Transport and Reaction Processes in Soil

In order to register agrochemicals in Europe it is necessary to have a detailed understanding of the processes in the environment that break down agrochemicals. The existing framework for environmental assessment includes a consideration of soil water movement and microbial breakdown of products in soil and these processes are relatively understood and represented in models. However the breakdown of agrochemicals by the action of light incident on the soil surface by a process termed photolysis is not so well represented in models of environmental fate. The problem brought by Syngenta (one of the worlds leading agrochemical companies) to the workshop was how to include the effects of light degradation of chemicals into predictive models of environmental fate. Photolysis is known to occur in a very thin layer at the surface of soil. The workshop was asked to consider how the very rough nature of the upper surface of a ploughed field might affect the degradation of chemicals by sunlight. The discussions were directed down two avenues: - firstly to determine how the very small distances over which photolysis occurs might be adequately incorporated into models of transport in soils and, - secondly to consider how the rough surface might modify the illumination of the surface and hence alter degradation. The rate of degradation by photolysis is measured in the laboratory by illuminating a thin, typically about 1 or 2 mm, layer of soil with very strong xenon lamps. The amount of chemical is measured at various intervals and is fitted to a first-order process. Field experiments where the chemical is sprayed on a bare field show evidence of photolysis indicated by biphasic degradation patterns and the presence of breakdown products only formed by photolysis. This report addresses methods for mathematically modelling the action of photolysis on particular relevant chemical species. We start with a general discussion of mechanisms that transport chemicals within soil §2. There is an existing computational model exploited by Syngenta for such modelling and we discuss how this performs and the predictions that can be derived using it §3. The particular mechanism of photolysis is then considered. One aspect of this mechanism that is investigated is how the roughness of the surface of the soil could be adequately incorporated into the modelling. Some results relating to this are presented §4.2. Some of the original experimental data used to derive aspects of the model of photolysis are revisited and a simple model of the process presented and shown to fit the data very well §5. By considering photolysis with a constant diffusion coefficient various analytical results are derived and general behaviour of the system outlined. This simple model is then applied to real field-based data and shown to give very good fit when simply extended to account for the moisture variations by utilising moisture dependent diffusion coefficients derived from the existing computational model §5.3. Some consequences of the simple model are then discussed §6

Investigation of nanodispersion in polystyrene-montmorillonite nanocomposites by solid state NMR

Nanocomposites result from combinations of materials with vastly different properties in the nanometer scale. These materials exhibit many unique properties such as improved thermal stability, reduced flammability, and improved mechanical properties. Many of the properties associated with polymer–clay nanocomposites are a function of the extent of exfoliation of the individual clay sheets or the quality of the nanodispersion. This work demonstrates that solid-state NMR can be used to characterize, quantitatively, the nanodispersion of variously modified montmorillonite (MMT) clays in polystyrene (PS) matrices. The direct influence of the paramagnetic Fe3, embedded in the aluminosilicate layers of MMT, on polymer protons within about 1 nm from the clay surfaces creates relaxation sources, which, via spin diffusion, significantly shorten the overall proton longitudinal relaxation time (T1 H). Deoxygenated samples were used to avoid the particularly strong contribution to the T1 H of PS from paramagnetic molecular oxygen. We used T1 H as an indicator of the nanodispersion of the clay in PS. This approach correlated reasonably well with X-ray diffraction and transmission electron microscopy (TEM) data. A model for interpreting the saturation-recovery data is proposed such that two parameters relating to the dispersion can be extracted. The first parameter, f, is the fraction of the potentially available clay surface that has been transformed into polymer–clay interfaces. The second parameter is a relative measure of the homogeneity of the dispersion of these actual polymer–clay interfaces. Finally, a quick assay of T1 H is reported for samples equilibrated with atmospheric oxygen. Included are these samples as well as 28 PS/MMT nanocomposite samples prepared by extrusion. These measurements are related to the development of highthroughput characterization techniques. This approach gives qualitative indications about dispersion; however, the more time-consuming analysis, of a few deoxygenated samples from this latter set, offers significantly greater insight into the clay dispersion. A second, probably superior, rapid-analysis method, applicable to oxygen-containing samples, is also demonstrated that should yield a reasonable estimate of the f parameter. Thus, for PS/MMT nanocomposites, one has the choice of a less complete NMR assay of dispersion that is significantly faster than TEM analysis, versus a slower and more complete NMR analysis with sample times comparable to TEM, information rivaling that of TEM, and a substantial advantage that this is a bulk characterization method. © 2003 Wiley Periodicals, Inc.* J Polym Sci Part B: Polym Phys 41: 3188–3213, 200

A Bayesian spatial random effects model characterisation of tumour heterogeneity implemented using Markov chain Monte Carlo (MCMC) simulation

The focus of this study is the development of a statistical modelling procedure for characterising intra-tumour heterogeneity, motivated by recent clinical literature indicating that a variety of tumours exhibit a considerable degree of genetic spatial variability. A formal spatial statistical model has been developed and used to characterise the structural heterogeneity of a number of supratentorial primitive neuroecto-dermal tumours (PNETs), based on diffusionweighted magnetic resonance imaging. Particular attention is paid to the spatial dependence of diffusion close to the tumour boundary, in order to determine whether the data provide statistical evidence to support the proposition that water diffusivity in the boundary region of some tumours exhibits a deterministic dependence on distance from the boundary, in excess of an underlying random 2D spatial heterogeneity in diffusion. Tumour spatial heterogeneity measures were derived from the diffusion parameter estimates obtained using a Bayesian spatial random effects model. The analyses were implemented using Markov chain Monte Carlo (MCMC) simulation. Posterior predictive simulation was used to assess the adequacy of the statistical model. The main observations are that the previously reported relationship between diffusion and boundary proximity remains observable and achieves statistical significance after adjusting for an underlying random 2D spatial heterogeneity in the diffusion model parameters. A comparison of the magnitude of the boundary-distance effect with the underlying random 2D boundary heterogeneity suggests that both are important sources of variation in the vicinity of the boundary. No consistent pattern emerges from a comparison of the boundary and core spatial heterogeneity, with no indication of a consistently greater level of heterogeneity in one region compared with the other. The results raise the possibility that DWI might provide a surrogate marker of intra-tumour genetic regional heterogeneity, which would provide a powerful tool with applications in both patient management and in cancer research

Scheme for Attophysics Experiments at a X-ray SASE FEL

We propose a concept for production of high power coherent attosecond pulses in X-ray range. An approach is based on generation of 8th harmonic of radiation in a multistage HGHG FEL (high gain high harmonic free electron laser) configuration starting from shot noise. Single-spike phenomena occurs when electron bunch is passed through the sequence of four relatively short undulators. The first stage is a conventional "long" wavelength (0.8 nm) SASE FEL which operates in the high-gain linear regime. The 0.1 nm wavelength range is reached by successive multiplication (0.8 nm $\to$ 0.4 nm $\to$ 0.2 nm $\to$ 0.1 nm) in a stage sequence. Our study shows that the statistical properties of the high-harmonic radiation from the SASE FEL, operating in linear regime, can be used for selection of radiation pulses with a single spike in time domain. The duration of the spikes is in attosecond range. Selection of single-spike high-harmonic pulses is achieved by using a special trigger in data acquisition system. The potential of X-ray SASE FEL at TESLA at DESY for generating attosecond pulses is demonstrated. Since the design of XFEL laboratory at TESLA is based on the use of long SASE undulators with tunable gap, no special place nor additional FEL undulators are required for attophysics experiments. The use of a 10 GW-level attosecond X-ray pulses at X-ray SASE FEL facility will enable us to track processes inside atoms.Comment: 21 pages, 12 figures, submitted to Optics Communication

SSthreshless Start: A Sender-Side TCP Intelligence for Long Fat Network

Measurement shows that 85% of TCP flows in the internet are short-lived flows that stay most of their operation in the TCP startup phase. However, many previous studies indicate that the traditional TCP Slow Start algorithm does not perform well, especially in long fat networks. Two obvious problems are known to impact the Slow Start performance, which are the blind initial setting of the Slow Start threshold and the aggressive increase of the probing rate during the startup phase regardless of the buffer sizes along the path. Current efforts focusing on tuning the Slow Start threshold and/or probing rate during the startup phase have not been considered very effective, which has prompted an investigation with a different approach. In this paper, we present a novel TCP startup method, called threshold-less slow start or SSthreshless Start, which does not need the Slow Start threshold to operate. Instead, SSthreshless Start uses the backlog status at bottleneck buffer to adaptively adjust probing rate which allows better seizing of the available bandwidth. Comparing to the traditional and other major modified startup methods, our simulation results show that SSthreshless Start achieves significant performance improvement during the startup phase. Moreover, SSthreshless Start scales well with a wide range of buffer size, propagation delay and network bandwidth. Besides, it shows excellent friendliness when operating simultaneously with the currently popular TCP NewReno connections.Comment: 25 pages, 10 figures, 7 table

The Effect of Boron-Containing Layered Hydroxy Salt (LHS) on the Thermal Stability and Degradation Kinetics of Poly (Methyl Methacrylate)

A boron-containing layered hydroxy salt (LHS), ZHTMDBB, was prepared and compounded with a highly flammable synthetic polymer, poly (methyl methacrylate) {PMMA}, via melt blending: the composite structure was intercalated with poor dispersion. The effect of this LHS on the flammability, thermal stability and degradation kinetics of PMMA was investigated via cone calorimetry and thermogravimetric analysis. The addition of 3-10% by mass of ZHTMDBB to PMMA resulted in significant reduction of peak heat release rate (22-48%) of the polymer and improvements in thermal stability were observed in both air and nitrogen. Effective activation energies for the degradation process were evaluated using Flynn-Wall-Ozawa, Friedman, and Kissinger methods. All three methods indicated that the additive increased the activation energies of the first step of the degradation process in both air and nitrogen. Activation energies of the second step were lowered in nitrogen but were not significantly affected in air

Theory of Polarization Attraction in Parametric Amplifiers Based on Telecommunication Fibers

We develop from first principles the coupled wave equations that describe polarization-sensitive parametric amplification based on four-wave mixing in standard (randomly birefringent) optical fibers. We show that in the small-signal case these equations can be solved analytically, and permit us to predict the gain experienced by the signal beam as well as its state of polarization (SOP) at the fiber output. We find that, independently of its initial value, the output SOP of a signal within the parametric gain bandwidth is solely determined by the pump SOP. We call this effect of pulling the polarization of the signal towards a reference SOP as polarization attraction, and such parametric amplifier as the FWM-polarizer. Our theory is valid beyond the zero polarization mode dispersion (PMD) limit, and it takes into account moderate deviations of the PMD from zero. In particular, our theory is capable of analytically predicting the rate of degradation of the efficiency of the parametric amplifier which is caused by the detrimental PMD effect

Longitudinal transformation of nitrogen and carbon in the hyporheic zone of an N-rich stream: A combined modelling and field study

A combined modelling and field study approach was used to examine biogeochemical functioning of the hyporheic zone in two gravel bars in an N-rich fourth-order stream (River Hers, south-west France). Surfacewater and interstitial water were sampledmonthly (August 1994–January 1995), the latter in a network of 29 piezometers in the first gravel bar and 17 in the second. In both gravel bars, the hyporheic zone was created only by advected channelwater without any connectionwith groundwater. Longitudinal chemical profiles of Dissolved Organic Carbon (DOC), nitrate (NO3–N), ammonium (NH4–N) and Dissolved Oxygen (DO) were established for both gravel bars. Ambient and potential denitrification weremeasured in the laboratory during the same period using the acetylene inhibition technique. Factors limiting denitrification were also examined by testing the separate effects of nitrate or nitrate + carbon additions. A 1D reactive-transport model was used to simulate longitudinal transformation of nitrogen in the hyporheic zone, and to estimate the role of organic matter (DOC and POC) in the biogeochemical functioning of the hyporheic zone. Denitrification measurements with nitrate and nitrate + carbon additions both showed increased denitrification, suggesting that denitrification might not be C-limited at this site. Observations and model results showed the hyporheic zone to be a sink of DOC and nitrate, but DOC consumption appeared insufficient to explain nitrate depletion measured in the two gravel bars. Field data were better modelled when an additional DOC source from the POC fraction degraded by anaerobic respiration was included in the model