Cu(II) adsorption at the calcite-water interface in the presence of natural organic matter: Kinetic studies and molecular-scale characterization

We have characterized the adsorption of Suwannee River humic acid (SRHA) and Cu(II) on calcite from preequilibrated solutions at pH 8.25. Sorption isotherms of SRHA on calcite follow Langmuir-type behavior at SRHA concentrations less than 15 mg C L⁻¹, whereas non-Langmuirian uptake becomes evident at concentrations greater than 15 mg C L⁻¹. The adsorption of SRHA on calcite is rapid and mostly irreversible, with corresponding changes in electrostatic properties. At pH 8.25, Cu(II) uptake by calcite in the presence of dissolved SRHA decreases with increasing dissolved SRHA concentration, suggesting that formation of Cu-SRHA aqueous complexes is the primary factor controlling Cu(II) sorption at the calcite surface under the conditions of our experiments. We also observed that surface-bound SRHA has little influence on Cu(II) uptake by calcite, suggesting that Cu(II) coordinates to calcite surface sites rather than to surface-bound SRHA.Cu K-edge X-ray absorption near edge structure (XANES) and extended X-ray absorption fine-structure (EXAFS) spectroscopic results show that the local coordination of Cu adsorbed at the calcite surface is very similar in the presence and absence of SRHA. Ca backscatterers at ∼3.90 Å indicate that Cu(II) forms tetragonally distorted inner-sphere adsorption complexes in both binary and ternary systems. Subtle differences in the XANES and EXAFS between binary sorption samples and ternary sorption samples, however, prevent us from ruling out the formation of ternary Cu-SRHA surface complexes. Our findings demonstrate that SRHA plays an important role in controlling the fate and transport of Cu(II) in calcite-bearing systems.     

Journeys to the street: the complex migration geographies of Ugandan street children

Children have generally been afforded little attention in migration research or unsatisfactorily included within family migration. Although they are an important consideration in family decisions to move, children also engage in autonomous, independent migration. Further, researchers now argue for the need to situate migration within political, economic and social conditions to obtain a full understanding of why people migrate. Through the use of children-centred research methods, and in-depth interviews with key informants, this paper considers children's journeys to the street in Uganda. By integrating an analysis of Ugandan street children's spatial origins with the familial and societal contexts of their migration decisions, this research highlights the complexity of their migration. In addition, an exploration of the impact of changing social, spatial and temporal conditions on street children's movements illustrates that their journeys are far more than just single processes.     

A generalized probabilistic approach for slope analysis: practical application to an open pit iron ore mine

Summary An example of the generalized probabilistic approach to slope analysis is given through a case study on an iron ore mine. A step by step engineering procedure is described, so that a practical application can be made to other structures under different field conditions.     

Computer modeling and simulation of coalbed methane resources

Coal seam gas reservoirs are complex both geologically and in the mechanism of gas production. Understanding these naturally fractured reservoirs for two-phase (gas–water) flow conditions is often limited by a lack of data. This paper illustrates that reservoir simulation is a powerful tool which can be used to determine key data requirements, and how variability in reservoir properties and operating practices affect performance at the field level. The paper presents examples of how reservoir simulation can be used to assess the efficiency of well completions (fracturing or cavitation), identify candidate wells for remedial treatment, examine methane drainage in advance of mining, and assess the impact of errors in measured data on long-term gas production forecasts.     

Local government, local economic development and quality of life in Poland

The establishment of local self-government was a key part of the post-1989 transformation in East and Central Europe. Local government in both Western and East and Central Europe has increasingly been expected to play a role in local economic development (LED). Local government is one important agent in the complex processes of building 'institutional thickness' to ensure the development of local economies and the quality of life of inhabitants. This paper presents the results of a national postal questionnaire survey of the LED role of the lowest level of local self-government in Poland, the gmina or commune. The paper establishes a baseline of knowledge regarding: the local economic problems faced by communes; their attitudinal, strategic and organisational responses; and the main factors which are hindering the communes' LED role. This revised version was published online in July 2006 with corrections to the Cover Date.     

Central England temperature since AD 1850: the potential of stable carbon isotopes in British oak trees to reconstruct past summer temperatures

In regions with seasonal temperate climatic regimes, tree growth is rarely controlled by any single environmental factor. As a consequence, the development of robust palaeoclimate reconstructions has proved challenging. Tree‐ring stable carbon isotope ratios (δ¹³C), however, are controlled primarily by photosynthetic rate, not by net growth. Therefore, at sites where climatic controls on tree‐ring growth are not strongly expressed, a robust (isotopic) palaeoclimate signal may still potentially be preserved. This hypothesis was tested using a 160‐year record of δ¹³C measured from the pooled latewood cellulose of six Quercus petraea L. (sessile oak) trees from Allt Lan‐las in West Wales, UK. Raw δ¹³C values were corrected for changes in the isotopic ratio of atmospheric carbon dioxide and for changes in the behaviour of trees due to the increasing availability of atmospheric CO₂ since AD 1850. Strong correlations with local summer temperature and sunshine are reported, and also with the Central England Temperature record over the full length of the isotopic chronology (AD 1850–2010) (r = 0.69, P < 0.001). We conclude that tree‐ring stable isotopes can be used to extract strong palaeoclimate signals even from oak trees growing in a temperate maritime climate. This demonstrates the potential for extracting robust palaeoclimatic information from the very long and well‐replicated oak chronologies which have been developed in western and central Europe primarily for dating rather than palaeoclimatic research purposes. Copyright © 2012 John Wiley & Sons, Ltd.     

A Closure Study of Aerosol Hygroscopic Growth Factor during the 2006 Pearl River Delta Campaign

Measurements of aerosol physical, chemical and optical parameterswere carried out in Guangzhou, China from 1 July to 31 July 2006 during thePearl River Delta Campaign. The dry aerosol scattering coefficient was measuredusing an integrating nephelometer and the aerosol scattering coefficient forwet conditions was determined by subtracting the sum of the aerosol absorptioncoefficient, gas scattering coefficient and gas absorption coefficient from theatmospheric extinction coefficient. Following this, the aerosol hygroscopicgrowth factor, f(RH), was calculated as the ratio of wet and dry aerosolscattering coefficients. Measurements of size-resolved chemical composition,relative humidity (RH), and published functional relationships between particlechemical composition and water uptake were likewise used to find the aerosolscattering coefficients in wet and dry conditions using Mie theory forinternally- or externally-mixed particle species [(NH₄)₂SO₄, NH₄NO₃, NaCl, POM, EC and residue]. Closure was obtained by comparingthe measured f(RH) values from the nephelometer and other in situ opticalinstruments with those computed from chemical composition and thermodynamics.Results show that the model can represent the observed f(RH) and isappropriate for use as a component in other higher-order models.     

Initialization and data assimilation experiments with a primitive equation model

The process of combining models of the ocean circulation with large data sets is known in meteorology as model initialization and data assimilation. This process is new to oceanographers, who only now are on the verge of having available world-wide synoptic maps of dynamic variables. In this paper we carry out a series of idealized initialization/assimilation experiments with a primitive equation (PE) model, which constitute a first step in developing a realistic process model and data assimilation techniques for the Gulf Stream system. The PE model is used in a spin-down mode and initialized with an analytic jet profile with geostrophically balanced fields.Two major questions are addressed in the present study. The first concerns the initialization process of a PE model during which internal/inertial gravity wave noise is produced. We ask: are the initialization shocks equally crucial for ocean models as they have been for their atmospheric counterparts? The results of an extensive series of balanced versus unbalanced initializations indicate that, for a PE model with a rigid lid, a brutally unbalanced initialization is required to produce strong internal gravity wave shocks. A geostrophically balanced initialization is sufficient to ensure smooth jet evolutions, with no apparent gravity waves, over long time durations in the spin-down mode. No sophisticated initialization procedures seem, therefore, to be required.The second question addressed is: which component of the flow is the most important in data assimilation to drive the model response towards a baseline reference ocean? We specifically compare the knowledge of the depth-integrated flow only, corresponding to measurements of the total transport, with the knowledge of the density field only, or equivalently the velocity shear. The knowledge of the interior density field is much more effective in decreasing the root-mean-square (r.m.s.) errors relative to the reference ocean. If the baroclinic structure is known, coarse horizontal resolutions of data insertion can be reached before significantly worsening the model estimates. If only the depth-averaged flow is known, a decrease in the horizontal resolution of data assimilation has an immediate effect: the r.m.s. errors sharply increase and the assimilation run diverges from the reference ocean. In the assimilation of the barotropic flow alone, even with dense resolution, the errors in the deep layers always show an increasing trend. The relative effectiveness of baroclinic versus barotropic data insertion can be rationalized in the context of geostrophic adjustment theory.     

Observations of boundary-layer convection cells measured by dual-Doppler radar and echosonde,and by microbarograph array

Three-dimensional air motion, observed with radar in a convective planetary boundary layer under light wind conditions, is organized in cellular structures scaled from 2 to 5 km; simultaneous acoustic echosonde measurements indicate that near the ground there are smaller cells than those observable by the radar. At heights of 400 m, cell scales become as large as those observable by the radar. Pressure fluctuations at the ground measured with spatial pressure transducers, at the same time as the radar and echosonde observations, traveled at the same speed and direction as the radar volume-averaged wind. The length scale determined at the ground with pressure fluctuation data was between 1.2 and 2.4 km, smaller than the largest radar-measured motion scales.