The partial oxidation of methane over Pd/Al2O3 catalyst nanoparticles studied in-situ by near ambient-pressure x-ray photoelectron spectroscopy

Near ambient-pressure X-ray photoelectron spectroscopy (NAP-XPS) is used to study the chemical state of methane oxidation catalysts in-situ. Al2O3{supported Pd catalysts are prepared with different particle sizes ranging from 4 nm to 10 nm. These catalysts were exposed to conditions similar to those used in the partial oxidation of methane (POM) to syn-gas and simultaneously monitored by NAP-XPS and mass spectrometry. NAP-XPS data show changes in the oxidation state of the palladium as the temperature in- creases, from metallic Pd0 to PdO, and back to Pd0. Mass spectrometry shows an increase in CO production whilst the Pd is in the oxide phase, and the metal is reduced back under presence of newly formed H2. A particle size effect is observed, such that CH4 conversion starts at lower temperatures with larger sized particles from 6 nm to 10 nm. We find that all nanoparticles begin CH4 conversion at lower temperatures than polycrystalline Pd foil.

The potential impact of changes in lower stratospheric water vapour on stratospheric temperatures over the past 30 years

This study investigates the potential contribution of observed changes in lower stratospheric water vapour to stratospheric temperature variations over the past three decades using a comprehensive global climate model (GCM). Three case studies are considered. In the first, the net increase in stratospheric water vapour (SWV) from 1980–2010 (derived from the Boulder frost-point hygrometer record using the gross assumption that this is globally representative) is estimated to have cooled the lower stratosphere by up to ∼0.2 K decade−1 in the global and annual mean; this is ∼40% of the observed cooling trend over this period. In the Arctic winter stratosphere there is a dynamical response to the increase in SWV, with enhanced polar cooling of 0.6 K decade−1 at 50 hPa and warming of 0.5 K decade−1 at 1 hPa. In the second case study, the observed decrease in tropical lower stratospheric water vapour after the year 2000 (imposed in the GCM as a simplified representation of the observed changes derived from satellite data) is estimated to have caused a relative increase in tropical lower stratospheric temperatures by ∼0.3 K at 50 hPa. In the third case study, the wintertime dehydration in the Antarctic stratospheric polar vortex (again using a simplified representation of the changes seen in a satellite dataset) is estimated to cause a relative warming of the Southern Hemisphere polar stratosphere by up to 1 K at 100 hPa from July–October. This is accompanied by a weakening of the westerly winds on the poleward flank of the stratospheric jet by up to 1.5 m s−1 in the GCM. The results show that, if the measurements are representative of global variations, SWV should be considered as important a driver of transient and long-term variations in lower stratospheric temperature over the past 30 years as increases in long-lived greenhouse gases and stratospheric ozone depletion.

Is Antarctic climate most sensitive to ozone depletion in the middle or lower stratosphere?

Antarctic stratospheric ozone depletion has been associated with an observed downward trend in tropospheric geopotential height and temperature. Stratospheric ozone depletion peaks in October–November, whereas tropospheric trends are largest in December–January, concurrent with maximum ozone changes close to the tropopause. Surface temperatures are most sensitive to ozone loss near the tropopause, therefore it has been suggested that the observed tropospheric response is forced mainly by ozone depletion in the lower stratosphere. In this study the climate response to ozone depletion exclusively below 164 hPa is simulated using HadSM3-L64, and compared with simulations in which ozone depletion is prescribed exclusively above 164 hPa. Results indicate that the tropospheric response is dominated by ozone changes above 164 hPa, with ozone changes in the lowermost stratosphere playing an insignificant role. A tropospheric response is also seen in fall/winter which agrees well with observations and has not been found in modeling studies previously.

Natural ventilation effects on temperatures within Stevenson screens

Thermometer screen properties are poorly characterised at low wind speeds. Temperatures from a large thermometer screen have been compared with those from an automatically shaded open-air fine-wire resistance thermometer. For the majority of 5-minute average measurements obtained between July 2008 and 2009, the screen and fine-wire temperatures agreed closely, with a median difference <0.05◦C. At low wind speeds however, larger temperature differences occurred. When calm (wind speed at 2 metres, u2, ≤ 0.1 m s−1), the difference between screen and open-air temperatures varied from −0.25◦C to +0.87◦C. At night with u2 < 0.5 m s−1, this difference was −0.14◦C to 0.39◦C, and, rarely, up to −0.68◦C to 1.38◦C. At the minimum in the daily temperature cycle, the semi-urban site at Reading had u2 < 1 m s−1 for 52% of the observations 1997–2008, u2 < 0.5 m s−1 for 34% and calm conditions for 20%. Consequently uncertainties in the minimum temperature measurements may arise from poor ventilation, which can propagate through calculations to daily average temperatures. In comparison with the daily minimum temperature, the 0900 UTC synoptic temperature measurement has a much lower abundance (5%) of calm conditions.

Coupled chemistry climate model simulations of stratospheric temperatures and their trends for the recent past

Temperature results from multi-decadal simulations of coupled chemistry climate models for the recent past are analyzed using multi-linear regression including a trend, solar cycle, lower stratospheric tropical wind, and volcanic aerosol terms. The climatology of the models for recent years is in good agreement with observations for the troposphere but the model results diverge from each other and from observations in the stratosphere. Overall, the models agree better with observations than in previous assessments, primarily because of corrections in the observed temperatures. The annually averaged global and polar temperature trends simulated by the models are generally in agreement with revised satellite observations and radiosonde data over much of their altitude range. In the global average, the model trends underpredict the radiosonde data slightly at the top of the observed range. Over the Antarctic some models underpredict the temperature trend in the lower stratosphere, while others overpredict the trends

Dynamics of the lower stratospheric circulation response to ENSO

A robust feature of the observed response to El Nin˜o–Southern Oscillation (ENSO) is an altered circulation in the lower stratosphere. When sea surface temperatures (SSTs) in the tropical Pacific are warmer there is enhanced upwelling and cooling in the tropical lower stratosphere and downwelling and warming in the midlatitudes, while the opposite is true of cooler SSTs. The midlatitude lower stratospheric response to ENSO is larger in the Southern Hemisphere (SH) than in the Northern Hemisphere (NH). In this study the dynamical version of the Canadian Middle Atmosphere Model (CMAM) is used to simulate 25 realizations of the atmospheric response to the 1982/83 El Nin˜o and the 1973/74 La Nin˜ a. This version ofCMAMis a comprehensive high-top general circulation model that does not include interactive chemistry. The observed lower stratospheric response to ENSO is well reproduced by the simulations, allowing them to be used to investigate the mechanisms involved. Both the observed and simulated responses maximize in December–March and so this study focuses on understanding the mechanisms involved in that season. The response in tropical upwelling is predominantly driven by anomalous transient synoptic-scale wave drag in the SH subtropical lower stratosphere, which is also responsible for the compensating SH midlatitude response. This altered wave drag stems from an altered upward flux of wave activity from the troposphere into the lower stratosphere between 208 and 408S. The altered flux of wave activity can be divided into two distinct components. In the Pacific, the acceleration of the zonal wind in the subtropics from the warmer tropical SSTs results in a region between the midlatitude and subtropical jets where there is an enhanced source of low phase speed eddies. At other longitudes, an equatorward shift of the midlatitude jet from the extratropical tropospheric response to El Nin˜o results in an enhanced source of waves of higher phase speeds in the subtropics. The altered resolved wave drag is only apparent in the SH and the difference between the two hemispheres can be related to the difference in the climatological jet structures in this season and the projection of the wind anomalies associated with ENSO onto those structures.

Microbial decomposition of skeletal muscle tissue (Ovis aries) in a sandy loam soil at different temperatures

A laboratory experiment was conducted to determine the effect of temperature (2, 12, 22 °C) on the rate of aerobic decomposition of skeletal muscle tissue (Ovis aries) in a sandy loam soil incubated for a period of 42 days. Measurements of decomposition processes included skeletal muscle tissue mass loss, carbon dioxide (CO2) evolution, microbial biomass, soil pH, skeletal muscle tissue carbon (C) and nitrogen (N) content and the calculation of metabolic quotient (qCO2). Incubation temperature and skeletal muscle tissue quality had a significant effect on all of the measured process rates with 2 °C usually much lower than 12 and 22 °C. Cumulative CO2 evolution at 2, 12 and 22 °C equaled 252, 619 and 905 mg CO2, respectively. A significant correlation (P<0.001) was detected between cumulative CO2 evolution and tissue mass loss at all temperatures. Q10s for mass loss and CO2 evolution, which ranged from 1.19 to 3.95, were higher for the lower temperature range (Q10(2– 12 °C)>Q10(12–22 °C)) in the Ovis samples and lower for the low temperature range (Q10(2–12 °C)lower microbial catabolic requirements at lower temperature.

Robust comparison of climate models with observations using blended land air and ocean sea surface temperatures

The level of agreement between climate model simulations and observed surface temperature change is a topic of scientific and policy concern. While the Earth system continues to accumulate energy due to anthropogenic and other radiative forcings, estimates of recent surface temperature evolution fall at the lower end of climate model projections. Global mean temperatures from climate model simulations are typically calculated using surface air temperatures, while the corresponding observations are based on a blend of air and sea surface temperatures. This work quantifies a systematic bias in model-observation comparisons arising from differential warming rates between sea surface temperatures and surface air temperatures over oceans. A further bias arises from the treatment of temperatures in regions where the sea ice boundary has changed. Applying the methodology of the HadCRUT4 record to climate model temperature fields accounts for 38% of the discrepancy in trend between models and observations over the period 1975–2014.

Global climatology of surface water temperatures of large lakes by remote sensing

Lake surface water temperatures (LSWTs) of 246 globally distributed large lakes were derived from Along-Track Scanning Radiometers (ATSR) for the period 1991–2011. The climatological cycles of mean LSWT derived from these data quantify on a global scale the responses of large lakes' surface temperatures to the annual cycle of forcing by solar radiation and the ambient meteorological conditions. LSWT cycles reflect the twice annual peak in net solar radiation for lakes between 1°S to 12°N. For lakes without a lake-mean seasonal ice cover, LSWT extremes exceed air temperatures by 0.5–1.7 °C for maximum and 0.7–1.9 °C for minimum temperature. The summer maximum LSWTs of lakes from 25°S to 35°N show a linear decrease with increasing altitude; −3.76 ± 0.17 °C km−1 (inline image = 0.95), marginally lower than the corresponding air temperature decrease with altitude −4.15 ± 0.24 °C km−1 (inline image = 0.95). Lake altitude of tropical lakes account for 0.78–0.83 (inline image) of the variation in the March to June LSWT–air temperature differences, with differences decreasing by 1.9 °C as the altitude increases from 500 to 1800 m above sea level (a.s.l.) We define an ‘open water phase’ as the length of time the lake-mean LSWT remains above 4 °C. There is a strong global correlation between the start and end of the lake-mean open water phase and the spring and fall 0 °C air temperature transition days, (inline image = 0.74 and 0.80, respectively), allowing for a good estimation of timing and length of the open water phase of lakes without LSWT observations. Lake depth, lake altitude and distance from coast further explain some of the inter-lake variation in the start and end of the open water phase.