Open Markov processes: A compositional perspective on non-equilibrium steady states in biology

In recent work, Baez, Fong and the author introduced a framework for describing Markov processes equipped with a detailed balanced equilibrium as open systems of a certain type. These `open Markov processes' serve as the building blocks for more complicated processes. In this paper, we describe the potential application of this framework in the modeling of biological systems as open systems maintained away from equilibrium. We show that non-equilibrium steady states emerge in open systems of this type, even when the rates of the underlying process are such that a detailed balanced equilibrium is permitted. It is shown that these non-equilibrium steady states minimize a quadratic form which we call `dissipation.' In some circumstances, the dissipation is approximately equal to the rate of change of relative entropy plus a correction term. On the other hand, Prigogine's principle of minimum entropy production generally fails for non-equilibrium steady states. We use a simple model of membrane transport to illustrate these concepts

Dimethyl disulfide (DMDS) and dimethyl sulfide (DMS) emissions from biomass burning in Australia

We identify dimethyl disulfide (DMDS) as the major reduced sulfur-containing gas emitted from bushfires in Australia's Northern Territory. Like dimethyl sulfide (DMS), DMDS is oxidized in the atmosphere to sulfur dioxide (SO2) and methane sulfonic acid (MSA), which are intermediates in the formation of sulfuric acid (H2SO4). The mixing ratios of DMDS and DMS were the highest we have ever detected, with maximum values of 113 and 35 ppbv, respectively, whereas background values were below the detection limit (10 pptv). Molar emission ratios relative to carbon monoxide (CO) were [1.6 ± 0.1] × 10-5 and [6.2 ± 0.3] × 10-6, for DMDS and DMS respectively, while molar emission ratios relative to carbon dioxide (CO2) were [4.7 ± 0.4] × 10 6 and [1.4 ± 0.4] × 10 7, respectively. Assuming these observations are representative of biomass burning, we estimate that biomass burning could yield up to 175 Gg/yr of DMDS (119 Gg S/yr) and 13 Gg/yr of DMS

Cosmology with photometric redshift surveys

We explore the utility of future photometric redshift imaging surveys for delineating the large-scale structure of the Universe, and assess the resulting constraints on the cosmological model. We perform the following two complementary types of analysis. (i) We quantify the statistical confidence and the accuracy with which such surveys will be able to detect and measure characteristic features in the clustering power spectrum such as the acoustic oscillations and the turnover, in a 'model-independent' fashion. We show for example that a 10 000-deg2 imaging survey with depth r= 22.5 and photometric redshift accuracy δz/(1 +z) = 0.03 will detect the acoustic oscillations with 99.9 per cent confidence, measuring the associated preferred cosmological scale with 2 per cent precision. Such a survey will also detect the turnover with 95 per cent confidence, determining the corresponding scale with 20 per cent accuracy. (ii) By assuming a Λ cold dark matter (ΛCDM) model power spectrum we calculate the confidence with which a non-zero baryon fraction can be deduced from such future galaxy surveys. We quantify 'wiggle detection' by calculating the number of standard deviations by which the baryon fraction is measured, after marginalizing over the shape parameter. This is typically a factor of 4 more significant (in terms of number of standard deviations) than the above 'model-independent' result. For both analyses, we quantify the variation of the results with magnitude depth and photometric redshift precision, and discuss the prospects for obtaining the required performance with realistic future surveys. We conclude that the precision with which the clustering pattern may be inferred from future photometric redshift surveys will be competitive with contemporaneous spectroscopic redshift surveys, assuming that systematic effects can be controlled. We find that for equivalent wiggle detection power, a photometric redshift survey requires an area approximately 12[δz/(1 +z)]/0.03 times larger than a spectroscopic survey, for a given magnitude limit. We also note that an analysis of luminous red galaxies in the Sloan Digital Sky Survey may yield a marginal detection of acoustic oscillations in the imaging survey, in addition to that recently reported for the spectroscopic component

Long-term decrease in the global atmospheric burden of tetrachloroethene (C2Cl4)

We present a 14-year record of tropospheric tetrachloroethene (C2Cl4) mixing ratios measured each season at remote surface locations throughout the Pacific Basin (71°N-47°S . Our calculated annual mean C2Cl4 mixing ratio for the extra-tropical northern hemisphere (NH) was 13.9 ± 0.5 pptv in 1989, but declined to less than half this value (to 6.5 ± 0.2 pptv) by 2002. Mid-latitude southern hemisphere (SH) mixing ratios, which were much smaller than NH values, showed interannual variations comparable to measured long-term changes, and the SH annual mean was slightly less in 2002 than in 1989. Driven by the relatively large decrease in NH values, the global C2Cl4, mixing ratio declined from 6.3 ± 0.6 pptv in 1989 to 3.5 ± 0.2 pptv in 2002. These values suggest that the global C2Cl4 burden decreased by roughly 205 Gg between 1989-2002, which is consistent with industrial estimates of declining NH emissions over a similar period. Copyright 2004 by the American Geophysical Union

Strong evidence for negligible methyl chloroform (CH3CCl3) emissions from biomass burning

With the phase-out of industrial methyl chloroform (MCF) production, the atmospheric burden of this ozone-depleting gas has rapidly declined. Therefore any non-industrial sources are taking on greater significance in the MCF budget. The only natural MCF source that has been proposed, biomass burning, has been reported to emit up to 2-10 Gg MCF yr-1. We have re-examined MCF data for thousands of airborne and ground-based air samples collected by our group since 1990 that were directly impacted by major biomass burning sources. Without exception, we have found no positive evidence that MCF is released from biomass burning. Our results indicate that global biomass burning emissions of MCF have been significantly overestimated and are unlikely to exceed 0.014 Gg MCF yr-1. Lowering the uncertainty regarding the magnitude of the global MCF biomass burning source may extend its period of usefulness for determining global abundances and trends of the hydroxyl radical (OH). Copyright 2007 by the American Geophysical Union

Isolation and characterisation of 2-Tert-butyl-8-hydroxyquinoline as a crystalline solid and its blue fluorescent Li complex

Copyright © 2014 Poopathy Kathirgamanathan et al. This is an open access article distributed under the Creative Commons Attribution License, which permits unrestricted use, distribution, and reproduction in any medium, provided the original work is properly cited.2-Tert-butyl-8-hydroxyquinoline (2-TB-8-hq) has been isolated as a crystalline solid and its X-ray structure elucidated, resolving three decades of controversy, since it was previously wrongly reported as yellow oil by some other workers. An improved synthetic method has been developed which increases the yield from 20% to 60%. The lithium complex of 2-TB-8-hq is blue emitting and the HOMO and LUMO levels are lowered by 0.86 eV and 0.74 eV, respectively, compared with the parent lithium 8-hydroxyquinolinolate (Li 8-hq)

SO₂ emissions from basaltic eruptions, and the excess sulfur issue

Volcanic SO2 can affect the Earth's environment. Where no direct measurements of SO2 in the atmosphere are available, a petrologic method of assessing sulfur release from the magma must be used. However, in studies of arc-derived eruptions, satellite-based measurements of SO2 emissions using Total Ozone Mapping Spectrometer (TOMS) data are orders of magnitude greater than those calculated petrologically, implying that a separate S-rich gas phase in the magma chamber may be responsible for the excess sulfur. We test whether this applies in other settings. For Icelandic and Hawaiian basalts we find that petrologic SO2 values are comparable to measurements of SO2 by TOMS. Thus, for non-arc basalts, the petrologic method gives reliable estimates of SO2 released. The implied absence of excess sulfur in non-arc basaltic magmas is a reflection of source magma conditions, notably lower fO2 and volatile contents than arc magmas, inhibiting the exsolution of a S-rich gas prior to eruption