Determination of the vapor pressures of select polychlorinated dibenzo-p-dioxins and dibenzofurans at 75-275 °C

Vapor pressures were determined for several polychlorinated dibenzo-p-dioxins (PCDDs) and polychlorinated dibenzofurans (PCDFs) at 75-275 °C, extending the available literature data to more relevant temperature regions and providing the first experimental data for 2,3,7-trichlorodibenzo-p-dioxin (2,3,7-TriCD). A modification of the effusion technique, based upon controlling the diffusion of the target compound and subsequent high resolution gas chromatography/low resolution mass spectrometry (HRGC/LRMS) analysis, was proven comparable to other accepted methods for determining the vapor pressures of semi-volatile organic compounds (SVOCs). Vapor pressures for octachlorodibenzo-p-dioxin (OCDD) and octachlorodibenzofuran (OCDF) were in excellent agreement with those reported in literature. The application of the current method for the vapor pressure determinations of eight polychlorinated dibenzo-p-dioxins/dibenzofurans (PCDDs/PCDFs) in the extended temperature range (up to 275 °C) is reported. The extension of the vapor pressures to such temperatures, unprecedented for the PCDDs/Fs, is important for vapor-particle partitioning modeling in regions relevant to PCDD/F formation and control. Estimates for the melting temperatures and enthalpies of sublimation and vaporization are also reported, the latter for which no experimentally determined values have been found in the literature. The use of the method to deliver reproducible, trace concentrations (ppt-ppb) of targets was applied to the calibration of the jet-REMPI/TOFMS as an online detector for low chlorinated PCDDs/Fs.     

Synthesis,structure and optical properties of x(CuO)/(1−x)Ni(OH)2 [x=0, 0.1 and 0.3] nanocomposites

The x(CuO)/(1−x)Ni(OH)₂ [x=0, 0.1 and 0.3] nanocomposites were prepared by the hydrothermal method in the presence of the surfactant polyethylenglycol-10000 (PEG-10000). X-ray diffraction (XRD), infrared (IR) spectroscopy, scanning electron microscopy (SEM) and transmission electron microscopy (TEM) were used to characterize the as-prepared samples. The increase of the CuO content led to the increase of the crystallite size of both, the β-Ni(OH)₂ and the CuO. The increase in the crystallite size greatly affects the band gap energy of the as-prepared nanocomposites. The band gap energies of the x(CuO)/(1−x)Ni(OH)₂ nanocomposites were estimated by UV–vis spectroscopic method. UV–vis spectroscopic results showed an apparent decrease in the direct band gap energies. The x(CuO)/(1−x)Ni(OH)₂ [x=0, 0.1 and 0.3] nanocomposites show low band gap energies compared to the Ni(OH)₂ bulk materials. The enhanced optical properties lead to their possible use in photocatalytic and photovoltaic applications.     

Extraction of Cadmium from Phosphoric Acid Media by Di(2‐ethylhexyl) Dithiophosphoric Acid

Di(2‐ethylhexyl) dithiophosphoric acid (D₂EHDTPA) was examined for cadmium removal from phosphoric acid solutions. High extraction performance was achieved. By means of slope and saturation methods, the stoichiometry of the complex was postulated. Both methods indicated the presence of anhydrous CdR₂ as being the metallic extracted complex, HR denoting the D₂EHDTPA molecule. The stripping of cadmium from the organic phase was ensured by aqueous solutions of HCl; quantitative stripping was achieved with either HCl (4 M) or an HCl‐NaCl mixture.     

Extraction of cadmium (II) from phosphoric acid media using the di(2-ethylhexyl)dithiophosphoric acid (D2EHDTPA): Feasibility of a continuous extraction-stripping process

The extraction of cadmium from phosphoric media has been studied. The D₂EHDTPA was used as extractant and dodecane as diluent. No third phase was observed in the investigated conditions.A continuous micro-pilot scale mixer-settler was successfully tested for both extraction and stripping. More than 99% extraction rate was obtained in steady-state conditions with a flow rate ratio Aqueous/Organic equal to 1.1. Continuous stripping was performed using HCl 4 M. More than 96% of the cadmium was stripped in one continuous mixer-settler stage for flow rate ratio equal to 0.7. Results were in good agreement with the predicted values based on the McCabe–Thiele method. Experimental mixer-settler stages behave as ideal ones (Murphree efficiency > 98%).An optimal flow sheet is proposed to purify the Wet Phosphoric Acid (WPA) and to recover a relatively concentrated cadmium solution (1 g L^? 1). Two ideal stages operating at phase ratio A/S equal to 5/1 are required for the extraction step leading to a very depleted raffinate (< 0.2 µg L^? 1). For the stripping step, six stages are required (S/A = 5/1). The recovered organic phase contains less than 2 µg L^? 1 and could be recycled in the extraction step.     

Persistent hyperinsulinemic hypoglycemia in the newborn and infants

Persistent hyperinsulinemic hypoglycaemia of infancy (PHHI) is the most frequent cause of hypoglycaemia in infancy. Clinical presentation is heterogeneous, with variable onset of hypoglycaemia and response to diazoxide, and presence of sporadic or familial forms. Underlying histopathological lesions can be focal or diffuse. Focal lesions are characterised by focal hyperplasia of pancreatic islet-like cells, whereas diffuse lesions implicate the whole pancreas. The distinction between the two forms is important because surgical treatment and genetic counselling are radically different. Focal lesions correspond to somatic defects which are totally cured by limited pancreatic resection, whereas diffuse lesions require a subtotal pancreatectomy exposing to high risk of diabetes mellitus. Diffuse lesions are due to functional abnormalities involving several genes and different transmission forms. Recessively inherited PHHI have been attributed to homozygote mutations for the beta-cell sulfonylurea receptor (SUR1) or the inward-rectifying potassium-channel (Kir6.2) genes. Dominantly inherited PHHI can implicate the glucokinase gene, particularly when PHHI is associated with diabetes, the glutamate dehydrogenase gene when hyperammonaemia is associated, or another locus.     

PCDD/F TEQ indicators and their mechanistic implications

Stack gas samples from two incinerator facilities with different operating conditions were investigated to understand how indicators of toxic equivalency (TEQ) from among the 210 polychlorinated dibenzo-p-dioxin/furan (PCDD/F) isomers varied. This effort was motivated by the need to find more easily monitored indicator compound(s) of TEQ and to reconcile the varying indicator compounds reported in the literature. The measured isomer patterns were compared with those expected from known formation mechanisms to identify the dominant mechanism(s) and explain why certain compounds are relevant TEQ indicators. Despite differences in the facility types and operating conditions, a common pattern was found for the highly chlorinated (4Cl and higher) PCDDs/Fs. A combination of chlorination/dechlorination reactions as the dominant formation mechanism for PCDF was consistent with the observed isomer patterns, whereas condensation reactions of phenolic precursors appeared to be responsible for PCDD formation. PCDF isomers, ratherthan the PCDD isomers, were more closely related to the TEQ measure, likely because the chlorination mechanism favors 2,3,7,8-Cl-substitution more than the phenol condensation mechanism. Unlike highly chlorinated PCDD/F isomer patterns, less chlorinated PCDD/F patterns (especially, mono- and di-CDF) were sensitive to operating conditions and facility type. Competing formation mechanisms were inferred from the variation of observed isomer distribution patterns; this sensitivity resulted in relatively low correlations of these isomers with PCDD/F TEQ values. This suggests that any use of the low-chlorinated compounds as TEQ indicators for online monitoring processes are likely best suited for plant-specific, rather than universal, applications. In addition to many of the highly chlorinated (penta-CDF, hexa-, and heptaCDD/F) isomers being identified as strong TEQ indicators, 1 of 12 (8%), 5 of 17 (29%), and 5 of 28 (18%) of the separable tri-CDD, tri-CDF, and tetra-CDF isomers, respectively, were identified as strong (R2 > 0.7) TEQ indicators in both incinerators.     

Real-time, on-line characterization of diesel generator air toxic emissions by resonance-enhanced multiphoton ionization time-of-flight mass spectrometry

The laser-based resonance-enhanced multiphoton ionization time-of-flight mass spectrometry (REMPI-TOFMS) technique has been applied to the exhaust gas stream of a diesel generator to measure, in real time, concentration levels of aromatic air toxics. Volatile organic compounds, as well as several polycyclic aromatic hydrocarbons were detected in the concentration range of 10-200 ppb in the steady-state diesel generator exhaust. The results were verified and compared with conventional extractive sampling and analytical techniques using gas chromatography/mass spectrometry (GC/MS). The high isomer selectivity of the REMPI-TOFMS instrument provided data for individual xylene isomers that are otherwise (partially) coeluting in standard GC/MS analyses. Good agreement was observed between results for volatile and semivolatile organic compounds obtained with REMPI-TOFMS and conventional extractive sampling. Transient events, such as cold start-ups of the diesel generator, resulted in sharp (less than 15 s) peak emissions that were, for benzene, up to a factor of 90 higher than the predominately constant concentrations observed during steady-state operation; warm restarts resulted in lower peak concentrations by a factor of 2.5. These fast transient emissions are only detectable using a real-time approach (1-s resolution) as demonstrated here using REMPI-TOFMS.     

Minimal Unroll Factor for Code Generation of Software Pipelining

We address the problem of generating compact code from software pipelined loops. Although software pipelining is a powerful technique to extract fine-grain parallelism, it generates lifetime intervals spanning multiple loop iterations. These intervals require periodic register allocation (also called variable expansion), which in turn yields a code generation challenge. We are looking for the minimal unrolling factor enabling the periodic register allocation of software pipelined kernels. This challenge is generally addressed through one of: (1) hardware support in the form of rotating register files, which solve the unrolling problem but are expensive in hardware; (2) register renaming by inserting register moves, which increase the number of operations in the loop, and may damage the schedule of the software pipeline and reduce throughput; (3) post-pass loop unrolling that does not compromise throughput but often leads to impractical code growth. The latter approach relies on the proof that MAXLIVE registers (maximal number of values simultaneously alive) are sufficient for periodic register allocation (Eisenbeis et al. in PACT ’95: Proceedings of the IFIP WG10.3 working conference on Parallel Architectures and Compilation Techniques, pages 264–267, Manchester, UK, 1995; Hendren et al. in CC ’92: Proceedings of the 4th International Conference on Compiler Construction, pages 176–191, London, UK, 1992). However, the best existing heuristic for controlling this code growth—modulo variable expansion (Lam in SIGPLAN Not 23(7):318–328, 1988)—may not apply the correct amount of loop unrolling to guarantee that MAXLIVE registers are enough, which may result in register spills Eisenbeis et al. in PACT ’95: Proceedings of the IFIP WG10.3 working conference on Parallel Architectures and Compilation Techniques, pages 264–267, Manchester, UK, 1995. This paper presents our research results on the open problem of minimal loop unrolling, allowing a software-only code generation that does not trade the optimality of the initiation interval (II) for the compactness of the generated code. Our novel idea is to use the remaining free registers after periodic register allocation to relax the constraints on register reuse. The problem of minimal loop unrolling arises either before or after software pipelining, either with a single or with multiple register types (classes). We provide a formal problem definition for each scenario, and we propose and study a dedicated algorithm for each problem. Our solutions are implemented within an industrial-strength compiler for a VLIW embedded processor from STMicroelectronics, and validated on multiple benchmarks suites.     

Feasibility and performance evaluation of a 6LoWPAN‐enabled platform for ubiquitous healthcare monitoring

Technology has revolutionized medical practices by enabling more convenient and non‐intrusive monitoring of patient's health, leading to next generation ubiquitous healthcare (u‐healthcare). The exploitation of the Internet protocol version 6 addressing space along with the miniaturization of electronic devices has fostered providing interoperability and connectivity of wearable sensor devices in wireless body area networks to the Internet of Things. In this paper, we propose to integrate the IPv6 over low power wireless personal area network (6LoWPAN) to the u‐healthcare monitoring system architecture. The main objective is to study the feasibility of the 6LoWPAN‐enabled platform in real‐world scenarios dealing with medical data. The performance evaluation of this platform is carried out initially through simulations using OMNet++ and then supported by an experimental study using sensor motes and a customized micro‐computing unit. Performance metrics such as throughput, end‐to‐end delay, packet error rate, and energy consumption are investigated under acute health conditions, where patient's health information has to be sent continuously and at maximum rate to the care provider. The obtained results show that the proposed 6LoWPAN solution fulfills the main quality of service requirements of u‐healthcare applications. Copyright © 2015 John Wiley & Sons, Ltd.