpersonal (sociometric status), and personal (self-esteem and gender) antecedents of the motivation to lead among young adults.Design/methodology/approachThe authors tested the model using two samples of Canadian undergraduate students (Sample 1: N = 174, M age = 20.02 years, 83% female; Sample 2: N = 217, M age = 18.8 years, 54% female). The authors tested the proposed measurement model using the first sample, and tested the hypothesized structural model using the second sample.FindingsThe proposed 5-factor measurement model provided an excellent fit to the data. The hypothesized model also provided a good fit to the data after controlling for potential threats from endogeneity. In addition, gender moderated the relationship between sociometric status and affective-identity motivation to lead, such that this interaction was significant for females but not males.Practical implicationsThe findings make a practical contribution in understanding how parents, teachers, and organizations can encourage greater motivation to lead, especially among young adults who have faced poverty and marginalization and tend to be excluded from leadership positions in organizations.Originality/valueThe authors conceptualize and test the contextual, interpersonal, and personal predictors of affective-identity motivation to lead among young adults.

Bridgesite-(Ce), (IMA2019-034), was discovered at Tynebottom Mine, Cumbria, UK. It occurs as thin (1–2 μm) translucent blue crystals with a lath-like to acicular habit, aggregated into thin crusts and is associated mainly with brochantite, malachite, serpierite, devilline, gypsum, aragonite, jarosite, pyrite, lanthanite-(Ce) and undifferentiated iron oxyhydroxides, it is often intergrown with these other minerals. The lustre, hardness, cleavage and parting could not be determined, nor could density be measured due to crystal size. It has a pale blue streak and is brittle with a splintery fracture. Bridgesite-(Ce) is biaxial (–), shows no pleochroism and has refractive indices (white light): α = 1.526(2), β = 1.564(2), γ = 1.572(2) and 2V(calc) = 48.3°. The empirical formula calculated on the basis of 44 negative charges is Ca0.86REEΣ1.99Al0.07Cu5.95(SO4)3.99(SiO4)0.05(PO4)0.02(OH)11.52⋅8H2O. The idealised formula is CaCe2Cu6(SO4)4(OH)12⋅8H2O, requiring (wt.%): 3.91 CaO, 22.89 Ce2O3, 33.28 CuO, 22.33 SO3 and 17.59 H2O. Bridgesite-(Ce) is monoclinic, space group C2/m, a = 24.801(5), b = 6.3520(13), c = 11.245(2) Å, β = 114.51(3)°, V = 1611.9(6) Å and Z = 2. The five most intense X-ray diffraction peaks in the measured pattern are [d in Å (I, %) (hkl)]: 11.3 (100) (200), 6.391 (15) (201), 2.770 (8) (420), 3.194 (6) (402) and 4.858 (5) (310). The crystal structure was solved using single crystal data and refined to an R1 index of 5.86%. Bridgesite-(Ce) contains three distinct Cu sites containing Cu2+, two are coordinated octahedrally and one is square pyramidal. The octahedra form chains through edge sharing parallel to the b-axis which are linked by the square pyramid to form sheets oriented parallel to {100}. Sulfate tetrahedra decorate the sheets which are held together by interstitial REE3+, Ca2+ and hydrogen bonding. The structure is unique. Despite apparent similarity in chemical formula, bridgesite-(Ce) is not closely related to any other natural Cu-sulfate mineral. An FTIR absorption spectra is presented for reference purposes.

Research on corporate greenwashing has expanded rapidly in recent years. At the same time, emerging studies in related literatures have found that employees are seeking out firms that are social and environmental leaders, and employee activism within firms is growing. However, the effect of firms’ exaggeration and misrepresentation of environmental claims, or greenwashing, on their own employees has been overlooked. Accordingly, we investigate greenwashing from an organizational psychology lens, exploring the impact it can have on employees, and whether these effects differ for different types of employees. Using data collected at three separate time points from a sample of employees educated in environmental science/sustainability, our results show that greenwashing was positively related to perceptions of corporate hypocrisy, which in turn, resulted in higher turnover intentions. We also found that these relationships were moderated by employees’ level of environmental education. By uncovering the deleterious effects greenwashing can have for employees and, by extension, for their employers, these findings generate insights into the extent to which corporate environmental communications can backfire.

Greenwashing is more virulent than ever. A profusion of environmental, social, and governance and net zero commitments are becoming fraught with questionable and misleading claims. At the same time, we are no closer to solving the pressing environmental and social issues of our time. In this review, we seek to examine this shift and summarize changes in greenwash research into three key phases: (a) 1.0 Static Communication; (b) 2.0 Dynamic Management; and (c) 3.0 Narratives about the Future. We analyze current key areas of developing literature and point to numerous open questions for future research. Next, we go beyond much of the published work to examine emerging tactics and lay out a forward-looking agenda for future research. We also propose a model of Corporate Miscommunication, integrating various streams in greenwash research. In doing so, we seek to lay a pathway for greenwashing researchers to finally find that elusive “end” to greenwashing.

Simple n-alcohols, such as 1-dodecanol, show anomalous film-forming and friction behaviour under elastohydrodynamic lubrication (EHL) conditions, as found inside bearings and gears. Using tribometer, diamond anvil cell (DAC), and differential scanning calorimetry (DSC) experiments, we show that liquid 1-dodecanol undergoes pressure-induced solidification when entrained into EHL contacts. Different solid polymorphs are formed inside the contact depending on the temperature and pressure conditions. Surprisingly, at moderate temperature and pressure, 1-dodecanol forms a polymorph that exhibits robust macroscale superlubricity. The DAC and DSC experiments show that superlubricity is facilitated by the formation of lamellar, hydrogen-bonded structures of hexagonally close-packed molecules, which promote interlayer sliding. This novel superlubricity mechanism is similar to that proposed for the two-dimensional materials commonly employed as solid lubricants, but it also enables the practical advantages of liquid lubricants to be maintained. When the pressure is increased, 1-dodecanol undergoes a polymorphic transformation into a phase that gives higher friction. The DAC and DSC experiments indicate that the high-friction polymorph is an orthorhombic crystal. The polymorphic transformation pressure coincides with the onset of dimple formation in the EHL films, revealing that the anomalous film shapes are caused by the formation of rigid orthorhombic crystals inside the contact. This is the first demonstration of macroscale superlubricity in an EHL contact lubricated by a non-aqueous liquid that arises from bulk effects rather than tribochemical transformations at the surfaces. Since the superlubricity observed here results from phase transformations, it is continuously self-replenishing and is insensitive to surface chemistry and topology. This discovery creates the possibility of implementing superlubricity in a wide range of machine components, which would result in enormous improvements in efficiency and durability.

We examine the role of custodianship in the renewal of the institution of public water services in Detroit, Michigan. Our longitudinal qualitative study begins prior to the 33,000 household water s...

Explanations for field change emphasize the role of purposeful strategic actors, paying little attention to uncoordinated but cohesive social groups, despite their profound impacts on fields ranging from autos and news to politics. Using a mixed methods approach, we study Millennials’ driving behaviours, focusing on the role of generation cohorts as field actors. Combining in‐depth qualitative analysis with an original nationwide survey (N = 2,225) we find that Millennials exhibit significantly different driving behaviour than earlier generations, driving for roughly 8 per cent fewer trips. These differences are primarily due to their attitudes, not, as commonly presumed, socio‐economic factors. Our results contribute to theory on fields and collective actors. First, we identify a new field phenomenon, correlated groups, uncoordinated actors behaving as collective agents due to shared experiences and characteristics. Second, we identify four mechanisms through which correlated groups impact fields: correlated imprinting, cohorts as conduit, cohort myth apathy, and cohort myth creation.

CM2 chondrites experienced widespread aqueous and short term thermal alteration on their parent bodies. Whilst previous Raman spectroscopic investigations have investigated insoluble organic matter (IOM), they have not taken into account the binary nature of IOM. Studies employing mass spectrometry have indicated that IOM also known as macromolecular organic matter (MOM) is in fact composed of two distinct fractions: labile organic matter (LOM) and refractory organic matter (ROM). The ROM component represents the aromatic rich and heteroatom poor component of IOM/MOM, whilst the LOM fraction represents a more heteroatom and aliphatic rich component. Here we report Raman 2D maps and spectroscopic data for Murchison and Mighei, both before and after chemical degradation, which attacks and liberates LOM. The removal of LOM simulates the effects of aqueous alteration, where ester and ether bonds are broken and is thought to release some components to the soluble organic matter (SOM) fraction, also known as the free organic matter fraction (FOM). Raman spectroscopy can be used to reveal the nature of bonding (sp2 and sp3) within carbonaceous materials such as meteoritic organic matter, through evaluation of the D and G band peak centres and FWHM values from the recorded data. The presence of sp3 orbitals indicates that the organic materials contain aliphatic linkages and/or heteroatoms. Statistical analysis of the Raman parameters obtained here indicates that the organic matter originating the Raman response is indistinguishable between the bulk (chemically untreated) and chemically degraded (treated with KOH and HI) samples. Such an observation indicates that the ROM fraction is the major contributor to the Raman response of meteoritic organic matter and thus Raman spectroscopy is unlikely to record any aqueous alteration processes that have affected meteoritic organic matter. Therefore, studies which use Raman to probe the IOM are investigating just one of the components of IOM and not the entire fraction. Studies that aim to investigate the effects of aqueous alteration on meteoritic organic matter should use alternate techniques to Raman spectroscopy. Furthermore, the indistinguishable nature of the Raman response of ROM from Murchison and Mighei suggests these meteorites inherited a ROM component that is chemically similar, reflecting either a common process for the formation of CM2 meteoritic ROM and/or that these meteorites probed the same ROM reservoir.

This study compares the chemical integrity of English Oak (Quercus robur) samples with an age range of four centuries by analysing the lignin degradation. The samples were collected from four historic British vessels and thus represent samples of diverse ages which have nonetheless experienced similar non-arboreal environments. We conclude that the Mary Rose, the oldest vessel studied and the recipient of the most intensive conservation efforts, has been well-preserved through treatment with PEG, and we present a baseline for assessing whether a ship has been biologically degraded.The work combines quantitative analytic chemistry techniques (e.g., THM-GC-MS) with the conservation of large historic artifacts.

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Recent space missions have identified organics, chlorinated and non-chlorinated, on Mars. Understanding the origin, current state and reactivity of this carbonaceous material is critical to efforts to detect organic signatures of possible past life on Mars. Environmental effects such as UV radiation, pressure, diagenesis, aqueous activity and presence of perchlorates have been previously been assessed using analog experiments. To this list, Fox, et al. adds and quantifies the effect of galactic cosmic rays and solar winds on organic material on the surface and in the near sub-surface of Mars. Their work, using laboratory analog materials and radiation, shows that the same organic acids, formic and oxalic acid, are produced after exposure equivalent to that over Martian history at depths of less than 5 cm, independent of mineral matrix or starting organic materials. These experiments suggest that planned sub-surface exploration using the drill on the Rosalind Franklin Rover (ExoMars) will sample organic ma...

Heavy oil is recovered from reservoirs using steam-assisted technology, which can lead to H2S generation if the oil is relatively sulfur-rich. We have used laboratory aquathermolysis to simulate the steam-assisted gravity drainage process and have compared free heavy oil to that contained within the mineral matrix. The presence of a mineral matrix was found to affect the amount of H2S produced and the chemical properties of the oil generated. Our findings show that H2S production is initiated by the presence of naturally occurring minerals at specific temperatures and pressures and production techniques that avoid these conditions will minimize H2S production.

As the COVID-19 pandemic spread around the world, it laid bare the long-standing intersecting and overlapping injustices of race and socioeconomic status. Our longitudinal qualitative study of the ...

Extraterrestrial organic matter has been widely studied; however, its response to pressure has not. Primitive organic matter bearing meteorites, such as CI and CM carbonaceous chondrites, have experienced variable pressures, up to 10 GPa. To appreciate the effects of these pressures on the organic content of these bodies, the model compounds isophthalic acid, vanillin and vanillic acid were subjected to pressures of up to 11.5 GPa and subsequently decompressed. High resolution synchrotron source Fourier Transform Infrared (FTIR) was used to determine the effects of different benzene substituents at high pressure on both the vibrational assignments of the benzene core of the molecules and the ability of the aromatic compounds to form intermolecular hydrogen bonds. The presence of additional peaks at high pressure was found to coincide with molecules that contain carboxyl groups, these features are interpreted as C-H---O intermolecular hydrogen bonds. The formation of these hydrogen bonds has implications for the origination of macromolecular organic matter (MOM), owing to the importance of such attractive forces during episodes of cross linking, such as esterification. Pressure-induced hydrogen bond formation is a process by which aromatic MOM precursors could have cross linked to generate the organic polymers found within extraterrestrial bodies today.

Research summary Social-benefit markets, such as those for carbon trading, are becoming increasingly popular for combating complex social and environmental problems. However, their unique characteristics pose substantial challenges to market creation and require novel entrepreneurial approaches. Integrating the entrepreneurship literature with that of management information systems, we conceptualize social-benefit markets as a new type of interorganizational arrangement and develop a model of social-benefit market creation. First, we argue that a core entrepreneurial collective, comprising a plurality of actors from government, business, and social movements, is essential. Second, we elaborate a six-phase process through which the interests of entrepreneurs are aligned and inscribed in a market artifact and the market is formed. The model is illustrated with reference to the Western Climate Initiative's carbon market creation efforts. Managerial summary Carbon markets have become a popular strategy for reducing greenhouse gas emissions, with similar market-based solutions being proposed for other social and environmental challenges. We refer to these new structures as social-benefit markets. Social-benefit market creation is a complex undertaking that will require novel entrepreneurial approaches and new interorganizational information systems. In an effort to reduce some of this complexity, we propose a model to explain how entrepreneurs from government, business, and social movements must work collectively to build social-benefit markets. We further elaborate a six-phase process through which entrepreneurs are able to align their diverse interests and create a stable market artifact. For managers from all sectors, our work offers actionable guidance for forming collective ventures that deliver real social benefits. Copyright © 2017 Strategic Management Society

The detection of chlorinated hydrocarbons by Curiosity on Mars has been attributed to the presence of unidentified indigenous organic matter. Similarly, oxychlorines on Earth have been proposed to be responsible for the apparent lack of organics in the Atacama Desert. The presence of perchlorate (ClO4-) poses a unique challenge to the measurement of organic matter due to the oxidizing power of oxychlorines during commonly used pyrolysis-gas chromatography-mass spectrometry (py-GC-MS) methods. Here, we show that perchlorates and other oxyanion salts inhibit the detection of organic compounds but that removing these problematic species prior to pyrolysis by using an optimal sample extraction duration and suitable ratios of water to sample mass enables analysis. We have characterized leached and unleached samples containing perchlorates from the Atacama Desert and have found that after leaching, the py-GC-MS chromatograms of the dried mineral residues show identifiable biomarkers associated with indigenous cyanobacteria. Samples which were pyrolyzed without leaching showed no detectable organic matter other than background siloxane and very weak or no trace of detectable polychlorinated benzenes. Dried sample residues remaining after leaching, the mineral matrix and water-insoluble organic matter, showed a strong organic response in all cases when analyzed by py-GC-MS. These residues are most likely the product of the pyrolysis of water-insoluble organics originally present in the samples. In addition, our results imply that previous soil analyses which contained high levels of oxyanions and concluded that organics were either not present or were present at extremely low levels should be reexamined.

As demands on global water resources intensify, battles are emerging over water ownership and governance. Evidence to support opposing views is scarce, however, especially with respect to the impact of ownership on water quality. Using a data set of 168,823 municipal water systems in the United States from 2010 to 2014, we find evidence that stakeholder attention moderates the effect of ownership on compliance with drinking water quality standards. Private systems’ compliance improves more rapidly with system size, consistent with greater social movement pressure, while public systems’ compliance improves more rapidly with local educational attainment, consistent with greater responsiveness to stakeholder attention and concern.

Significance It has remained an unresolved question whether microorganisms recovered from the most arid environments on Earth are thriving under such extreme conditions or are just dead or dying vestiges of viable cells fortuitously deposited by atmospheric processes. Based on multiple lines of evidence, we show that indigenous microbial communities are present and temporally active even in the hyperarid soils of the Atacama Desert (Chile). Following extremely rare precipitation events in the driest parts of this desert, where rainfall often occurs only once per decade, we were able to detect episodic incidences of biological activity. Our findings expand the range of hyperarid environments temporarily habitable for terrestrial life, which by extension also applies to other planetary bodies like Mars., Traces of life are nearly ubiquitous on Earth. However, a central unresolved question is whether these traces always indicate an active microbial community or whether, in extreme environments, such as hyperarid deserts, they instead reflect just dormant or dead cells. Although microbial biomass and diversity decrease with increasing aridity in the Atacama Desert, we provide multiple lines of evidence for the presence of an at times metabolically active, microbial community in one of the driest places on Earth. We base this observation on four major lines of evidence: (i) a physico-chemical characterization of the soil habitability after an exceptional rain event, (ii) identified biomolecules indicative of potentially active cells [e.g., presence of ATP, phospholipid fatty acids (PLFAs), metabolites, and enzymatic activity], (iii) measurements of in situ replication rates of genomes of uncultivated bacteria reconstructed from selected samples, and (iv) microbial community patterns specific to soil parameters and depths. We infer that the microbial populations have undergone selection and adaptation in response to their specific soil microenvironment and in particular to the degree of aridity. Collectively, our results highlight that even the hyperarid Atacama Desert can provide a habitable environment for microorganisms that allows them to become metabolically active following an episodic increase in moisture and that once it decreases, so does the activity of the microbiota. These results have implications for the prospect of life on other planets such as Mars, which has transitioned from an earlier wetter environment to today’s extreme hyperaridity.

Corporate claims about environmental performance have increased rapidly in recent years, as has the incidence of greenwash, that is, communication that misleads people into forming overly positive beliefs about an organization’s environmental practices or products. References to greenwash in the literature have grown rapidly since the term was introduced more than 2 decades ago, with a sharp increase in articles since 2011. We review and synthesize this fragmented and multidisciplinary literature, showing that greenwash is a broad umbrella term that encompasses a variety of specific forms of misleading environmental communication. More research is needed that identifies and catalogues the varieties of greenwash, theorizes and models their mechanisms drawing on existing social science research, and measures their impacts on corporate performance and social welfare.

World water resources, once seen as plentiful and virtually infinite, are under increasing pressure from population growth, urbanization, industrial demands, and climate change. Although isolated a...

We theorize that social media will reduce the incidence of corporate greenwash. Drawing on the management literature on decoupling and the economic literature on information disclosure, we characterize specifically where this effect is likely to be most pronounced. We identify important differences between social media and traditional media, and present a theoretical framework for understanding greenwash in which corporate environmental communications may backfire if citizens and activists feel a company is engaging in excessive self-promotion. The framework allows us to draw out a series of propositions regarding the impact of social media on corporate decisions whether to greenwash, and what channels to use for environmental communication. We conclude with a number of suggestions for future research.

To better understand the hot water-mediated organic transformation process (aquathermolysis) that occurs during the steam-assisted recovery of heavy oils and bitumen we have performed a series of experiments that subject a heavy oil to progressively higher temperatures and pressures in the presence of liquid water. As temperature and pressure increases, from ambient conditions to 300 °C and 1250 psig (8.6 MPa), a floating oil (flotate) is generated and is composed of mostly aliphatic hydrocarbons that appear to be generated at the expense of polars and asphaltenes. Analyses of hopane maturity parameters for the flotate indicate lower temperatures than the starting material suggesting the liberation of hopanes and, therefore, other hydrocarbons, from asphaltenes. Infrared spectra confirm changes in overall organic constitution as the relative abundance of hydrocarbons to oxygen-containing functional groups increases in the flotate. At the highest temperatures and pressures (325 °C, 1750 psig (13.8 MPa)) the flotate is at a maximum relative amount, the untransformed heavy oil is at a minimum and significant amounts of methane are generated indicating the onset of cracking. Steam-assisted recovery of heavy oil, therefore, leads to changes in the chemical constitution of a number of chemical fractions generating a lighter oil and gases that must be taken into account when planning field operations for production.

Lycopodium sporopollenin, a natural copolymer, shows exceptional stability under high hydrostatic pressures (10 GPa) as determined by in situ high pressure synchrotron source Fourier transform infrared spectroscopy. This stability is evaluated in terms of the component compounds of the sporopollenin: p-coumaric acid, phloretic acid, ferulic acid, and palmitic and sebacic acids, which represent the additional n-acid and n-diacid components. This high stability is attributed to interactions between these components, rather than the exceptional stability of any one molecular component. This study proposes a biomimetic solution for the creation of polymer materials that can withstand high pressures for a multitude of uses in aeronautics, vascular autografts, ballistics, and light-weight protective materials.

The influence of polycyclic aromatic nitrogen heterocycles (PANHs), which have been suggested as contributors to the interstellar IR emission bands, on interstellar emission features is difficult to constrain because their infrared characteristics are strongly similar to those for polycyclic aromatic hydrocarbons (PAHs). One possible solution is to seek a means of visualizing the presence of PANHs that provides information that is distinct from that for PAHs. Although PANHs and PAHs have similar infrared characteristics in many settings, this relationship may not be universally maintained. We have used in situ high-pressure synchrotron-source Fourier transform infrared spectroscopy to determine that the responses of two representative molecules, acridine and anthracene, differ at high pressures (>ca. 1 GPa). Because there are a number of high-pressure environments that can be remotely observed by infrared spectroscopy, they represent a potential to glimpse the distribution of PANHs across the cosmos.

In this paper, we move beyond the typical focus on the role of individuals in leading social change to examine “collective social entrepreneurship”, the role multiple actors collaboratively play to address social problems, create new institutions, and dismantle outdated institutional arrangements. Specifically, we examine collective social entrepreneurship across a diverse range of collaborative activities including movements, alliances and markets for social good. We identify resource utilization approaches and three associated sets of activities that illustrate the work of collective social entrepreneurs—framing, convening, and multivocality. Using illustrative case studies to examine the phenomenon, we highlight the capacity of collective action across sectors to create markets, institutions and organizations and, to derive success by resonating through embeddedness in broader social movements.

The stability and evolution of organic materials found in carbonaceous and ordinary chondrites in the evolution of terrestrial planet interiors are unknown. It has been determined that massive amounts of carbonaceous material fell on the early Earth during the Late Hadean, but the processes by which this material became the Earth's hydrosphere, atmosphere and biosphere are also unknown. We here demonstrate that reactions between these primordial organic molecules and the silicate mineral montmorillonite clay occur at the pressures associated with the upper mantle and planetary assembly. These reactions have consequences for the origin of complex organic chemistry on Earth. Using synchrotron-source Fourier transform infrared (FTIR) spectroscopy with high spatial resolution and the diamond anvil cell (DAC) to reach pressures up to 9.1 GPa, we were able to observe the formation of new peaks (i.e., new bonds) at 952, 969, and 1026 cm − 1 in situ . These peaks, which appear in formic acid (HCOOH) in the presence of montmorillonite clay, may represent either the formation of organo-silicate molecules, or the formation of more complex organic molecules via templating of the crystalline structure of the minerals.

Explanations for field change have privileged the role of exogenous shocks and powerful strategic actors. In contrast, little attention has been paid to non-strategic and unorganized but cohesive s...

The majority of global petroleum is in the form of highly viscous heavy oil. Traditionally heavy oil in sands at shallow depths is accessed by large scale mining activities. Recently steam has been used to allow heavy oil extraction with greatly reduced surface disturbance. However, in situ thermal recovery processes can generate hydrogen sulphide, high levels of which are toxic to humans and corrosive to equipment. Avoiding hydrogen sulphide production is the best possible mitigation strategy. Here we use laboratory aquathermolysis to reproduce conditions that may be experienced during thermal extraction. The results indicate that hydrogen sulphide generation occurs within a specific temperature and pressure window and corresponds to chemical and physical changes in the oil. Asphaltenes are identified as the major source of sulphur. Our findings reveal that for high sulphur heavy oils, the generation of hydrogen sulphide during steam assisted thermal recovery is minimal if temperature and pressure are maintained within specific criteria. This strict pressure and temperature dependence of hydrogen sulphide release can allow access to the world's most voluminous oil deposits without generating excessive amounts of this unwanted gas product.

We have determined the melting temperature of formic acid (HCOOH) as a function of pressure to 8.5 GPa using infrared absorption spectroscopy, Raman spectroscopy and visual observation of samples in a resistively heated diamond-anvil cell. The experimentally determined incongruent melting curve compares favorably with a two-phase thermodynamic model. Decomposition reactions were observed above the melting temperature up to a pressure of 6.5 GPa, with principal products being CO2, H2O, and CO. At pressures above 6.5 GPa, decomposition led to reaction products that could be quenched as solids to zero pressure, and infrared and Raman spectra indicate that pressure leads to the presence of sp3 carbon-carbon bonding in these reaction products.

We explore how changes from private to public ownership, and vice versa, affect service quality. We develop hypotheses drawing on multiple streams of literature, and test them using a panel of data...

The production of gaseous sulfur-containing species during the steam-assisted recovery of heavy oil and bitumen have important consequences for both economics and safety. Factors such as the effects of mineral matrices require laboratory data to produce accurate models. To study mineral effects on gas production we studied a well-characterized oil-containing core and the isolated crude oil from that core. The samples were run at 250–300°C in the continued presence of liquid water for 24 hours. The reaction products of all experiments include gases, oil flotate, oil sinkate, water-soluble products, and water-insoluble residues. All reaction products were studied with a variety of analytical techniques, including FTIR spectroscopy, chromatographic fractionation (SARA analysis), GC-MS, pyrolysis GCMS and GC-FPD/TCD. These techniques were applied to whole oil, maltenes and asphaltene fractions. Physical properties including viscosity and density were also measured. Our data provide insights into the physical and chemical consequences of steam assisted recovery of heavy oils and bituments from sedimentary rock reservoirs and reveal that geological and geochemical context is an essential consideration.

The production of gaseous sulfur-containing species during the steam-assisted recovery of heavy oil and bitumen presents problems owing to their toxicity, corrosion properties and odor. In order to quantitatively study aquathermolysis sulfur chemistry during the thermal (steam-assisted) recovery of heavy oils we have subjected a well-characterized and sulfur-rich bitumen core sample to 150 - 325°C and 70 - 1740 psia (0.48 - 12 MPa) conditions in the continued presence of liquid water for 24 hours. The reaction products include gases, oil flotate, oil sinkate, water-soluble products, and water- insoluble residues. All have been studied with a variety of analytical techniques, including FTIR spectroscopy, chromatographic fractionation (SARA analysis), GC-FPD and GC-MS. Moreover, these techniques have been extended to analysis of the asphaltene fractions. Results suggest that some in-situ upgrading of the oil occurs under these conditions; additionally, gaseous hydrogen sulfide is released at temperatures at and above 250 °C. Variations in the relative abundances of solubility classes and chemical fractions imply that the source of sulfur is via the thermal degradation of resins and/or asphaltenes. The experimental methods, results and quantification approach discussed herein will be useful to support the development of models for engineering design of facilities for the steam-assisted recovery of heavy oils and bitumen.

Using a qualitative case study of the Detroit water shutoffs from 2013 through 2015, I explore how a macro-level institutional and field change, the passage of the Human Right to Water and Sanitati...

The high-pressure behavior of Keokuk kaolinite has been studied to 9.5 GPa by infrared spectroscopy using synchrotron radiation. The kaolinite-I -> kaolinite-II and kaolinite-II -> kaolinite-III transformations have clear spectroscopic expression, with discontinuities coinciding with the transformation pressures bracketed by X-ray diffraction (Welch and Crichton in Am Mineral 95: 651654, 2010). The experimental spectra have been interpreted from band assignments derived from density functional theory for the structures of kaolinite-II and kaolinite-III, using as starting models the ab initio structures reported by Mercier and Le Page (Acta Crystallogr A B64:131-143, 2008, Mater Sci Technol 25:437-442, 2009) and unit-cell parameters from Welch and Crichton (Am Mineral 95: 651654, 2010). The relaxed theoretical structures are very similar to those reported by Mercier and Le Page (Acta Crystallogr A B64: 131-143, 2008, Mater Sci Technol 25: 437-442, 2009) in their theoretical investigation of kaolinite polytypes at high pressure. The vibrational spectra calculated from the quantum-mechanical analysis allow band assignments of the IR spectra to be made and provide insights into the behavior of different OH environments in the two high-pressure polytypes. The single perpendicular-interlayer OH group of kaolinite-III has a distinctive spectroscopic signature that is diagnostic of this polytype (v = 3,595 cm(-1) at 9.5 GPa) and is sensitive to the compression/expansion of the interlayer space. This OH group also has a distinctive signature in the calculated spectra. The spectra collected on decompression are those of kaolinite-III and persist largely unchanged to 4.6 GPa, except for a continuous blue shift of the 3,595 cm(-1) band to 3,613 cm(-1). Finally, kaolinite-I is recovered at 0.6 GPa, confirming the kaolinite-III -> kaolinite-I transformation previously observed by X-ray diffraction, and the irreversibility of the kaolinite-II -> kaolinite-III transformation. The ambient spectra collected at the start and finish of the experiment are those of kaolinite-I, and start/finish band frequencies agree to within 6 cm(-1).

The infrared response of coronene (C(24)H(12)) under pressure and temperature conditions up to 10 GPa and 300 °C is examined in situ using a diamond anvil cell and synchrotron-source Fourier transform infrared (FTIR) spectroscopy. Coronene is a polycyclic aromatic hydrocarbon that is present in the interstellar medium and meteorites which may have contributed to the Earth's primordial carbon budget. It appears to undergo a reversible phase transition between 2 and 3.2 GPa at ambient temperature; new intramolecular bonds in the region 840-880 cm(-1) result from compression. We document the shift of spectral features to higher wavenumbers with increasing pressure but find this change suppressed by increased temperature. By investigating the stability of coronene over a range of naturally occurring conditions found in a range of environments, we assess the survival of the molecule through various terrestrial and extraterrestrial processes. Coronene has previously been shown to survive atmospheric entry during Earth accretion; this can now be extended to include survival through geological processes such as subduction and silicate melting of the rock cycle, opening the possibility of extraterrestrial coronene predating terrestrial accretion existing on Earth.

We have studied cyanuric acid (H(3)C(3)N(3)O(3)) at static pressures up to 8.1 GPa and simultaneous temperatures up to 750 K, using primarily infrared absorption spectroscopy and visual observation. The corresponding phase diagram compares favorably with theoretical predictions of metastable organic materials. Two reactions were observed and characterized; both are irreversible. Below 2 GPa, melting is accompanied by a decomposition reaction, and upon cooling, cyanuric acid is not recovered. Above 2 GPa, heating results in a solid product recoverable at ambient conditions. Corresponding infrared spectra suggest that pressure leads to the formation of heterocycles of increasing complexity and biological potential, with the composition determined by the pressure of formation. Cyanuric acid is of interest at these conditions because it and its monomer, isocyanic acid, are "prebiotic" compounds found in stellar dust clouds, meteorites, and other remnants of the early Earth.

We have successfully completed the research outlined in our proposal: Organic Chemistry at High Pressures and Temperatures. We have experimentally determined a phase diagram which documents the phases and reaction regimes of cyanuric acid , H{sub 3}C{sub 3}N{sub 3}O{sub 3} (1,3,5-triazine-2,4,6-trione), from 300 - 750 K and 0 - 8.1 GPa. We utilized a comparatively new technique to study thin samples of cyanuric acid in the diamond anvil cell in order to collect ambient temperature, high pressure FTIR and Raman data as well as the high-pressure, high-temperature data used in the phase diagram. These experiments made use of the CMLS High-pressure lab's diamond anvil facilities as well as the FTIR and Raman systems.

We compare the performance of private versus public water systems in terms of their compliance with water quality and treatment technique standards. We present a simple theoretical model of multi-t...

The study of field and institutional change has grown rapidly, yet we continue to understand relatively little about the actors and activities of maintenance in the face of such pressures. As actor...

We report Raman, infrared, and x-ray diffraction (XRD) measurements, along with ab initio calculations on formic acid (FA) under pressure up to 50 GPa. We find an infinite chain Pna2(1) structure to be a high-pressure phase at room temperature. Our data indicate the symmetrization and a partially covalent character of the intrachain hydrogen bonds above approximately 20 GPa. Raman spectra and XRD patterns indicate a loss of long-range order at pressures above 40 GPa, with a large hysteresis upon decompression. We attribute this behavior to a three-dimensional polymerization of FA.

There are a number of key structures that can be used to reveal the formation and modification history of organic matter in the cosmos. For instance, the susceptibility of organic matter to heat is well documented and the relative thermal stabilities of different isomers can be used as cosmothermometers. Yet despite being an important variable, no previously recognized organic marker of pressure exists. The absence of a pressure marker is unfortunate considering our ability to effectively recognize extraterrestrial organic structures both remotely and in the laboratory. There are a wide variety of pressures in cosmic settings that could potentially be reflected by organic structures. Therefore, to develop an organic cosmic pressure marker, we have used state-of-the-art diamond anvil cell (DAC) and synchrotron-source Fourier transform infrared (FTIR) spectroscopy to reveal the effects of pressure on the substitution patterns for representatives of the commonly encountered methyl substituted naphthalenes, specifically the dimethylnaphthalenes. Interestingly, although temperature and pressure effects are concordant for many isomers, pressure appears to have the opposite effect to heat on the final molecular architecture of the 1,5-dimethylnaphthalene isomer. Our data suggest the possibility of the first pressure parameter or cosmo-barometer (1,5-dimethylnaphthalene/total dimethylnaphthalenes) that can distinguish pressure from thermal effects. Information can be obtained from the new pressure marker either remotely by instrumentation on landers or rovers or directly by laboratory measurement, and its use has relevance for all cases where organic matter, temperature, and pressure interplay in the cosmos.