Orders Of Magnitude Variation Research Articles

Reactive Liftoff of Crystalline Cellulose Particles.

The condition of heat transfer to lignocellulosic biomass particles during thermal processing at high temperature (>400 °C) dramatically alters the yield and quality of renewable energy and fuels. In this work, crystalline cellulose particles were discovered to lift off heated surfaces by high speed photography similar to the Leidenfrost effect in hot, volatile liquids. Order of magnitude variation in heat transfer rates and cellulose particle lifetimes was observed as intermediate liquid cellulose droplets transitioned from low temperature wetting (500–600 °C) to fully de-wetted, skittering droplets on polished surfaces (>700 °C). Introduction of macroporosity to the heated surface was shown to completely inhibit the cellulose Leidenfrost effect, providing a tunable design parameter to control particle heat transfer rates in industrial biomass reactors.

The growth of instabilities in annular liquid sheets

An annular liquid sheet surrounded by parallel co-flowing gas is an effective atomiser. However, the initial instabilities which determine the primary break-up of the liquid sheet are not well understood. Lack of agreement on the influence of the boundary conditions and the non-dimension scaling of the initial instability persists between theoretical stability analyses and experiments, since there is little experimental data available on the near-field behaviour of the instability. To address this matter, we have undertaken an experimental parametric study of an aerodynamically-driven, non-swirling annular water sheet. The effects of sheet thickness, inner and outer gas–liquid momentum ratio were investigated over an order of magnitude variation in Reynolds and Weber number. From high-speed image correlation measurements in the near-nozzle region, we propose new empirical correlations for the frequency of the instability as a function of the total gas–liquid momentum ratio, with good non-dimensional collapse. From analysis of the instability velocity probability densities, we find two persistent and distinct superimposed instabilities with different growth rates. The first is a short-lived, rapidly saturating sawtooth-like instability. The second is a slower-growing stochastic instability which persists through the break-up of the sheet. The presence of multiple instabilities whose growth rates do not strongly correlate with the shear velocities may explain some of the discrepancies between experiments and stability analyses.

Controls on residence time and exchange in a system of shallow coastal bays

Patterns of transport and residence time influence the morphology, ecology and biogeochemistry of shallow coastal bay systems in important ways. To better understand the factors controlling residence time and exchange in coastal bays, a three-dimensional finite-volume coastal ocean model was set up and validated with field observations of circulation in a system of 14 shallow coastal bays on the Atlantic coast of the USA (Virginia Coast Reserve). Residence times of neutrally buoyant particles as well as exchange among the bays in the system and between the bays and the ocean were examined with Lagrangian particle tracking. There was orders of magnitude variation in the calculated residence time within most of the bays, ranging from hours in the tidally refreshed (repletion) water near the inlets to days–weeks in the remaining (residual) water away from the inlets. Residence time in the repletion waters was most sensitive to the tidal phase (low vs. high) when particles were released whereas residence time in the residual waters was more sensitive to wind forcing. Wind forcing was found to act as a diffuser that shortens particle residence within the bays; its effect was higher away from the inlets and in relatively confined bays. Median residence time in the bays significantly decreased with an increase in the ratio between open water area and total area (open water plus marsh). Exchange among the bays and capture areas of inlets (i.e., exchange between the bays and the ocean) varied considerably but were insensitive to tidal phase of release, wind, and forcing conditions in different years, in contrast to the sensitivity of residence time to these factors. We defined a new quantity, termed shortest-path residence time, calculated as distance from the closest inlet divided by root-mean-square velocity at each point in model domain. A relationship between shortest-path residence time and particle-tracking residence time provides a means of estimating residence time over an entire model domain.

Correlation between experimental human and murine skin sensitization induction thresholds

Quantitative risk assessment for skin sensitization is directed towards the determination of levels of exposure to known sensitizing substances that will avoid the induction of contact allergy in humans. A key component of this work is the predictive identification of relative skin sensitizing potency, achieved normally by the measurement of the threshold (the “EC3” value) in the local lymph node assay (LLNA). In an extended series of studies, the accuracy of this murine induction threshold as the predictor of the absence of a sensitizing effect has been verified by conduct of a human repeated insult patch test (HRIPT). Murine and human thresholds for a diverse set of 57 fragrance chemicals spanning approximately four orders of magnitude variation in potency have been compared. The results confirm that there is a useful correlation, with the LLNA EC3 value helping particularly to identify stronger sensitizers. Good correlation (with half an order of magnitude) was seen with three-quarters of the dataset. The analysis also helps to identify potential outlier types of (fragrance) chemistry, exemplified by hexyl and benzyl salicylates (an over-prediction) and trans-2-hexenal (an under-prediction).

Catalytic Consequences of the Thermodynamic Activities at Metal Cluster Surfaces and Their Periodic Reactivity Trend for Methanol Oxidation

AbstractThe periodic reactivity trend and the connection of kinetics to the thermodynamic activity of oxygen are established for the oxidation of methanol on metal clusters. First‐order rate coefficients are a single‐valued function of the O2‐to‐CH3OH ratio, because this ratio, together with the rate constants for O2 and CH3OH activation, determine the oxygen chemical potential, thus the relative abundance of active sites and bulk chemical state of the clusters. CH3OH activation rate constants on oxygen‐covered Ag, Pt, and Pd and on RuO2 clusters vary with the metal–oxygen binding strength in a classical volcano‐type relation, because the oxygen‐binding strength directly influences the reactivities of oxygen as H abstractors during the kinetically relevant CH3OH activation step. The differences in oxygen thermodynamic activity lead to five orders of magnitude variation in rates (Pt>Pd>RuO2>Ag, 373 K), because of its strong effects on the activation enthalpy and more prominently activation entropy in CH3OH activation.

Catalytic consequences of the thermodynamic activities at metal cluster surfaces and their periodic reactivity trend for methanol oxidation.

The periodic reactivity trend and the connection of kinetics to the thermodynamic activity of oxygen are established for the oxidation of methanol on metal clusters. First-order rate coefficients are a single-valued function of the O2 -to-CH3OH ratio, because this ratio, together with the rate constants for O2 and CH3OH activation, determine the oxygen chemical potential, thus the relative abundance of active sites and bulk chemical state of the clusters. CH3OH activation rate constants on oxygen-covered Ag, Pt, and Pd and on RuO2 clusters vary with the metal-oxygen binding strength in a classical volcano-type relation, because the oxygen-binding strength directly influences the reactivities of oxygen as H abstractors during the kinetically relevant CH3OH activation step. The differences in oxygen thermodynamic activity lead to five orders of magnitude variation in rates (Pt>Pd>RuO2>Ag, 373 K), because of its strong effects on the activation enthalpy and more prominently activation entropy in CH3OH activation.

Symmetrical windowing for quantum states in quasi-classical trajectory simulations: application to electron transfer.

It has recently been shown [S. J. Cotton and W. H. Miller, J. Chem. Phys. 139, 234112 (2013)] that a symmetrical windowing quasi-classical (SQC) approach [S. J. Cotton and W. H. Miller, J. Phys. Chem. A 117, 7190 (2013)] applied to the Meyer-Miller model [H.-D. Meyer and W. H. Miller, J. Chem. Phys. 70, 3214 (1979)] for the electronic degrees of freedom in electronically non-adiabatic dynamics is capable of quantitatively reproducing quantum mechanical results for a variety of test applications, including cases where "quantum" coherence effects are significant. Here we apply this same SQC methodology, within a flux-side correlation function framework, to calculate thermal rate constants corresponding to several proposed models of electron transfer processes [P. Huo, T. F. Miller III, and D. F. Coker, J. Chem. Phys. 139, 151103 (2013); A. R. Menzeleev, N. Ananth, and T. F. Miller III, J. Chem. Phys. 135, 074106 (2011)]. Good quantitative agreement with Marcus Theory is obtained over several orders of magnitude variation in non-adiabatic coupling. Moreover, the "inverted regime" in thermal rate constants (with increasing bias) known from Marcus Theory is also reproduced with good accuracy by this very simple classical approach. The SQC treatment is also applied to a recent model of photoinduced proton coupled electron transfer [C. Venkataraman, A. V. Soudackov, and S. Hammes-Schiffer, J. Chem. Phys. 131, 154502 (2009)] and population decay of the photoexcited donor state is found to be in reasonable agreement with results calculated via reduced density matrix theory.

Multi-order bunched soliton pulse generation by nonlinear polarization rotation mode-locking erbium-doped fiber lasers with weak or strong polarization-dependent loss

With the assistance of weak or strong polarization-dependent loss (PDL) in the cavity, nonlinear polarization rotation mode-locking (NPRML) of an erbium-doped fiber laser (EDFL) is demonstrated to show transformation on the soliton from a single to multiple bunched state with nearly one order of magnitude variation on pulsewidth. With the bent intracavity fiber providing the weak PDL, the NPRML shortens the pulsewidth from only 5.3 ps to 4.9 ps and correspondingly broadens the spectral linewidth from 0.43 nm to 0.56 nm when enlarging the pump power from 100 mW to 325 mW. With the use of an inserted polarizer providing strong PDL in an EDFL, the fundamental soliton pulsewidth is significantly compressed to 390 fs, with the spectral linewidth as wide as 7.14 nm. In particular, the parameters of the soliton pulses are nearly unchanged at different pump powers; however, the soliton pulses split to form tightly bunched pulses circulating in the EDFL cavity. There are as many as 18 solitons tightly bunched together at the maximum pump power of up to 325 mW. Such a tightly bunched package can be elucidated by soliton energy quantization and long-range soliton interaction according to the perturbation theory in a passively mode-locked EDFL.

Measuring and analyzing excitation-induced decoherence in rare-earth-doped optical materials

A method is introduced for quantitatively analyzing photon echo decay measurements to characterize excitation-induced decoherence resulting from the phenomenon of instantaneous spectral diffusion. Detailed analysis is presented that allows fundamental material properties to be extracted that predict and describe excitation-induced decoherence for a broad range of measurements, applications and experimental conditions. Motivated by the need for a method that enables systematic studies of ultra-low decoherence systems and direct comparison of properties between optical materials, this approach employs simple techniques and analytical expressions that avoid the need for difficult to measure and often unknown material parameters or numerical simulations. This measurement and analysis approach is demonstrated for the 3H6 to 3H4 optical transition of three thulium-doped crystals, Tm3+:YAG, Tm3+:LiNbO3 and Tm3+:YGG, that are currently employed in quantum information and classical signal processing demonstrations where minimizing decoherence is essential to achieve high efficiencies and large signal bandwidths. These new results reveal more than two orders of magnitude variation in sensitivity to excitation-induced decoherence among the materials studied and establish that the Tm3+:YGG system offers the longest optical coherence lifetimes and the lowest levels of excitation-induced decoherence yet observed for any known thulium-doped material.

Inter- and intra-individual variation in urinary biomarker concentrations over a 6-day sampling period. Part 2: Personal care product ingredients

An intensive study was conducted to provide data on intra- and inter-individual variation in urinary excretion of a series of ingredients in personal care products (parabens, triclosan, benzophenones) and bisphenol A (BPA, not expected to be an ingredient) in 8 volunteers over 6 days. Exposure diaries recorded use of personal care products with identified target analytes as ingredients. Participants' usual products were replaced with products without the target analytes for 2 of the 6 days. Urine void volumes and times were recorded. Methyl, ethyl, and n-propylparabens, triclosan, benzophenone-3, and BPA were frequently detected (≥70% of samples). Urinary concentrations of the parabens and triclosan were lower on product replacement days. First morning void concentrations correlated moderately to highly with 24-h composite concentrations for all analytes. Intraclass correlation coefficients (ICCs) for spot samples collected on days with usual product use were low for BPA (0.15), moderate for n-propylparaben and methylparaben (0.39 and 0.56, respectively), and high for ethylparaben, benzophenone-3, and triclosan (0.76, 0.81, and 0.934, respectively); ICCs were consistently higher on the basis of cr-adjusted concentrations. Hydration status adjustment methods were assessed by comparing unadjusted and adjusted concentrations to urinary excretion rates (ER, ng/kg-h) for all analytes and samples. Specific gravity-adjusted concentrations correlated slightly better with ER than creatinine-adjusted concentrations. Within-individual variation in biomarker concentrations was highest for methyl and ethylparabens (2 orders of magnitude variation in spot sample concentrations) and lower for the other analytes (1–1.5 orders of magnitude). This dataset provides insight into the design and interpretation of urinary biomonitoring studies for non-persistent chemicals.

Growth and calcification of marine bryozoans in a changing ocean.

Bryozoans are colonial benthic marine invertebrate calcifiers, important and especially abundant and diverse in southern hemisphere shelf environments. Large heavily calcified colonies can be up to 50 years old, but most longer-lived bryozoans are limited to 10-20 y. Many smaller species are annual. Radial extension in flat encrusting bryozoans is generally on the order of 1-5 mm/y. Erect calcified species generally grow vertically 2-15 mm/y, though articulated species such as Cellaria may reach rates of 40 mm/y. Corresponding calcification rates are generally 10(1)-10(2) mg/y, but there can be an order of magnitude variation in rate among years in high-latitude bryozoans. Multi-branched bryozoans produce up to 24 g of CaCO3/y. The carbonate produced by bryozoans varies from calcite to aragonite and mixtures of both. Skeletal carbonate mineralogy of bryozoans is complex and appears to be strongly genetically controlled. Global climate change, leading to increasing water temperatures, will generally increase marine bryozoan metabolic rates, and may increase Mg in calcite. On the other hand, decreasing pH (ocean acidification) causes corrosion, changes in mineralogy, and decreased survival. This review of bryozoan growth and calcification allows a general perspective, but also reveals gaps in our knowledge which need to be addressed.

Development of Comparative Toxicity Potentials of 14 cationic metals in freshwater

Site-dependent and site-generic Comparative Toxicity Potentials (CTPs) (also known as Characterization Factors (CFs)) were calculated for 14 cationic metals (Al(III), Ba, Be, Cd, Co, Cr(III), Cs, Cu(II), Fe(II), Fe(III), Mn(II), Ni, Pb, Sr and Zn), to be applied in Life Cycle Impact Assessment. CTPs were calculated for 7 EU-archetypes, taking bioavailability and speciation pattern into account. The resulting site-dependent CTPs showed up to 2.4–6.5 orders of magnitude variation across archetypes for those metals that form stable hydroxyl compounds in slightly alkaline waters (Al(III), Be, Cr(III), Cu(II) and Fe(III)), emphasizing the importance of using site-dependent CTPs for these metals where possible. For the other metals, CTPs stayed within around 0.9 orders of magnitude, making spatial differentiation less important. In acidic waters (pH<6.4), Al(III) and Cu(II) had the highest CTPs, while Cd ranked highest in other waters. Based on the site-dependent CTPs, site-generic CTPs were developed applying different averaging principle. Emission weighted average of 7 EU-archetype CTPs was recommended as site-generic CTP for use in LCA studies, where receiving location is unclear. Compared to previous studies by Gandhi et al. (2010, 2011a), new site-dependent CTPs were similar or slightly higher for Cd, Co, Ni, Pb and Zn, but 1–2 orders of magnitude higher for Cu. Compared to the default site-generic CTPs in the frequently used characterization models USES-LCA and USEtox, new site-generic CTPs were mostly higher or similar, within up to ∼2 orders of magnitude difference.

Microbial communities in uranium mine tailings and mine water sediment from Jaduguda U mine, India: A culture independent analysis

Microbial diversity within uranium mine tailings and mine water sediment from the Jaduguda uranium mine, India was characterized by metagenome-derived 16S rRNA gene clone libraries. Samples from fresh tailings (JFT244), abandoned (vegetated) tailings (JOT245) and mine water sediment (J1-5) having wide ranges of pH (5.7 to 10.4), nitrogen, phosphorus and organic carbon [150–5700 ppm, 800–9100 ppm and 0.18–6.5% (w/w)] and elevated metals (Ni, Cu, Zn and U) were used to explore the inhabitant bacterial and archaeal community structures. Consistent to the sample's physicochemical properties, up to four orders of magnitude variation in bacterial CFU counts was observed. The data showed that with increasing metal and decreasing nutrient (organic C, N, P, etc.) contents, microbial diversity indices decrease within the samples. Culture-independent analyses revealed predominance of phyla Proteobacteria and/or Acidobacteria within the samples along with members of Actinobacteria, Cyanobacteria, Chloroflexi, Genera incertae sedis OP10, Firmicutes and Planctomycete as relatively minor groups. Abundance of Crenarchaeota in tailings samples and Euryachaeota in mine water sediment was noted. Diversity of dissimilatory sulfate reductase gene (dsr) was studied. Putative metabolic properties as derived from taxonomy and phylogenetic lineages indicated presence of chemolithotrophic and heteotrophic aerobic and anaerobic organisms capable of nitrogen fixation, nitrate reduction and biogeochemical cycling of metals, sulfur and methane. The data indicated that indigenous microbial populations are capable of maintaining self-sustenance in these highly hazardous environments and possess catalytic potential for their use in in situ bioremediation.

Nanosecond switching in GeSe phase change memory films by atomic force microscopy

Nanosecond scale threshold switching is investigated with conducting atomic force microscopy (AFM) for an amorphous GeSe film. Switched bits exhibit 2–3 orders of magnitude variations in conductivity, as demonstrated in phase change based memory devices. Through the nm-scale AFM probe, this crystallization was achieved with pulse durations of as low as 15 ns, the fastest reported with scanning probe based methods. Conductance AFM imaging of the switched bits further reveals correlations between the switched volume, pulse amplitude, and pulse duration. The influence of film heterogeneities on switching is also directly detected, which is of tremendous importance for optimal device performance.

Controlling the CO oxidation rate over Pt/TiO2 catalysts by defect engineering of the TiO2 support

The activity and selectivity of supported metal clusters can in principle be manipulated by controlling the electronic properties of the support, as initially proposed by Schwab. To quantitatively demonstrate this effect, a series of anatase TiO2 thin films with an order of magnitude variation in the carrier concentration were grown by atomic layer deposition. The change in the TiO2 carrier concentration influences the electronic properties of supported Pt clusters, as shown by photoelectron spectroscopy. The gradual increase in the carrier concentration increases the CO oxidation rate over the Pt/TiO2 catalysts by 70% for excess CO conditions and decreases the rate by 30% for excess O2 conditions, providing a quantitative connection between the support properties and the measured reaction rate. Density functional theory calculations and natural bond analysis show that charge injection into Pt clusters reduces the CO adsorption energy due to increased Pauli repulsion, which is consistent with the observed changes in the reaction rate.

Fast nanomechanical spectroscopy of soft matter

A method that combines high spatial resolution, quantitative and non-destructive mapping of surfaces and interfaces is a long standing goal in nanoscale microscopy. The method would facilitate the development of hybrid devices and materials made up of nanostructures of different properties. Here we develop a multifrequency force microscopy method that enables simultaneous mapping of nanomechanical spectra of soft matter surfaces with nanoscale spatial resolution. The properties include the Young's modulus and the viscous or damping coefficients. In addition, it provides the peak force and the indentation. The method does not limit the data acquisition speed nor the spatial resolution of the force microscope. It is non-invasive and minimizes the influence of the tip radius on the measurements. The same tip is used to measure in air heterogeneous interfaces with near four orders of magnitude variations in the elastic modulus, from 1 MPa to 3 GPa.

Thermoluminescence measurements of neutron streaming through JET Torus Hall ducts

Thermoluminescence detectors (TLD) were used for dose measurements at JET. Several hundreds of LiF detectors of various types, standard LiF:Mg,Ti and highly sensitive LiF:Mg,Cu,P were produced. LiF detectors consisting of natural lithium are sensitive to slow neutrons, their response to neutrons being enhanced by 6Li-enriched lithium or suppressed by using lithium consisting entirely of 7Li. Pairs of 6LiF/7LiF detectors allow distinguishing between neutron/non-neutron components of a radiation field. For detection of neutrons of higher energy, polyethylene (PE-300) moderators were used. TLDs, located in the centre of cylindrical moderators, were installed at eleven positions in the JET hall and the hall labyrinth in July 2012, and exposure took place during the last two weeks of the experimental campaign. Measurements of the gamma dose were obtained for all positions over a range of about five orders of magnitude variation. As the TLDs were also calibrated in a thermal neutron field, the neutron fluence at the experimental position could be derived. The experimental results are compared with calculations using the MCNP code. The results confirm that the TLD technology can be usefully applied to measurements of neutron streaming through JET Torus Hall ducts.

Delayed life history effects, multilevel selection, and evolutionary trade‐offs in the California tiger salamander

Delayed life history effects (DLHEs) occur when fitness in one life stage affects fitness in subsequent life stages. Given their biphasic life cycle, pond-breeding amphibians provide a natural system for studying DLHEs, although these effects are not restricted to species with biphasic life histories. In this study, we used multiple mark-recapture techniques enabled by a large trapping array to monitor components of fitness and resulting DLHEs in a population of the endangered California tiger salamander (Ambystoma californiense). We found that DLHEs are prominent across all life stage transitions and that there is variation in whether selection acts primarily at the individual or cohort level. We also demonstrated that there is more than an order of magnitude variation in mean cohort fitness, providing tremendous variation for DLHEs to act upon. We documented an evolutionary trade-off between mass at emergence and date of emergence, which may play a role in maintaining the variation in mass (fitness) at emergence. A literature review revealed that such high levels of intercohort variation occur in many other pond-breeding amphibians, and that appropriately documenting the magnitude of intercohort variation requires long-term studies (roughly two population turnovers). Given the profound effect that DLHEs can have on population dynamics, quantifying intercohort variation in mean fitness and the level(s) at which selection acts will be very important for developing accurate models of population dynamics. In general, when developing models of population dynamics, more attention should be paid to variation in mean fitness and not just variation in total numbers.

Influence of surface treatment on adhesion of iCVD PGMA thin films for wafer-level bonding

ABSTRACTThis work demonstrates wafer bonding using initiated chemical vapor deposition (iCVD) poly(glycidylmethacrylate) (PGMA) thin films, and studies the impact of surface treatment to manipulate adhesion energy between polymer film and silicon substrate. Substrates were modified with organosilanes or nitrogen plasma prior to iCVD and bonding. Adhesion was characterized by measuring critical energy release rate (Gc) using a 4-point bend technique. Results demonstrate a correlation between substrate surface energy and polymer-substrate adhesion energy where, depending on the functional group, close to an order of magnitude variation in adhesion energy was observed. These results point to minimal covalent interaction between polymer and substrate for these samples. Exposing the bonded wafers to a thermal anneal step led to an improved grafting of PGMA to substrate. For grafted films, the sample failure mode shifted from adhesive to cohesive, with drastic increase in Gc. These findings demonstrate that the adhesion energy and failure mode of iCVD-PGMA bonded wafers can be manipulated through surface functionalization and thermal treatment, which enable both temporary and permanent chip-bonding applications using iCVD polymer films as adhesives.

Compaction and gas loss in welded pyroclastic deposits as revealed by porosity, permeability, and electrical conductivity measurements of the Shevlin Park Tuff

Pyroclastic flows produced by large volcanic eruptions commonly densify after emplacement. Processes of gas escape, compaction, and welding in pyroclastic-flow deposits are controlled by the physical and thermal properties of constituent material. Through measurements of matrix porosity, permeability, and electrical conductivity, we provide a framework for understanding the evolution of pore structure during these processes. Using data from the Shevlin Park Tuff in central Oregon, United States, and from the literature, we find that over a porosity range of 0%–70%, matrix permeability varies by almost 10 orders of magnitude (from 10 –20 to 10 –11 m 2 ), with over three orders of magnitude variation at any given porosity. Part of the variation at a given porosity is due to permeability anisotropy, where oriented core samples indicate higher permeabilities parallel to foliation (horizontally) than perpendicular to foliation (vertically). This suggests that pore space is flattened during compaction, creating anisotropic crack-like networks, a geometry that is supported by electrical conductivity measurements. We find that the power law equation: k 1 = 1.3 × 10 –21 × ϕ 5.2 provides the best approximation of dominant horizontal gas loss, where k 1 = permeability, and ϕ = porosity. Application of Kozeny-Carman fluid-flow approximations suggests that permeability in the Shevlin Park Tuff is controlled by crack- or disk-like pore apertures with minimum widths of 0.3 and 7.5 μm. We find that matrix permeability limits compaction over short times, but deformation is then controlled by competition among cooling, compaction, water resorption, and permeable gas escape. These competing processes control the potential for development of overpressure (and secondary explosions) and the degree of welding in the deposit, processes that are applicable to viscous densification of volcanic deposits in general. Further, the general relationships among porosity, permeability, and pore geometry are relevant for flow of any fluid through an ignimbritic host.