Verification and intercomparison of reactive transport codes to describe root-uptake

Several mathematical models have been developed to simulate processes and interactions in the plant rhizosphere. Most of these models are based on a rather simplified description of the soil chemistry and interactions of plant roots in the rhizosphere. In particular the feedback loops between exudation, water and solute uptake are mostly not considered, although their importance in the bioavailability of mineral elements for plants has been demonstrated. The aim of this work was to evaluate three existing coupled speciation-transport tools to model rhizosphere processes. In the field of hydrogeochemistry, such␣computational tools have been developed to␣describe acid-base and redox reactions, complexation and ion exchange, adsorption and precipitation of chemical species in soils and aquifers using thermodynamic and kinetic relationships. We implemented and tested a simple rhizosphere model with three geochemical computational tools (ORCHESTRA, MIN3P, and PHREEQC). The first step was an accuracy analysis of the different solution strategies by comparing the numerical results to the analytical solution of solute uptake (K or Ca) by a single cylindrical root. All models are able to reproduce the concentration profiles as well as the uptake flux. The relative error of the simulated concentration profile decreases with increasing distance from the root. The uptake flux was simulated for all codes with less than 5% error for K and less than 0.4% for Ca. The strength of the codes presented in this paper is that they can also be used to investigate more complex and coupled biogeochemical processes in rhizosphere models. This is shown exemplarily with simulations involving both exudation and uptake and the simultaneous uptake of solute and wate

Acoustic signal typing for evaluation of voice quality in tracheoesophageal speech

Summary: Because of the aperiodicity of many tracheoesophageal voices, acoustic analysis of the tracheoesophageal voice is less straightforward than that of the normal voice. This study presents the development and testing of an acoustic signal typing system based on visual inspection of a narrow-band spectrogram that can be used by researchers for classification of voice quality in tracheoesophageal speech. In addition to this classification system, a selection of acoustic measures [median fundamental frequency, standard deviation of fundamental frequency, jitter, percentage of voiced (%Voiced), harmonics-to-noise ratio (HNR), glottal-to-noise excitation (GNE) ratio, and band energy difference (BED)] was computed to provide more insight into the acoustic components of tracheoesophageal voice quality. For clinical relevance, relationships between the acoustic signal types and an overall judgment of the voice were investigated as well. Results showed that the four acoustic signal types form a good basis for performing more acoustic analyses and give a good impression of the overall quality of the voice

Automatic recognition of schwa variants in spontaneous Hungarian speech

This paper analyzes the nature of the process involved in optional vowel reduction in Hungarian, and the acoustic structure of schwa variants in spontaneous speech. The study focuses on the acoustic patterns of both the basic realizations of Hungarian vowels and their realizations as neutral vowels (schwas), as well as on the design, implementation, and evaluation of a set of algorithms for the recognition of both types of realizations from the speech waveform. The authors address the question whether schwas form a unified group of vowels or they show some dependence on the originally intended articulation of the vowel they stand for. The acoustic study uses a database consisting of over 4,000 utterances extracted from continuous speech, and recorded from 19 speakers. The authors propose methods for the recognition of neutral vowels depending on the various vowels they replace in spontaneous speech. Mel-Frequency Cepstral Coefficients are calculated and used for the training of Hidden Markov Models. The recognition system was trained on 2,500 utterances and then tested on 1,500 utterances. The results show that a neutral vowel can be detected in 72% of all occurrences. Stressed and unstressed syllables can be distinguished in 92% of all cases. Neutralized vowels do not form a unified group of phoneme realizations. The pronunciation of schwa heavily depends on the original articulation configuration of the intended vowel

Developing and testing a nurse-led intervention to support bereavement in relatives in the intensive care (BRIC study): a protocol of a pre-post intervention study

BACKGROUND: When a patient is approaching death in the intensive care unit (ICU), patients' relatives must make a rapid transition from focusing on their beloved one's recovery to preparation for their unavoidable death. Bereaved relatives may develop complicated grief as a consequence of this burdensome situation; however, little is known about appropriate options in quality care supporting bereaved relatives and the prevalence and predictors of complicated grief in bereaved relatives of deceased ICU patients in the Net

The kinetics of sorption by retarded diffusion into soil aggregate pores

This study investigates time-dependent sorption of pesticides in soil aggregates. We tested if the sorption kinetics of pesticides in soil aggregates can be described by modeling diffusion into aggregates for a range of soils and pesticides. Our hypothesis is that the rate of sorption is negatively related to sorption strength due to retardated diffusion. Natural aggregates of 3 - 5 mm diameter were separated from three soils: a clay, a silty clay loam, and a clay loam. The aggregates werestabilized with alginate gel, and adsorption of azoxystrobin, chlorotoluron, and atrazine was measured in batch experiments with eight equilibration times up to 28 days. Equilibrium sorption appeared to be reached within the 28-day period for each pesticide. An intra-aggregate diffusion model was employed to describe the increase of sorption with time. The model describes diffusion of the dissolved pesticides through the pore space inside the aggregates and sorption on internal surfaces. Sorption could be described by pore diffusion into the aggregates with diffusion coefficients between 0.5 × 10-10 and 1.5 × 10-10 m 2 s-1. The model fits support the theory that pore diffusion is the rate-limiting process for sorption of pesticides in aggregates, although the diffusion coefficients were a factor 3 - 10 smaller than the theoretical diffusion coefficient for diffusion in water. Comparing the results from the different pesticide - soil combinations showed that the extent of nonequilibrium increased with increasing sorption strength. This confirmed that sorption takes longer to reach equilibrium for pesticides and soils with stronger sorption. The differences between the different pesticides and soils were fully accounted for in the model by stronger retardation of the more strongly sorbed pesticides. The results imply that diffusion into aggregates may be the major time-limiting process for sorption of pesticides in structured soils. Commonly performed sorption experiments with sieved soil fail to account for this process. © 2009 American Chemical Society.Peer Reviewe

Reanalysis of experiments to quantify irreversibility of pesticide sorption-desorption in soil

6 pages, 4 figures, 2 tables, 19 references.Previously published research used an isotope-exchange technique to measure irreversibility of pesticide sorption-desorption in soil. Results indicated significant irreversibility (6-51%) in sorption in five pesticide-soil systems measured over 72 h. Here, we propose a three-site model to reanalyze the experimental data. The model adds a slow but reversible binding on nonequilibrium sorption sites in addition to instantaneously reversible sites and irreversible sites. The model was able to match experimental data very closely, but only if irreversible sorption was assumed to be absent. Observed asymmetry in the binding of 12C- and 14C-pesticide was explained on the basis of nonattainment of sorption equilibrium over the study period. Results suggest that irreversible sorption may be less significant than previously considered with important implications for understanding the fate of pesticides applied to soil.EPSRC and Syngenta Ltd are gratefully acknowledged for funding this research.Peer Reviewe

Pesticide sorption and diffusion in natural clay loam aggregates

Pesticide sorption in soils is controlled by time-dependent processes such as diffusion into soil aggregates and microscopic sorbent particles. This study examines the rate-controlling step for time-dependent sorption in clay loam aggregates. Aggregates (5 mm) were stabilized with alginate, and adsorption of azoxystrobin, chlorotoluron, and cyanazine was measured in batch systems equilibrated for periods between 1 h and 7 days. Stepwise desorption was measured at 1- or 3-day intervals following 1 or 7 days of adsorption. Time-dependent adsorption was also measured on dispersed soil. Results were interpreted using process-based modeling. Adsorption on dispersed soil was described by intraparticle sorption and diffusion. Adsorption in the aggregates was much less than in suspension, suggesting that part of the sorption capacity of the dispersed soil was not available within the aggregates (50%). Adsorption and desorption were reversible and could be described by pore diffusion into the aggregate with effective diffusion coefficients between 0.5 × 10-10 and 1 × 10-10 m2 s-1, a factor 3−6 slower than estimated theoretically. Intraparticle diffusion did not seem to contribute to sorption in the aggregates at this time scale. Apparent hysteresis was explained by nonattainment of equilibrium during the adsorption and desorption steps

Modeling transport of protons and calcium ions in an alginate gel bead system : The effects of physical non-equilibrium and non-linear competitive sorption

Solute transport in heterogeneous soil systems is determined by a combination of physical and chemical processes. Heterogeneity can cause physical nonequilibrium, which results in asymmetrical breakthrough curves with early initial breakthrough and tailing. In the case of reactive transport, the shape of the breakthrough curve is also effected by the sorption isotherm and by multicomponent effects. The combined effects of physical nonequilibrium and nonlinear multicomponent chemistry are the subject of this study. We show how an experimental system composed of alginate gel beads, together with two-region transport modeling, can be used to study transport phenomena in reactive heterogeneous systems. Proton transport through the gel column with ion exchange of protons and calcium ions was measured and simulated. The results show the combined effects of nonlinear sorption and of competition, which add to the effects of physical nonequilibrium. The results emphasize the importance of a thorough understanding of both physical and chemical processes for a reliable prediction of reactive solute transport