On the pH-dependent formation constants of iron(III)-sulfur(IV) transient complexes

An experimental study is described of Fe(III)-S(IV) formation constants measured as a function of pH (1–3), ionic strength (0.2–0.5 M) and [Fe(III)] _T (2.5–5.0×10^–4 M) using a continuous-flow spectrophotometric technique to make observations 160 ms after mixing. Preliminary experiments using pulse-accelerated-flow (PAF) spectrophotometry to measure rate constants on a microsecond timescale are also described. The conditional formation constant at 25 °C can be modeled with the following equation: {ie307-1} where {ie307-2}K ₇ andK ₈ can be interpreted as intrinsic constants for the coordination of HSO ₃ ^– by FeOH²⁺ and Fe³⁺, respectively, but until further evidence is obtained they should be regarded as fitting constants. PAF spectrophotometry showed that the initial reaction of Fe(III) with S(IV) (pH 2.0) is characterized by a second-order rate constant of 4×10⁶ M^–1 s^–1 which is comparable to rate of reaction of FeOH²⁺ with SO ₄ ^2– . However, the PAF results should be regarded as preliminary since unexpected features in the initial data indicate that the reaction may be more complex than expected.     

COSMO-CLM2: a new version of the COSMO-CLM model coupled to the Community Land Model

This study presents an evaluation of a new biosphere-atmosphere Regional Climate Model. COSMO-CLM² results from the coupling between the non-hydrostatic atmospheric model COSMO-CLM version 4.0 and the Community Land Model version 3.5 (CLM3.5). In this coupling, CLM3.5 replaces a simpler land surface parameterization (TERRA_ML) used in the standard COSMO-CLM. Compared to TERRA_ML, CLM3.5 comprises a more complete representation of land surface processes including hydrology, biogeophysics, biogeochemistry and vegetation dynamics. Historical climate simulations over Europe with COSMO-CLM and with the new COSMO-CLM² are evaluated against various data products. The simulated climate is found to be substantially affected by the coupling with CLM3.5, particularly in summer. Radiation fluxes as well as turbulent fluxes at the surface are found to be more realistically represented in COSMO-CLM². This subsequently leads to improvements of several aspects of the simulated climate (cloud cover, surface temperature and precipitation). We show that a better partitioning of turbulent fluxes is the central factor allowing for the better performances of COSMO-CLM² over COSMO-CLM. Despite these improvements, some model deficiencies still remain, most notably a substantial underestimation of surface net shortwave radiation. Overall, these results highlight the importance of land surface processes in shaping the European climate and the benefit of using an advanced land surface model for regional climate simulations.     

Momentum and Turbulent Kinetic Energy Budgets Within the Park Avenue Street Canyon During the Joint Urban 2003 Field Campaign

Very few attempts have so far been made to quantify the momentum and turbulent kinetic energy (TKE) budgets within real urban canopies. In this study, sonic anemometer data obtained during the Joint Urban 2003 field campaign in Oklahoma City, U.S.A. were used for calculating the momentum and TKE budgets within a real-world urban street canyon. Sonic anemometers were deployed on multiple towers in the lower half of the canyon. Gradients in all three principal directions were included in the analyses. The storage and buoyancy terms were found to have negligible contributions to both the momentum and TKE budgets. The momentum budgets were generally found to be more complex than a simple balance of two physical processes. The horizontal terms were found to have significant and sometimes dominant contributions to the momentum and TKE budgets.     

Coupled climate impacts of the Drake Passage and the Panama Seaway

Tectonically-active gateways between ocean basins have modified ocean circulation over Earth history. Today, the Atlantic and Pacific are directly connected via the Drake Passage, which forms a barrier to the time-mean geostrophic transport between the subtropics and Antarctica. In contrast, during the warm early Cenozoic era, when Antarctica was ice-free, the Drake Passage was closed. Instead, at that time, the separation of North and South America provided a tropical seaway between the Atlantic and Pacific that remained open until the Isthmus of Panama formed in the relatively recent geological past. Ocean circulation models have previously been used to explore the individual impacts of the Drake Passage and the Panama Seaway, but rarely have the two gateways been considered together, and most explorations have used very simple atmospheric models. Here we use a coupled ocean–ice–atmosphere model (GFDL’s CM2Mc), to simulate the impacts of a closed Drake Passage both with and without a Panama Seaway. We find that the climate response to a closed Drake Passage is relatively small when the Panama Seaway is absent, similar to prior studies, although the coupling to a dynamical atmosphere does increase the temperature change. However, with a Panama Seaway, closing Drake Passage has a much larger effect, due to the cessation of deep water formation in the northern hemisphere. Both gateways alter the transport of salt by ocean circulation, with the Panama Seaway allowing fresh Pacific water to be imported to the North Atlantic, and the Drake Passage preventing the flow of saline subtropical water to the circum-Antarctic, a flow that is particularly strong when the Panama Seaway is open. Thus, with a Panama Seaway and a closed Drake Passage, the Southern Ocean tends to be relatively salty, while the North Atlantic tends to be relatively fresh, such that the deep ocean is ventilated from the circum-Antarctic. Ensuing changes in the ocean heat transport drive a bi-polar shift of surface ocean temperatures, and the Intertropical Convergence Zone migrates toward the warmer southern hemisphere. The response of clouds to changes in surface ocean temperatures amplifies the climate response, resulting in temperature changes of up to 9 °C over Antarctica, even in the absence of land-ice feedbacks. These results emphasize the importance of tectonic gateways to the climate history of the Cenozoic, and support a role for ocean circulation changes in the glaciation of Antarctica.     

Similarity Scaling Over a Steep Alpine Slope

In this study, we investigate the validity of similarity scaling over a steep mountain slope (30–41 $^\circ $ ). The results are based on eddy-covariance data collected during the Slope Experiment near La Fouly (SELF-2010); a field campaign conducted in a narrow valley of the Swiss Alps during summer 2010. The turbulent fluxes of heat and momentum are found to vary significantly with height in the first few metres above the inclined surface. These variations exceed by an order of magnitude the well-accepted maximum 10 % required for the applicability of Monin–Obukhov similarity theory in the surface layer. This could be due to a surface layer that is too thin to be detected or to the presence of advective fluxes. It is shown that local scaling can be a useful tool in these cases when surface-layer theory breaks down. Under convective conditions and after removing the effects of self-correlation, the normalized standard deviations of slope-normal wind velocity, temperature and humidity scale relatively well with $z/\varLambda $ , where $z$ is the measurement height and $\varLambda (z)$ the local Obukhov length. However, the horizontal velocity fluctuations are not correlated with $z/\varLambda $ under all stability regimes. The non-dimensional gradients of wind velocity and temperature are also investigated. For those, the local scaling appears inappropriate, particularly at night when shallow drainage flows prevail and lead to negative wind-speed gradients close to the surface.     

Large-Scale Structures over a Single Street Canyon Immersed in an Urban-Type Boundary Layer

An analysis of the dynamics of the flow over a street canyon immersed in an atmospheric boundary layer is presented, using particle image velocimetry measurements in a wind tunnel. Care was taken to generate a 1:200 model scale urban type boundary layer that is correctly scaled to the size of the canyon buildings. Using proper orthogonal decomposition (POD) of the velocity field and conditional averaging techniques, it is first shown that the flow above the opening of the canyon consists of a shear layer separating from the upstream obstacle, animated by a coherent flapping motion and generating large-scale vortical structures. These structures are alternately injected into the canyon or shed off the obstacle into the outer flow. It is shown that unsteady fluid exchanges between the canyon and the outer flow are mainly driven by the shear layer. Finally, using POD, the non-linear interaction between the large-scale structures of the oncoming atmospheric boundary layer and the flow over the canyon is demonstrated.     

Intraseasonal variability of sea level and circulation in the Gulf of Thailand: the role of the Madden–Julian Oscillation

Intraseasonal variability of the tropical Indo-Pacific ocean is strongly related to the Madden–Julian Oscillation (MJO). Shallow seas in this region, such as the Gulf of Thailand, act as amplifiers of the direct ocean response to surface wind forcing by efficient setup of sea level. Intraseasonal ocean variability in the Gulf of Thailand region is examined using statistical analysis of local tide gauge observations and surface winds. The tide gauges detect variability on intraseasonal time scales that is related to the MJO through its effect on local wind. The relationship between the MJO and the surface wind is strongly seasonal, being most vigorous during the monsoon, and direction-dependent. The observations are then supplemented with simulations of sea level and circulation from a fully nonlinear barotropic numerical ocean model (Princeton Ocean Model). The numerical model reproduces well the intraseasonal sea level variability in the Gulf of Thailand and its seasonal modulations. The model is then used to map the wind-driven response of sea level and circulation in the entire Gulf of Thailand. Finally, the predictability of the setup and setdown signal is discussed by relating it to the, potentially predictable, MJO index.     

Enhancing the relevance of Shared Socioeconomic Pathways for climate change impacts,adaptation and vulnerability research

This paper discusses the role and relevance of the shared socioeconomic pathways (SSPs) and the new scenarios that combine SSPs with representative concentration pathways (RCPs) for climate change impacts, adaptation, and vulnerability (IAV) research. It first provides an overview of uses of social–environmental scenarios in IAV studies and identifies the main shortcomings of earlier such scenarios. Second, the paper elaborates on two aspects of the SSPs and new scenarios that would improve their usefulness for IAV studies compared to earlier scenario sets: (i) enhancing their applicability while retaining coherence across spatial scales, and (ii) adding indicators of importance for projecting vulnerability. The paper therefore presents an agenda for future research, recommending that SSPs incorporate not only the standard variables of population and gross domestic product, but also indicators such as income distribution, spatial population, human health and governance.     

Bertin’s matrix concepts reconsidered: transformations of semantics and semiotics to support geovisualization use

A system for managing and visualizing archaeological finds and their spatio-temporal properties is presented. The system is an attempt to combine archaeologists' interest to keep track of time with interests related to the representation and visualization of the spatio-temporal component of archaeological excavations, with the help of cartographic and GIS methods and techniques. Several parameters of a prehistoric excavation such as finds, their thematic characteristics, and their spatio-temporal distributions are examined. A three-dimensional GIS/cartographic environment and its user interface to the excavation database have been developed as a tool for enhancing archaeological interpretation in an exploratory environment. The development of the system is an ongoing task; the article describes its current use as a prototype.     

Electricity consumption patterns within cities: application of a data-driven settlement characterization method

ABSTRACT

Urban areas presently consume around 75% of global primary energy supply, which is expected to significantly increase in the future due to urban growth. Having sustainable, universal energy access is a pressing challenge for most parts of the globe. Understanding urban energy consumption patterns may help to address the challenges to urban sustainability and energy security. However, urban energy analyses are severely limited by the lack of urban energy data. Such datasets are virtually non-existent for the developing countries. As per current projections, most of the new urban growth is bound to occur in these data-starved regions. Hence, there is an urgent need of research methods for monitoring and quantifying urban energy utilization patterns. Here, we apply a data-driven approach to characterize urban settlements based on their formality, which is then used to assess intra-urban urban energy consumption in Johannesburg, South Africa; Sana’a, Yemen; and Ndola, Zambia. Electricity is the fastest growing energy fuel. By analyzing the relationship between the settlement types and the corresponding nighttime light emission, a proxy of electricity consumption, we assess the differential electricity consumption patterns. Our study presents a simple and scalable solution to fill the present data void to understand intra-city electricity consumption patterns.