Hydrologic Transport of Dissolved Inorganic Carbon and Its Control on Chemical Weathering

Chemical weathering is one of the major processes interacting with climate and tectonics to form clays, supply nutrients to soil microorganisms and plants, and sequester atmospheric CO2. Hydrology and dissolution kinetics have been emphasized as factors controlling chemical weathering rates. However, the interaction between hydrology and transport of dissolved inorganic carbon (DIC) in controlling weathering has received less attention. In this paper, we present an analytical model that couples subsurface water and chemical molar balance equations to analyze the roles of hydrology and DIC transport on chemical weathering. The balance equations form a dynamical system that fully determines the dynamics of the weathering zone chemistry as forced by the transport of DIC. The model is formulated specifically for the silicate mineral albite, but it can be extended to other minerals, and is studied as a function of percolation rate and water transit time. Three weathering regimes are elucidated. For very small or large values of transit time, the weathering is limited by reaction kinetics or transport, respectively. For intermediate values, the system is transport controlled and is sensitive to transit time. We apply the model to a series of watersheds for which we estimate transit times and identify the type of weathering regime. The results suggest that hydrologic transport of DIC may be as important as reaction kinetics and dilution in determining chemical weathering rates

Arsenite sorption and co-precipitation with calcite

Sorption of As(III) by calcite was investigated as a function of As(III) concentration, time and pH. The sorption isotherm, i.e. the log As(III) vs. log [As(OH)3 degrees / Assat] plot is S-shaped and has been modelled on an extended version of the surface precipitation model. At low concentrations, As(OH)3 degrees is adsorbed by complexation to surface Ca surface sites, as previously described by the X-ray standing wave technique. The inflexion point of the isotherm, where As(OH)3 degrees is limited by the amount of surface sites (ST), yields 6 sites nm-2 in good agreement with crystallographic data. Beyond this value, the amount of sorbed arsenic increases linearly with solution concentration, up to the saturation of arsenic with respect to the precipitation of CaHAsO3(s). The solid solutions formed in this concentration range were examined by X-ray and neutron diffraction. The doped calcite lattice parameters increase with arsenic content while c/a ratio remains constant. Our results made on bulk calcite on the atomic displacement of As atoms along [0001] direction extend those published by Cheng et al., (1999) on calcite surface. This study provides a molecular-level explanation for why As(III) is trapped by calcite in industrial treatments.Comment: 9 page

Mechanisms of goethite dissolution in the presence of desferrioxamine B and Suwannee River fulvic acid at pH 6.5

Siderophores are Fe3+ specific low MW chelating ligands secreted by microorganisms in response to Fe stress. Low MW organic acids such as oxalate have been shown to enhance siderophore mediated dissolution of Fe3+ oxides. However, the effect of fulvic acid presence on siderophore function remains unknown. We used batch dissolution experiments to investigate Fe release from goethite in the goethite-fulvic acid desferrioxamine B (goethite-SRFA-DFOB) ternary system. Experiments were conducted at pH 6.5 while varying reagent addition sequence. FTIR and UV-Vis spectroscopy were employed to characterise the Fe-DFOB, Fe-SRFA and DFOB–SRFA complexes. Iron released from goethite in the presence of SRFA alone was below detection limit. In the presence of both SRFA and DFOB, dissolved Fe increased with reaction time, presence of the DFOB-SRFA complex, and where SRFA was introduced prior to DFOB. FTIR data show that in the ternary system, Fe3+ is complexed primarily to oxygen of the DFOB hydroxamate group, whilst the carboxylate C=O of SRFA forms an electrostatic association with the terminal NH3+ of DFOB. We propose that SRFA sorbed to goethite lowers the net positive charge of the oxide surface, thus facilitating adsorption of cationic DFOB and subsequent Fe3+ chelation and release. Furthermore, the sorbed SRFA weakens Fe-O bonds at the goethite surface, increasing the population of kinetically labile Fe. This work demonstrates the positive, though indirect role of SRFA in increasing the bioavailability of Fe3+

Serum level of serotonin during real and during exercise in paraplegic patients

The purpose of this study was to evaluate the serum level of serotonin (5-HT) during rest and response to exercise in subjects with spinal cord injury (SCI) with different levels of physical activity. Twenty-five male subjects with traumatic paraplegia, the neurological levels being between T1 and T12, volunteered for the study. They were divided into two groups matched for age, weight and time since injury, according to the level of physical activity: 14 inactive and 11 subjects regularly involved in sports activity and considered active. They all performed a maximal spiroergometric test with an arm crank ergometer. Two samples of blood were collected for 5-HT determination, during rest (PRE) and immediately after exercise test (POST). Serum 5-HT concentration was measured by high performance liquid chromatography using electrochemical detection (HPLC-ED). the results showed that peak oxygen uptake ((V) over dot O-2peak) was higher in the active group (27.08 +/- 2.60 vs 18.89 +/- 5.58 mL.kg(-1).min(-1), P0.05) or POST values (275.44 vs 311.05 ng.mL(-1), P>0.05). Both groups showed an increment in 5-HT after maximal exercise, but only in the active group it reached statistical significance (Wilcoxon test, P<0.02). Our results show that chronic paraplegic individuals have normal resting serum serotonin levels and normal response to exercise. the relationship between training status, mood elevation and 5-HT in SCI could not be established in the present study, and further investigation is needed to clarify this issue.Universidade Federal de São Paulo, Dept Physiol, São Paulo, BrazilUniversidade Federal de São Paulo, Dept Orthopaed & Traumatol, São Paulo, BrazilUniversidade Federal de São Paulo, Dept Psychobiol, São Paulo, BrazilUniversidade Federal de São Paulo, Dept Biochem, São Paulo, BrazilUniversidade Federal de São Paulo, Dept Neurol, São Paulo, BrazilUniv Fed Goias Catalao, Goiania, Go, BrazilUniversidade Federal de São Paulo, Dept Physiol, São Paulo, BrazilUniversidade Federal de São Paulo, Dept Orthopaed & Traumatol, São Paulo, BrazilUniversidade Federal de São Paulo, Dept Psychobiol, São Paulo, BrazilUniversidade Federal de São Paulo, Dept Biochem, São Paulo, BrazilUniversidade Federal de São Paulo, Dept Neurol, São Paulo, BrazilWeb of Scienc

Bioavailability in soils

The consumption of locally-produced vegetables by humans may be an important exposure pathway for soil contaminants in many urban settings and for agricultural land use. Hence, prediction of metal and metalloid uptake by vegetables from contaminated soils is an important part of the Human Health Risk Assessment procedure. The behaviour of metals (cadmium, chromium, cobalt, copper, mercury, molybdenum, nickel, lead and zinc) and metalloids (arsenic, boron and selenium) in contaminated soils depends to a large extent on the intrinsic charge, valence and speciation of the contaminant ion, and soil properties such as pH, redox status and contents of clay and/or organic matter. However, chemistry and behaviour of the contaminant in soil alone cannot predict soil-to-plant transfer. Root uptake, root selectivity, ion interactions, rhizosphere processes, leaf uptake from the atmosphere, and plant partitioning are important processes that ultimately govern the accumulation ofmetals and metalloids in edible vegetable tissues. Mechanistic models to accurately describe all these processes have not yet been developed, let alone validated under field conditions. Hence, to estimate risks by vegetable consumption, empirical models have been used to correlate concentrations of metals and metalloids in contaminated soils, soil physico-chemical characteristics, and concentrations of elements in vegetable tissues. These models should only be used within the bounds of their calibration, and often need to be re-calibrated or validated using local soil and environmental conditions on a regional or site-specific basis.Mike J. McLaughlin, Erik Smolders, Fien Degryse, and Rene Rietr

A Comparison of Computerized Chemical Models for Equilibrium Calculations in Aqueous Systems

A survey of computer programs which are currently being used to calculate the distribution of species in aqueous solutions, especially natural waters, has been made in order to 1) provide an inventory of available programs with a short description of their uses, 2) compare the consistency of their output for two given test solutions and 3) identify major weaknesses or problems encountered from their use. More than a dozen active programs which can be used for distribution of species and activity calculations for homogeneos equilibria among the major anions and cations of natural waters have been inventoried. Half of these programs can also accept several trace elements including Fe, Al, Mn, Cu, Ni, Zn, Cd, Pb, Ag, Hg, As, Ba, Sr, and B. Consistency between programs was evaluated by comparing the log of the molal concentrations of free ions and complexes for two test solutions: a hypothetical seawater analysis and a hypothetical river water analysis. Comparison of the free major ion concentrations in the river water test case shows excellent agreement for the major species. In the seawater test case there is less agreement and for both test cases the minor species commonly show orders of magnitude differences in concentrations. These differences primarily reflect differences in the thermodynamic data base of each chemical model although other factors such as activity coefficient calculations, redox assumptions, temperature corrections, alkalinity corrections and the number of complexes used all have an affect on the output

Mobility of Cr, Pb, Cd, Cu and Zn in a loamy sand soil : a comparative study

Interest in soil contamination has been growing in recent years due to the ongoing degradation of soil environments. Therefore, the development of remediation techniques and the study of contaminant sorption and migration are areas of intense research. In this study, the authors sought to evaluate the scenario of co-contamination of a loamy sand soil by multiple heavy metals. To that end, the sorption and transport of five metals—Cr, Pb, Cd, Cu and Zn—was evaluated using representative samples of a soil from the north of Portugal. The tests were conducted in batch and continuous systems using single- and multiple-metal acid solutions to evaluate the effect of metal competition. In accordance with the type of assay—batch or continuous—Langmuir or Convection Dispersion Two-Site Nonequilibrium models were adjusted to explain the sorption/transport data. FTIR analyses were performed on the final samples of the continuous systems. Generally, the results revealed good fitting of the tested models for the metals in competitive and noncompetitive scenarios, with the exception of Zn that was originally present in soil samples at higher concentrations. As expected, the influence of competition was observed in both batch and continuous systems, but with different tendencies. The FTIR spectra also revealed a strong influence of clay minerals and organic matter on the sorption of the metals.The PhD grants of Bruna Fonseca and Hugo Figueiredo and the research grant of Joana Rodrigues were financially supported by Fundacao para a Ciencia e Tecnologia, Ministerio da Ciencia e Tecnologia, Portugal and Fundo Social Europeu (FSE)

Consideration of the bioavailability of metal/metalloid species in freshwaters: experiences regarding the implementation of biotic ligand model-based approaches in risk assessment frameworks

After the scientific development of Biotic Ligand Models (BLMs) in recent decades these models are now considered suitable for implementation in regulatory risk assessment of metals in freshwater bodies. The approach has been developed over several years and has been described in many peer-reviewed publications. The original complex BLMs have been applied in prospective risk assessment reports for metals and metal compounds and are also recommended as suitable concepts for the evaluation of monitoring data in the context of the European Water Framework Directive. Currently, several user-friendly BLM-based bioavailability software tools are available for assessing the aquatic toxicity of a limited number of metals (mainly copper, nickel, and zinc). These tools need only a basic set of water parameters as input (e.g., pH, hardness, dissolved organic matter and dissolved metal concentration). Such tools seem appropriate to foster the implementation in routine water quality assessments. This work aims to review the existing bioavailability-based regulatory approaches and the application of available BLM-based bioavailability tools for this purpose. Advantages and possible drawbacks of these tools (e.g., feasibility, boundaries of validity) are discussed, and recommendations for further implementation are given

Not simply a matter of fish intake

Recent findings have highlighted enhanced fish consumption as a potential measure to increase intake of healthy fatty acids, particularly omega-3. The generalizability of this recommendation, however, may fall short of differences in fish species and cooking techniques. Hence, we investigated how these 2 variables affect the lipid content in fish flesh. Nine species of freshwater, deep sea or shore fish were grilled, steamed or fried with or without the addition of soybean oil, olive oil or butter. The lipid composition was analysed and a significant difference was observed in cholesterol, saturated fatty acids, polyunsaturated fatty acids, omega-3 fatty acids and omega-6 fatty acids contents between species (p<0.05). The use of soybean or olive oil was associated with a significant change in flesh concentration of polyunsaturated, omega-3 and omega-6 fatty acids (p<0.05). This study calls attention to the specific lipid content that must be expected from different fish species and cooking techniques135676678CONSELHO NACIONAL DE DESENVOLVIMENTO CIENTÍFICO E TECNOLÓGICO - CNPQFUNDAÇÃO DE AMPARO À PESQUISA DO ESTADO DE SÃO PAULO - FAPESPsem informação2012/18044-