Real-time organic aerosol chemical speciation in the indoor environment using extractive electrospray ionization mass spectrometry

Understanding the sources and composition of organic aerosol (OA) in indoor environments requires rapid measurements, since many emissions and processes have short timescales. However, real-time molecular-level OA measurements have not been reported indoors. Here, we present quantitative measurements, at a time resolution of five seconds, of molecular ions corresponding to diverse aerosol-phase species, by applying extractive electrospray ionization mass spectrometry (EESI-MS) to indoor air analysis for the first time, as part of the highly instrumented HOMEChem field study. We demonstrate how the complex spectra of EESI-MS are screened in order to extract chemical information and investigate the possibility of interference from gas-phase semivolatile species. During experiments that simulated the Thanksgiving US holiday meal preparation, EESI-MS quantified multiple species, including fatty acids, carbohydrates, siloxanes, and phthalates. Intercomparisons with Aerosol Mass Spectrometer (AMS) and Scanning Mobility Particle Sizer suggest that EESI-MS quantified a large fraction of OA. Comparisons with FIGAERO-CIMS shows similar signal levels and good correlation, with a range of 100 for the relative sensitivities. Comparisons with SV-TAG for phthalates and with SV-TAG and AMS for total siloxanes also show strong correlation. EESI-MS observations can be used with gas-phase measurements to identify co-emitted gas- and aerosol-phase species, and this is demonstrated using complementary gas-phase PTR-MS observations.     

Changes in Lake Ontario Total Phosphorus Concentrations 1976–1978

An apparent decrease in total phosphorus concentrations of approximately 4.l μgP/L has been reported recently for the spring values of 1977 and 1978 in Lake Ontario. Investigation of the loading reduction for this period independent of sedimentation factors can account for only 10% of the change. The results indicate that changes in the sedimentation rate of total phosphorus during this period offer an explanation for the majority of the change in concentration.     

Interval based MINLP superstructure synthesis of mass exchange networks

A new simultaneous synthesis approach for mass exchange networks (MENs) is presented. The technique is adapted from the interval based mixed integer non-linear program (MINLP) superstructure (IBMS) synthesis of heat exchanger networks (HENs). The superstructure interval boundary compositions are defined by the supply and target compositions of either the rich or lean set of streams. Each rich and lean stream in the superstructure has the potential of exchanging mass with streams of opposite kind in each interval based on mass transfer feasibility. The model harnesses the strengths of the stagewise superstructure and the pinch technology methods for mass exchange network synthesis (MENS). The IBMS approach simultaneously trades-off the capital and operating costs for MENs. The superstructure composition interval defining approach introduced in this paper enforces the mixing of split streams at equal compositions, hence there is no need to include mixing equations in the model. Fixing the interval boundaries helps to eliminate the complexities involved in initialisations, thus the region of search for the optimum solution is reduced. The IBMS model is applied to MENS problems involving continuous contact and staged columns. It is also extended to problems involving multiple mass separating agents (MSAs) and regeneration. The results obtained compare well with those in the literature.     

Heterochromatin effects on the frequency and duration of LCR-mediated gene transcription

Organ transplantation is associated with an early bone loss that subsequently increases the risk of osteopenia and bone fractures. It is not known whether bone loss continues in long-term survivors, but persistent bone demineralization could further jeopardize an already diminished bone mass. To better define long-term bone status of kidney transplant recipients (KTR), we conducted cross-sectional and longitudinal evaluations of bone mineral density (BMD) in 70 KTR with a mean posttransplantation time of 8.1 years. BMD was determined by dual-energy X-ray absorptiometry and was repeated in 55 of the patients after a mean follow-up period of 22 +/- 5 months. Lumbar and femoral osteopenia, defined as a BMD lower than 2 standard deviations from mean value of sex- and age-matched controls, was present in 28.6% and 10.5% of patients, respectively. There was a significant negative correlation between cumulative prednisone dose and adjusted lumbar as well as femoral BMD (R = 0.45, P < 0.001 and R = 0.29, P < 0.05, respectively). Five patients had a vertebral BMD below a fracture threshold of 0.777 g/cm2. Vertebral fractures (VF) were found in four men and were associated with higher prednisone dosage (P < 0.05), larger cumulative prednisone dose (P < 0.05), and significantly lower BMD values. According to World Health Organization recent criteria for women, prevalences of lumbar and femoral osteopenia and lumbar and femoral osteoporosis in female patients reach 75%, 65%, 33%, and 10%, respectively. The longitudinal part of the study showed a persistent pathological lumbar demineralization process. Over the study period, BMD, expressed as a percentage of that of controls, decreased from 89 +/- 14% to 86 +/- 14% (P < 0.001). Annual change of bone mass was -1.7 +/- 2.8% per year. Accelerated vertebral bone loss (defined as a decrease of BMD, expressed as a percentage of that of controls, of more than 1% per year) was present in 56% of patients and was associated with higher prednisone dosage (P < 0.01). In conclusion, although VF are relatively infrequent in long-term survivors of renal transplantation, osteopenia is a frequent finding, and a substantial proportion of women present lumbar osteoporosis. An ongoing demineralization process of the spine is also demonstrated and probably contributes to long-term spinal osteoporosis incidence. Prednisone dosage remains the most constantly isolated risk factor.     

Inertia-friction welding of SiC-reinforced 8009 aluminium

Inertia-drive friction welding (IFRW) of an 8009 Al alloy (Al-8.5 Fe-1.7 Si-1.3 V, wt%) reinforced with 11 volume per cent SiC particles (8009/SiC/11_p) has been investigated. Inertia-drive friction welds were made with constant energy at two levels of axial force. The microstructures of the base material and the welds were characterized using optical and scanning electron microscopy, while the mechanical properties were evaluated using microhardness and tensile testing. Examination of weld sections revealed that the hot deformation experienced during welding produced a homogenized microstructure with a uniform distribution of SiC particles along the bond line. No evidence of a chemical reaction between the SiC and the matrix was found in any of the welds, but cracking of some of the larger SiC particles was observed in the base material as well as in the IFR welds. The average microhardness of the various heat-and-deformation affected zones (HDZs) of the welds did not vary greatly from that of the base material, and no weld induced weak regions were discerned. The room-temperature (RT) tensile strength of the IFR welds exceeded 90 per cent of the base material. The weld tensile specimens failed at the outer edge of the HDZ for all of the welds tested. The fracture surface of the 8009 matrix of tensile samples for both the base material and the welds exhibited a dimpled appearance indicating a ductile failure, while fracture through the SiC appeared to occur in a brittle fashion. IFRW has proven effective in joining 8009/SiC/11_p with little loss in RT hardness and tensile properties.     

A study of the effects of the location of flashing inception on maximum and minimum critical two-phase flow rates:: Part II: analysis and modelling

A general unified model is developed to predict one-component critical two-phase pipe flow. An extension of the Henry [Henry, R.E., 1970. The Two-Phase Critical Discharge of Initially Saturated or Subcooled Liquid. Nucl. Sci. Eng. 41, 336-342.] and Henry and Fauske [Henry, R.E., Fauske, H.K., 1970. The two-Phase critical Flow of One-Component Mixtures in Nozzles; Orifices and Short Tubes, ASME J. Heat Transfer, May 1970.] models to incorporate the effects of wall friction and the location of flashing inception is proposed. Modelling of the two-phase flow is accomplished by describing the evolution of the flow between the location of flashing inception and the exit (critical) plane. The model approximates the nonequilibrium phase change process via thermodynamic equilibrium paths. Included are the relative effects of varying the location of flashing inception, pipe geometry, fluid properties and length to diameter ratio. The model predicts that a range of critical mass fluxes exist and is bound by a maximum and minimum value for a given thermodynamic state. This range is more pronounced at lower subcooled stagnation states and can be attributed to the variation in the location of flashing inception. The model is based on the experimental study of critical two-phase flow rates of saturated and subcooled water through long tubes given in Part I of this work. In that study, the location of flashing inception was accurately controlled and adjusted through the use of a new device. The data obtained revealed that for fixed stagnation conditions, the maximum critical mass fluxes occurred with flashing inception located near the pipe exit; while minimum critical mass fluxes occurred with the flashing front located further upstream. The results of the present study, as well as available data since 1970 are compared with the model predictions. These data cover a wide range of conditions and include test section L/D ratios from 25 to 302 and a temperature and pressure range of 110-280°C and 0.16-6.9 Mpa, respectively. The predicted maximum and minimum critical mass fluxes show an excellent agreement with the range observed in the experimental data.     

Modeling the tensile properties in β-processed α/β Ti alloys

The development of a set of computational tools that permit microstructurally based predictions for the tensile properties of commercially important titanium alloys, such as Ti-6Al-4V, is a valuable step toward the accelerated maturation of materials. This paper will discuss the development of neural network models based on a Bayesian framework to predict the yield and ultimate tensile strengths of Ti-6Al-4V at room temperature. The development of such rules-based model requires the population of extensive databases, which in the present case are microstructurally based. The steps involved in database development include producing controlled variations of the microstructure using novel approaches to heat treatments, the use of standardized stereology protocols to characterize and quantify microstructural features rapidly, and mechanical testing of the heat-treated specimens. These databases have been used to train and test neural network models for prediction of tensile properties. In addition, these models have been used to identify the influence of individual microstructural features on the tensile properties, consequently guiding the efforts toward development of more robust mechanistically based models. Based on the neural network model, it is possible to investigate the influence of individual microstructural features on the tensile properties, and in certain cases these dependencies can point toward unrecognized phenomena. For example, the apparently unexpected trend of increase in tensile strength with increasing prior β-grain size has led to the determination of the pronounced role of the basketweave microstructure in strengthening these alloys, especially in case of larger prior β grains. This article is based on a presentation made in the symposium “Computational Aspects of Mechanical Properties of Materials,” which occurred at the 2005 TMS Annual Meeting, February 13–17, 2005, in San Francisco, CA, under the auspices of the MPMD-Computational Materials Science & Engineering (Jt. ASM-MSCTS) Committee.     

Chemical vapor deposition of amorphous ruthenium-phosphorus alloy films

Chemical vapor deposition growth of amorphous ruthenium-phosphorus films on SiO₂ containing ∼ 15% phosphorus is reported. cis-Ruthenium(II)dihydridotetrakis-(trimethylphosphine), cis-RuH₂(PMe₃)₄ (Me = CH₃) was used at growth temperatures ranging from 525 to 575 K. Both Ru and P are zero-valent. The films are metastable, becoming increasingly more polycrystalline upon annealing to 775 and 975 K. Surface studies illustrate that demethylation is quite efficient near 560 K. Precursor adsorption at 135 K or 210 K and heating reveal the precursor undergoes a complex decomposition process in which the hydride and trimethylphosphine ligands are lost at temperatures as low at 280 K. Phosphorus and its manner of incorporation appear responsible for the amorphous-like character. Molecular dynamics simulations are presented to suggest the local structure in the films and the causes for phosphorus stabilizing the amorphous phase.