A rotating disc voltammetry study of the 1,8-dihydroxyanthraquinone mediated reduction of colloidal indigo

Colloidal indigo is reduced to an aqueous solution of leuco-indigo in a mediated two-electron process converting the water-insoluble dye into the water-soluble leuco form. The colloidal dye does not interact directly with the electrode surface, and to employ an electrochemical process for this reduction, the redox mediator 1,8-dihydroxyanthraquinone (1,8-DHAQ) is used to transfer electrons from the electrode to the dye. The mediated reduction process is investigated at a (500-kHz ultrasound-assisted) rotating disc electrode, and the quantitative analysis of voltammetric data is attempted employing the Digisim numerical simulation software package. At the most effective temperature, 353 K, the diffusion coefficient for 1,8-DHAQ is (0.84 +/- 0.08)x10(-9) m(2) s(-1), and it is shown that an apparently kinetically controlled reaction between the reduced form of the mediator and the colloidal indigo occurs within the diffusion layer at the electrode surface. The apparent bimolecular rate constant k (app)=3 mol m(-3) s(-1) for the rate law d[leuco-indigo]/dt = k(app) x [mediator] x [indigo] is determined and attributed to a mediator diffusion controlled dissolution of the colloid particles. The average particle size and the number of molecules per particles are estimated from the apparent bimolecular rate constant and confirmed by scanning electron microscopy.

Recent oppositely directed trends in solar climate forcings and the global mean surface air temperature. II. Different reconstructions of the total solar irradiance variation and dependence on response time scale

We have previously placed the solar contribution to recent global warming in context using observations and without recourse to climate models. It was shown that all solar forcings of climate have declined since 1987. The present paper extends that analysis to include the effects of the various time constants with which the Earth’s climate system might react to solar forcing. The solar input waveform over the past 100 years is defined using observed and inferred galactic cosmic ray fluxes, valid for either a direct effect of cosmic rays on climate or an effect via their known correlation with total solar irradiance (TSI), or for a combination of the two. The implications, and the relative merits, of the various TSI composite data series are discussed and independent tests reveal that the PMOD composite used in our previous paper is the most realistic. Use of the ACRIM composite, which shows a rise in TSI over recent decades, is shown to be inconsistent with most published evidence for solar influences on pre-industrial climate. The conclusions of our previous paper, that solar forcing has declined over the past 20 years while surface air temperatures have continued to rise, are shown to apply for the full range of potential time constants for the climate response to the variations in the solar forcings.

Effective livelihood adaptation to climate change disturbance: scale dimensions of practice in Mozambique

Natural resource-dependent societies in developing countries are facing increased pressures linked to global climate change. While social-ecological systems evolve to accommodate variability, there is growing evidence that changes in drought, storm and flood extremes are increasing exposure of currently vulnerable populations. In many countries in Africa, these pressures are compounded by disruption to institutions and variability in livelihoods and income. The interactions of both rapid and slow onset livelihood disturbance contribute to enduring poverty and slow processes of rural livelihood renewal across a complex landscape. We explore cross-scale dynamics in coping and adaptation response, drawing on qualitative data from a case study in Mozambique. The research characterises the engagements across multiple institutional scales and the types of agents involved, providing insight into emergent conditions for adaptation to climate change in rural economies, The analysis explores local responses to climate shocks, food security and poverty reduction, through informal institutions, forms of livelihood diversification and collective land-use systems that allow reciprocity, flexibility and the ability to buffer shocks. However, the analysis shows that agricultural initiatives have helped to facilitate effective livelihood renewal, through the reorganisation of social institutions and opportunities for communication, innovation and micro-credit. Although there are challenges to mainstreaming adaptation at different scales, this research shows why it is critical to assess how policies can protect conditions for emergence of livelihood transformation. (C) 2008 Elsevier Ltd. All rights reserved.

Consistent large-scale temperature responses in warm and cold climates

Climate-model simulations of the large-scale temperature responses to increased radiative forcing include enhanced land-sea contrast, stronger response at higher latitudes than in the tropics, and differential responsesin warm and cool season climates to uniform forcing. Here we show that these patterns are also characteristic of model simulations of past climates. The differences in the responses over land as opposed to over the ocean, between high and low latitudes, and between summer and winter are remarkably consistent (proportional and nearly linear) across simulations of both cold and warm climates. Similar patterns also appear in historical observations and paleoclimatic reconstructions, implying that such responses are characteristic features of the climate system, and not simple model artifacts, thereby increasing our confidence in the ability of climate models to correctly simulate different climatic states.

Synoptic-scale controls of persistent low temperature and icy weather over southern China in January 2008

In January 2008, central and southern China experienced persistent low temperatures, freezing rain, and snow. The large-scale conditions associated with the occurrence and development of these snowstorms are examined in order to identify the key synoptic controls leading to this event. Three main factors are identified: 1) the persistent blocking high over Siberia, which remained quasi-stationary around 65°E for 3 weeks, led to advection of dry and cold Siberian air down to central and southern China; 2) a strong persistent southwesterly flow associated with the western Pacific subtropical high led to enhanced moisture advection from the Bay of Bengal into central and southern China; and 3) the deep inversion layer in the lower troposphere associated with the extended snow cover over most of central and southern China. The combination of these three factors is likely responsible for the unusual severity of the event, and hence a long return period

Transition from suppressed to active convection modulated by a weak-temperature gradient derived large-scale circulation

Numerical simulations are performed to assess the influence of the large-scale circulation on the transition from suppressed to active convection. As a model tool, we used a coupled-column model. It consists of two cloud-resolving models which are fully coupled via a large-scale circulation which is derived from the requirement that the instantaneous domain-mean potential temperature profiles of the two columns remain close to each other. This is known as the weak-temperature gradient approach. The simulations of the transition are initialized from coupled-column simulations over non-uniform surface forcing and the transition is forced within the dry column by changing the local and/or remote surface forcings to uniform surface forcing across the columns. As the strength of the circulation is reduced to zero, moisture is recharged into the dry column and a transition to active convection occurs once the column is sufficiently moistened to sustain deep convection. Direct effects of changing surface forcing occur over the first few days only. Afterward, it is the evolution of the large-scale circulation which systematically modulates the transition. Its contributions are approximately equally divided between the heating and moistening effects. A transition time is defined to summarize the evolution from suppressed to active convection. It is the time when the rain rate within the dry column is halfway to the mean value obtained at equilibrium over uniform surface forcing. The transition time is around twice as long for a transition that is forced remotely compared to a transition that is forced locally. Simulations in which both local and remote surface forcings are changed produce intermediate transition times.

Energy-balance mechanisms underlying consistent large-scale temperature responses in warm and cold climates

Climate simulations show consistent large-scale temperature responses including amplified land–ocean contrast, high-latitude/low-latitude contrast, and changes in seasonality in response to year-round forcing, in both warm and cold climates, and these responses are proportional and nearly linear across multiple climate states. We examine the possibility that a small set of common mechanisms controls these large-scale responses using a simple energy-balance model to decompose the temperature changes shown in multiple lgm and abrupt4 × CO 2 simulations from the CMIP5 archive. Changes in the individual components of the energy balance are broadly consistent across the models. Although several components are involved in the overall temperature responses, surface downward clear-sky longwave radiation is the most important component driving land–ocean contrast and high-latitude amplification in both warm and cold climates. Surface albedo also plays a significant role in promoting high-latitude amplification in both climates and in intensifying the land–ocean contrast in the warm climate case. The change in seasonality is a consequence of the changes in land–ocean and high-latitude/low-latitude contrasts rather than an independent temperature response. This is borne out by the fact that no single component stands out as being the major cause of the change in seasonality, and the relative importance of individual components is different in cold and warm climates.

Simple measures of climate, soil properties and plant traits predict national scale grassland soil carbon stocks

1. Soil carbon (C) storage is a key ecosystem service. Soil C stocks play a vital role in soil fertility and climate regulation, but the factors that control these stocks at regional and national scales are unknown, particularly when their composition and stability are considered. As a result, their mapping relies on either unreliable proxy measures or laborious direct measurements. 2. Using data from an extensive national survey of English grasslands we show that surface soil (0-7cm) C stocks in size fractions of varying stability can be predicted at both regional and national scales from plant traits and simple measures of soil and climatic conditions. 3. Soil C stocks in the largest pool, of intermediate particle size (50-250 µm), were best explained by mean annual temperature (MAT), soil pH and soil moisture content. The second largest C pool, highly stable physically and biochemically protected particles (0.45-50 µm), was explained by soil pH and the community abundance weighted mean (CWM) leaf nitrogen (N) content, with the highest soil C stocks under N rich vegetation. The C stock in the small active fraction (250-4000 µm) was explained by a wide range of variables: MAT, mean annual precipitation, mean growing season length, soil pH and CWM specific leaf area; stocks were higher under vegetation with thick and/or dense leaves. 4. Testing the models describing these fractions against data from an independent English region indicated moderately strong correlation between predicted and actual values and no systematic bias, with the exception of the active fraction, for which predictions were inaccurate. 5. Synthesis and Applications: Validation indicates that readily available climate, soils and plant survey data can be effective in making local- to landscape-scale (1-100,000 km2) soil C stock predictions. Such predictions are a crucial component of effective management strategies to protect C stocks and enhance soil C sequestration.

Using Distributed Temperature Sensing to monitor field scale dynamics of ground surface temperature and related substrate heat flux

We present one of the first studies of the use of Distributed Temperature Sensing (DTS) along fibre-optic cables to purposely monitor spatial and temporal variations in ground surface temperature (GST) and soil temperature, and provide an estimate of the heat flux at the base of the canopy layer and in the soil. Our field site was at a groundwater-fed wet meadow in the Netherlands covered by a canopy layer (between 0-0.5 m thickness) consisting of grass and sedges. At this site, we ran a single cable across the surface in parallel 40 m sections spaced by 2 m, to create a 40×40 m monitoring field for GST. We also buried a short length (≈10 m) of cable to depth of 0.1±0.02 m to measure soil temperature. We monitored the temperature along the entire cable continuously over a two-day period and captured the diurnal course of GST, and how it was affected by rainfall and canopy structure. The diurnal GST range, as observed by the DTS system, varied between 20.94 and 35.08◦C; precipitation events acted to suppress the range of GST. The spatial distribution of GST correlated with canopy vegetation height during both day and night. Using estimates of thermal inertia, combined with a harmonic analysis of GST and soil temperature, substrate and soil-heat fluxes were determined. Our observations demonstrate how the use of DTS shows great promise in better characterising area-average substrate/soil heat flux, their spatiotemporal variability, and how this variability is affected by canopy structure. The DTS system is able to provide a much richer data set than could be obtained from point temperature sensors. Furthermore, substrate heat fluxes derived from GST measurements may be able to provide improved closure of the land surface energy balance in micrometeorological field studies. This will enhance our understanding of how hydrometeorological processes interact with near-surface heat fluxes.

Sensitivity of large-scale atmospheric analyses to humidity observations and its impact on the global water cycle and tropical and extratropical weather systems in ERA40

Reanalysis data obtained from data assimilation are increasingly used for diagnostic studies of the general circulation of the atmosphere, for the validation of modelling experiments and for estimating energy and water fluxes between the Earth surface and the atmosphere. Because fluxes are not specifically observed, but determined by the data assimilation system, they are not only influenced by the utilized observations but also by model physics and dynamics and by the assimilation method. In order to better understand the relative importance of humidity observations for the determination of the hydrological cycle, in this paper we describe an assimilation experiment using the ERA40 reanalysis system where all humidity data have been excluded from the observational data base. The surprising result is that the model, driven by the time evolution of wind, temperature and surface pressure, is able to almost completely reconstitute the large-scale hydrological cycle of the control assimilation without the use of any humidity data. In addition, analysis of the individual weather systems in the extratropics and tropics using an objective feature tracking analysis indicates that the humidity data have very little impact on these systems. We include a discussion of these results and possible consequences for the way moisture information is assimilated, as well as the potential consequences for the design of observing systems for climate monitoring. It is further suggested, with support from a simple assimilation study with another model, that model physics and dynamics play a decisive role for the hydrological cycle, stressing the need to better understand these aspects of model parametrization. .

Climate response to basin-scale warming and cooling of the North Atlantic Ocean

Using experiments with an atmospheric general circulation model, the climate impacts of a basin-scale warming or cooling of the North Atlantic Ocean are investigated. Multidecadal fluctuations with this pattern were observed during the twentieth century, and similar variations--but with larger amplitude--are believed to have occurred in the more distant past. It is found that in all seasons the response to warming the North Atlantic is strongest, in the sense of highest signal-to-noise ratio, in the Tropics. However there is a large seasonal cycle in the climate impacts. The strongest response is found in boreal summer and is associated with suppressed precipitation and elevated temperatures over the lower-latitude parts of North and South America. In August­-September-­October there is a significant reduction in the vertical shear in the main development region for Atlantic hurricanes. In winter and spring, temperature anomalies over land in the extratropics are governed by dynamical changes in circulation rather than simply reflecting a thermodynamic response to the warming or cooling of the ocean. The tropical climate response is primarily forced by the tropical SST anomalies, and the major features are in line with simple models of the tropical circulation response to diabatic heating anomalies. The extratropical climate response is influenced both by tropical and higher-latitude SST anomalies and exhibits nonlinear sensitivity to the sign of the SST forcing. Comparisons with multidecadal changes in sea level pressure observed in the twentieth century support the conclusion that the impact of North Atlantic SST change is most important in summer, but also suggest a significant influence in lower latitudes in autumn and winter. Significant climate impacts are not restricted to the Atlantic basin, implying that the Atlantic Ocean could be an important driver of global decadal variability. The strongest remote impacts are found to occur in the tropical Pacific region in June­-August and September­-November. Surface anomalies in this region have the potential to excite coupled ocean­atmosphere feedbacks, which are likely to play an important role in shaping the ultimate climate response.

Precipitating convection in cold air: virtual potential temperature structure

Simulations of precipitating convection are used to illustrate the importance of the turbulent kinetic energy (TKE) budget in determining the virtual potential-temperature structure of the convecting atmosphere. Two sets of simulations are presented: in one the surface temperature was increased to simulate cold air flowing over a warmer surface and in the second a cooling profile, representing cold-air advection, was imposed. It is shown that the terms in the TKE budgets for both sets of simulations scale in the same way, but that the non-dimensional profiles are different. It is suggested that this is associated with the effects of sublimation of ice. It is shown that the magnitudes of the transport and precipitation terms in the virtual potential temperature budget are determined by the scaling of the TKE budget. Some implications of these results for parametrizations of moist convection are discussed. Copyright © 2007 Royal Meteorological Society

Perturbation growth at the convective scale for CSIP IOP18

The Met Office Unified Model is run for a case observed during Intensive Observation Period 18 (IOP18) of the Convective Storms Initiation Project (CSIP). The aims are to identify the physical processes that lead to perturbation growth at the convective scale in response to model-state perturbations and to determine their sensitivity to the character of the perturbations. The case is strongly upper-level forced but with detailed mesoscale/convective-scale evolution that is dependent on smaller-scale processes. Potential temperature is perturbed within the boundary layer. The effects on perturbation growth of both the amplitude and typical scalelength of the perturbations are investigated and perturbations are applied either sequentially (every 30 min throughout the simulation) or at specific times. The direct effects (within one timestep) of the perturbations are to generate propagating Lamb and acoustic waves and produce generally small changes in cloud parameters and convective instability. In exceptional cases a perturbation at a specific gridpoint leads to switching of the diagnosed boundary-layer type or discontinuous changes in convective instability, through the generation or removal of a lid. The indirect effects (during the entire simulation) are changes in the intensity and location of precipitation and in the cloud size distribution. Qualitatively different behaviour is found for strong (1K amplitude) and weak (0.01K amplitude) perturbations, with faster growth after sunrise found only for the weaker perturbations. However, the overall perturbation growth (as measured by the root-mean-square error of accumulated precipitation) reaches similar values at saturation, regardless of the perturbation characterisation.

Evaluating the efficacy of planktonic foraminifer calcite and 18O data for sea surface temperature reconstruction for the Late Miocene

This study examines the efficacy of published δ18O data from the calcite of Late Miocene surface dwelling planktonic foraminifer shells, for sea surface temperature estimates for the pre-Quaternary. The data are from 33 Late Miocene (Messinian) marine sites from a modern latitudinal gradient of 64°N to 48°S. They give estimates of SSTs in the tropics/subtropics (to 30°N and S) that are mostly cooler than present. Possible causes of this temperature discrepancy are ecological factors (e.g. calcification of shells at levels below the ocean mixed layer), taphonomic effects (e.g. diagenesis or dissolution), inaccurate estimation of Late Miocene seawater oxygen isotope composition, or a real Late Miocene cool climate. The scale of apparent cooling in the tropics suggests that the SST signal of the foraminifer calcite has been reset, at least in part, by early diagenetic calcite with higher δ18O, formed in the foraminifer shells in cool sea bottom pore waters, probably coupled with the effects of calcite formed below the mixed layer during the life of the foraminifera. This hypothesis is supported by the markedly cooler SST estimates from low latitudes—in some cases more than 9 °C cooler than present—where the gradients of temperature and the δ18O composition of seawater between sea surface and sea bottom are most marked, and where ocean surface stratification is high. At higher latitudes, particularly N and S of 30°, the temperature signal is still cooler, though maximum temperature estimates overlap with modern SSTs N and S of 40°. Comparison of SST estimates for the Late Miocene from alkenone unsaturation analysis from the eastern tropical Atlantic at Ocean Drilling Program (ODP) Site 958—which suggest a warmer sea surface by 2–4 °C, with estimates from oxygen isotopes at Deep Sea Drilling Project (DSDP) Site 366 and ODP Site 959, indicating cooler than present SSTs, also suggest a significant impact on the δ18O signal. Nevertheless, much of the original SST variation is clearly preserved in the primary calcite formed in the mixed layer, and records secular and temporal oceanographic changes at the sea surface, such as movement of the Antarctic Polar Front in the Southern Ocean. Cooler SSTs in the tropics and sub-tropics are also consistent with the Late Miocene latitude reduction in the coral reef belt and with interrupted reef growth on the Queensland Plateau of eastern Australia, though it is not possible to quantify absolute SSTs with the existing oxygen isotope data. Reconstruction of an accurate global SST dataset for Neogene time-slices from the existing published DSDP/ODP isotope data, for use in general circulation models, may require a detailed re-assessment of taphonomy at many sites.

Industrial radioactive barite scale: suppression of radium uptake by introduction of competing ions

Incorporation of radioactive isotopes during the formation of barite mineral scale is a widespread phenomenon occurring within the oil, mining and process industries. In a series of experiments radioactive barite/celestite solid solutions (SSBarite-Celcstite) have been synthesized under controlled conditions by the counter diffusion of Ra-226, Ba2+, Sr24+ and SO42- ions through a porous medium (silica gel), to investigate inhibiting effects in Ra uptake associated with the introduction of a competing ion (Sr2+). From characterization studies, the particle size and the morphology of the crystals appear to be related to the initial [Sr]/[Ba] molar ratio of the starting solution. Typically, systems richer in Sr produce smaller sized crystals and clusters characterized by a lower degree of order. The activity introduced to the system is mainly incorporated in the crystals generated from the barite/celestite solid solution as suggested by the activity profiles of the hydrogel columns analysed by gamma-spectrometry. There is a relationship between the initial [Sr]/[Ba] molar ratio of the starting solution and the activity exhibited by the synthesized crystals. An effective inhibition of the Ra-226 uptake during formation of the crystals (SSBarite-Celestite) was obtained through the introduction of a competing ion (Sr2+): the higher the initial [Sr]/[Ba] molar ratio of the starting solution, the lower the intensity of the activity peak in the crystals. (C) 2003 Published by Elsevier Ltd.