Kinetic multi-layer model of gas-particle interactions in aerosols and clouds (KM-GAP): linking condensation, evaporation and chemical reactions of organics, oxidants and water

We present a novel kinetic multi-layer model for gas-particle interactions in aerosols and clouds (KM-GAP) that treats explicitly all steps of mass transport and chemical reaction of semi-volatile species partitioning between gas phase, particle surface and particle bulk. KM-GAP is based on the PRA model framework (Pöschl-Rudich-Ammann, 2007), and it includes gas phase diffusion, reversible adsorption, surface reactions, bulk diffusion and reaction, as well as condensation, evaporation and heat transfer. The size change of atmospheric particles and the temporal evolution and spatial profile of the concentration of individual chemical species can be modelled along with gas uptake and accommodation coefficients. Depending on the complexity of the investigated system, unlimited numbers of semi-volatile species, chemical reactions, and physical processes can be treated, and the model shall help to bridge gaps in the understanding and quantification of multiphase chemistry and microphysics in atmo- spheric aerosols and clouds. In this study we demonstrate how KM-GAP can be used to analyze, interpret and design experimental investigations of changes in particle size and chemical composition in response to condensation, evaporation, and chemical reaction. For the condensational growth of water droplets, our kinetic model results provide a direct link between laboratory observations and molecular dynamic simulations, confirming that the accommodation coefficient of water at 270 K is close to unity. Literature data on the evaporation of dioctyl phthalate as a function of particle size and time can be reproduced, and the model results suggest that changes in the experimental conditions like aerosol particle concentration and chamber geometry may influence the evaporation kinetics and can be optimized for eðcient probing of specific physical effects and parameters. With regard to oxidative aging of organic aerosol particles, we illustrate how the formation and evaporation of volatile reaction products like nonanal can cause a decrease in the size of oleic acid particles exposed to ozone.

The role of water vapour in Earth’s energy flows

Water vapour modulates energy flows in Earth's climate system through transfer of latent heat by evaporation and condensation and by modifying the flows of radiative energy both in the longwave and shortwave portions of the electromagnetic spectrum. This article summarizes the role of water vapour in Earth's energy flows with particular emphasis on (1) the powerful thermodynamic constraint of the Clausius Clapeyron equation, (2) dynamical controls on humidity above the boundary layer (or free-troposphere), (3) uncertainty in continuum absorption in the relatively transparent "window" regions of the radiative spectrum and (4) implications for changes in the atmospheric hydrological cycle.

Power, nature and neoliberalism: the political ecology of water in Chile

Since the 1990s, international water sector reforms have centred heavily on economic and market approaches. In regard to water resources management, tradable water rights have been promoted, often supported by the neoliberal model adopted in Chile. Chile's 1981 Water Code was reformed to comprise a system of water rights that could be freely traded with few restrictions. International financial institutions have embraced the Chilean model, claiming that it results in more efficient water use, and potentially fosters social and environmental benefits. However, in Chile the Water Code is deeply contested. It has been criticised for being too permissive and has produced a number of problems in practice. Moreover, attempts to modify it have become the focus of a lengthy polemic debate. This paper employs a political ecology perspective to explore the socio-environmental outcomes of water management in Chile, drawing on a case study of agriculture in the semi-arid Norte Chico. The case illustrates how large-scale farmers exert greater control over water, while peasant farmers have increasingly less access. I argue that these outcomes are facilitated by the mode of water management implemented within the framework of the Water Code. Through this preliminary examination of social equity and the environmental aspects of water resources management in Chile, I suggest that the omission of these issues from the international debates on water rights markets is a cause for concern.

Biotic carbon feedbacks in a materially-closed soil-vegetation-atmosphere system

The magnitude and direction of the coupled feedbacks between the biotic and abiotic components of the terrestrial carbon cycle is a major source of uncertainty in coupled climate–carbon-cycle models1, 2, 3. Materially closed, energetically open biological systems continuously and simultaneously allow the two-way feedback loop between the biotic and abiotic components to take place4, 5, 6, 7, but so far have not been used to their full potential in ecological research, owing to the challenge of achieving sustainable model systems6, 7. We show that using materially closed soil–vegetation–atmosphere systems with pro rata carbon amounts for the main terrestrial carbon pools enables the establishment of conditions that balance plant carbon assimilation, and autotrophic and heterotrophic respiration fluxes over periods suitable to investigate short-term biotic carbon feedbacks. Using this approach, we tested an alternative way of assessing the impact of increased CO2 and temperature on biotic carbon feedbacks. The results show that without nutrient and water limitations, the short-term biotic responses could potentially buffer a temperature increase of 2.3 °C without significant positive feedbacks to atmospheric CO2. We argue that such closed-system research represents an important test-bed platform for model validation and parameterization of plant and soil biotic responses to environmental changes.

Kinetic multi-layer model of gas-particle interactions in aerosols and clouds (KM-GAP): linking condensation, evaporation and chemical reactions of organics, oxidants and water

We present a novel kinetic multi-layer model for gas-particle interactions in aerosols and clouds (KMGAP) that treats explicitly all steps of mass transport and chemical reaction of semi-volatile species partitioning between gas phase, particle surface and particle bulk. KMGAP is based on the PRA model framework (P¨oschl-Rudich- Ammann, 2007), and it includes gas phase diffusion, reversible adsorption, surface reactions, bulk diffusion and reaction, as well as condensation, evaporation and heat transfer. The size change of atmospheric particles and the temporal evolution and spatial profile of the concentration of individual chemical species can be modeled along with gas uptake and accommodation coefficients. Depending on the complexity of the investigated system and the computational constraints, unlimited numbers of semi-volatile species, chemical reactions, and physical processes can be treated, and the model shall help to bridge gaps in the understanding and quantification of multiphase chemistry and microphysics in atmospheric aerosols and clouds. In this study we demonstrate how KM-GAP can be used to analyze, interpret and design experimental investigations of changes in particle size and chemical composition in response to condensation, evaporation, and chemical reaction. For the condensational growth of water droplets, our kinetic model results provide a direct link between laboratory observations and molecular dynamic simulations, confirming that the accommodation coefficient of water at 270K is close to unity (Winkler et al., 2006). Literature data on the evaporation of dioctyl phthalate as a function of particle size and time can be reproduced, and the model results suggest that changes in the experimental conditions like aerosol particle concentration and chamber geometry may influence the evaporation kinetics and can be optimized for efficient probing of specific physical effects and parameters. With regard to oxidative aging of organic aerosol particles, we illustrate how the formation and evaporation of volatile reaction products like nonanal can cause a decrease in the size of oleic acid particles exposed to ozone.

A novel satellite mission concept for upper air water vapour, aerosol and cloud observations using integrated path differential absorption LiDAR limb sounding

We propose a new satellite mission to deliver high quality measurements of upper air water vapour. The concept centres around a LiDAR in limb sounding by occultation geometry, designed to operate as a very long path system for differential absorption measurements. We present a preliminary performance analysis with a system sized to send 75 mJ pulses at 25 Hz at four wavelengths close to 935 nm, to up to 5 microsatellites in a counter-rotating orbit, carrying retroreflectors characterized by a reflected beam divergence of roughly twice the emitted laser beam divergence of 15 µrad. This provides water vapour profiles with a vertical sampling of 110 m; preliminary calculations suggest that the system could detect concentrations of less than 5 ppm. A secondary payload of a fairly conventional medium resolution multispectral radiometer allows wide-swath cloud and aerosol imaging. The total weight and power of the system are estimated at 3 tons and 2,700 W respectively. This novel concept presents significant challenges, including the performance of the lasers in space, the tracking between the main spacecraft and the retroreflectors, the refractive effects of turbulence, and the design of the telescopes to achieve a high signal-to-noise ratio for the high precision measurements. The mission concept was conceived at the Alpbach Summer School 2010.

Analysis of Direct Outdoor Air Cooling Efficency for Combined Variable Air Volume Air-conditioning System in Stores in Cold Climates of China

Direct outdoor air cooling contributes a lot not only to the improvement of the indoor air quality but also to the energy saving. Its full use will reduce the water chiller’s running time especially in some stores where cooling load keeps much higher and longer than that in other buildings. A novel air-conditioning system named Combined Variable Air Volume system (CVAV), combining a normal AHU with a separate outdoor air supply system, was proposed firstly by the authors. The most attractive feature of the system is its full utilization of cooling capacity and freshness of outdoor air in the transition period of the year round. On the basis of the obtain of the dynamic cooling loads of the typical shopping malls in different four cities located in cold climates in China with the aid of DOE-2, the possibility of increasing the amount of outdoor air volume of CVAV system in the transition period instead of operating the water chillers was confirmed. Moreover, a new concept, Direct Outdoor Air Cooling Efficiency (DOACE), was defined as the ratio of cooling capacity of outdoor air to the water chiller, indicating the degree of outdoor air’s utilization. And the DOACE of the CVAV was calculated and compared with that of conventional all-air constant volume air-conditioning systems, the results showed that CVAV bear much more energy saving potential with the 10%~19% higher DOACE and it is a kind of energy efficient systems and can improve the indoor air quality as well.

Water quality trends in the Windrush catchment: Nitrogen speciation and sediment interactions

For the predominantly agricultural River Windrush catchment, spatial variations in concentrations of nitrogen species and suspended sediment were strongly related to geology and land use. Temporal patterns of NO3- and NO2- concentrations during the three year study were highly correlated with seasonal variations in baseflow. Suspended sediment concentrations were mainly controlled by storm discharge. Variations in total ammonium concentrations reflected both flow controls. Suspended sediment effects total ammonium and organic nitrogen transport to the aquatic system, and in-stream cycling processes. Organic nitrogen did not display consistent seasonal variations, but concentrations occasionally exceeding those of NO3-. Overall, NO3- and organic nitrogen were the most important at 60% and -40%, of total nitrogen load, respectively. Future assessments of agriculture impact on river water quality should consider the total nitrogen load, and not solely that of NO3-.

Modelling the impact of land use change on water quality in agricultural catchments

Export coefficient modelling was used to model the impact of agriculture on nitrogen and phosphorus loading on the surface waters of two contrasting agricultural catchments. The model was originally developed for the Windrush catchment where the highly reactive Jurassic limestone aquifer underlying the catchment is well connected to the surface drainage network, allowing the system to be modelled using uniform export coefficients for each nutrient source in the catchment, regardless of proximity to the surface drainage network. In the Slapton catchment, the hydrological path-ways are dominated by surface and lateral shallow subsurface flow, requiring modification of the export coefficient model to incorporate a distance-decay component in the export coefficients. The modified model was calibrated against observed total nitrogen and total phosphorus loads delivered to Slapton Ley from inflowing streams in its catchment. Sensitivity analysis was conducted to isolate the key controls on nutrient export in the modified model. The model was validated against long-term records of water quality, and was found to be accurate in its predictions and sensitive to both temporal and spatial changes in agricultural practice in the catchment. The model was then used to forecast the potential reduction in nutrient loading on Slapton Ley associated with a range of catchment management strategies. The best practicable environmental option (BPEO) was found to be spatial redistribution of high nutrient export risk sources to areas of the catchment with the greatest intrinsic nutrient retention capacity.

August Thienemann and Loch Lomond - an approach to the design of a system for monitoring the state of north-temperate standing waters

Limnologists had an early preoccupation with lake classification. It gave a necessary structure to the many chemical and biological observations that were beginning to form the basis of one of the earliest truly environmental sciences. August Thienemann was the doyen of such classifiers and his concept with Einar Naumann of oligotrophic and eutrophic lakes remains central to the world-view that limnologists still have. Classification fell into disrepute, however, as it became clear that there would always be lakes that deviated from the prescriptions that the classifiers made for them. Continua became the de rigeur concept and lakes were seen as varying along many chemical, biological and geographic axes. Modern limnologists are comfortable with this concept. That all lakes are different guarantees an indefinite future for limnological research. For those who manage lakes and the landscapes in which they are set, however, it is not very useful. There may be as many as 300000 standing water bodies in England and Wales alone and maybe as many again in Scotland. More than 80 000 are sizable (> 1 ha). Some classification scheme to cope with these numbers is needed and, as human impacts on them increase, a system of assessing and monitoring change must be built into such a scheme. Although ways of classifying and monitoring running waters are well developed in the UK, the same is not true of standing waters. Sufficient understanding of what determines the nature and functioning of lakes exists to create a system which has intellectual credibility as well as practical usefulness. This paper outlines the thinking behind a system which will be workable on a north European basis and presents some early results.

Brussels French une fois: Transfer-induced innovation or system-internal development?

In language contact studies, specific features of the contact languages are often seen to be the result of transfer (interference), but it remains difficult to disentangle the role of intra-systemic and inter-systemic factors. We propose to unravel these factors in the analysis of a feature of Brussels French which many researchers attribute to transfer from (Brussels) Dutch: the adverbial use of une fois. We compare the use of this particle in Brussels French with its occurrence in corpora of other varieties of French, including several that have not been influenced by a Germanic substrate or adstrate. A detailed analysis of the frequency of occurrence, the functions and the distribution of the particle over different syntactic positions shows that some uses of une fois can be traced back to sixteenth-century French, but that there is also ample evidence for overt and covert transfer (Mougeon and Beniak, 1991) from Brussels Dutch.

The earth, the sky and the water's edge: changing beliefs in the earlier prehistory of Northern Europe

There have been two kinds of study of ancient beliefs in the earlier prehistory of Scandinavia. One considers the impact of ideas which originated further to the south and east. It considers a cosmology based on the movements of the sun. A second tradition develops out of the ethnography of the circumpolar region and combines archaeological evidence with the beliefs of hunter-gatherers. It postulates the existence of a three-tier cosmology in which people could communicate between different worlds. This paper argues that certain elements that are thought to epitomize the ‘Southern’ system might have been suggested by existing ideas within Scandinavia itself. Both sets of beliefs came to influence one another, but they became increasingly distinct towards the end of the Bronze Age. This paper reconsiders the rock carvings, metalwork and mortuary cairns of that period and the Iron Age in relation to the process of religious change.

Reconciling observed and modelled phytoplankton dynamics in a major lowland UK river system, the Thames

This study aims to elucidate the key mechanisms controlling phytoplankton growth and decay within the Thames basin through the application of a modified version of an established river-algal model and comparison with observed stream water chlorophyll-a concentrations. The River Thames showed a distinct simulated phytoplankton seasonality and behaviour having high spring, moderate summer and low autumn chlorophyll-a concentrations. Three main sections were identified along the River Thames with different phytoplankton abundance and seasonality: (i) low chlorophyll-a concentrations from source to Newbridge; (ii) steep concentration increase between Newbridge and Sutton; and (iii) high concentrations with a moderate increase in concentration from Sutton to the end of the study area (Maidenhead). However, local hydrologic (e.g. locks) and other conditions (e.g. radiation, water depth, grazer dynamics, etc.) affected the simulated growth and losses. The model achieved good simulation results during both calibration and testing through a range of hydrological and nutrient conditions. Simulated phytoplankton growth was controlled predominantly by residence time, but during medium–low flow periods available light, water temperature and herbivorous grazing defined algal community development. These results challenge the perceived importance of in-stream nutrient concentrations as the perceived primary control on phytoplankton growth and death.

The global atmospheric water cycle

Water vapour plays a key role in the Earth's energy balance. Almost 50% of the absorbed solar radiation at the surface is used to cool the surface, through evaporation, and warm the atmosphere, through release of latent heat. Latent heat is the single largest factor in warming the atmosphere and in transporting heat from low to high latitudes. Water vapour is also the dominant greenhouse gas and contributes to a warming of the climate system by some 24°C (Kondratev 1972). However, water vapour is a passive component in the troposphere as it is uniquely determined by temperature and should therefore be seen as a part of the climate feedback system. In this short overview, we will first describe the water on planet Earth and the role of the hydrological cycle: the way water vapour is transported between oceans and continents and the return of water via rivers to the oceans. Generally water vapour is well observed and analysed; however, there are considerable obstacles to observing precipitation, in particular over the oceans. The response of the hydrological cycle to global warming is far reaching. Because different physical processes control the change in water vapour and evaporation/precipitation, this leads to a more extreme distribution of precipitation making, in general, wet areas wetter and dry areas dryer. Another consequence is a transition towards more intense precipitation. It is to be expected that the changes in the hydrological cycle as a consequence of climate warming may be more severe that the temperature changes.

On the determination of atmospheric water vapor from GPS measurements

Surface-based GPS measurements of zenith path delay (ZPD) can be used to derive vertically integrated water vapor (IWV) of the atmosphere. ZPD data are collected in a global network presently consisting of 160 stations as part of the International GPS Service. In the present study, ZPD data from this network are converted into IWV using observed surface pressure and mean atmospheric water vapor column temperature obtained from the European Centre for Medium-Range Weather Forecasts' (ECMWF) operational analyses (OA). For the 4 months of January/July 2000/2001, the GPS-derived IWV values are compared to the IWV from the ECMWF OA, with a special focus on the monthly averaged difference (bias) and the standard deviation of daily differences. This comparison shows that the GPS-derived IWV values are well suited for the validation of OA of IWV. For most GPS stations, the IWV data agree quite well with the analyzed data indicating that they are both correct at these locations. Larger differences for individual days are interpreted as errors in the analyses. A dry bias in the winter is found over central United States, Canada, and central Siberia, suggesting a systematic analysis error. Larger differences were mainly found in mountain areas. These were related to representation problems and interpolation difficulties between model height and station height. In addition, the IWV comparison can be used to identify errors or problems in the observations of ZPD. This includes errors in the data itself, e.g., erroneous outlier in the measured time series, as well as systematic errors that affect all IWV values at a specific station. Such stations were excluded from the intercomparison. Finally, long-term requirements for a GPS-based water vapor monitoring system are discussed.