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.     

Crystallization behavior of oxyethylene/oxybutylene diblock and triblock copolymers

The crystallization behavior of poly(oxyethylene)-b-poly(oxybutylene) block copolymers with different compositions, morphologies and architectures (E_mB_n diblock copolymers and E_mB_nE_m, B_nE_mB_n triblock copolymers) were investigated and the effect of volume fraction and architecture on the crystallization temperature (T_c) in non-isothermal crystallization was determined. It is found that the E_mB_n diblock copolymers having long E blocks exhibit similar crystallization temperatures, irrespective of volume fraction and morphology, but for the block copolymers with shorter E blocks the crystallization temperature increases with both the volume fraction, φ_E, and the length, m, of the E block. Some block copolymers with extremely low T_c, which fall into the temperature range normally associated with homogenous nucleation, were chosen for time-resolved small-angle X-ray scattering (SAXS) and isothermal crystallization kinetics experiments. The results show that breakout crystallization occurs in all these block copolymers. Therefore, unlike E_mB_n/B_h blends, there is no obvious relationship between T_c and crystallization behavior in neat block copolymers and homogeneous nucleation does not definitely lead to confined crystallization. The values of χ_c/χ_ODT for all the block copolymers with hex and bcc morphology were also calculated. It is found that all the block copolymers have χ_c/χ_ODT<3, in agreement with the previously reported critical value and consistent with their breakout crystallization behavior.     

A Fully Continuous Supercritical Fluid Extraction System for Contaminated Soil

A fully continuous lab scale supercritical fluid extraction system has been designed, built and tested. The system continuously pumps carbon dioxide under supercritical conditions and soil slurry into a counter‐current contacting column. Delhi Loamy Sand, spiked with approximately 10 mg/g of naphthalene, was used as the testing soil. The soil slurry ranged from 0.0028 g dry soil per g slurry to 0.072 g/g. The operating temperature was 43°C and the operating pressure was 7.7 MPa. Near steady state, fully continuous flow was achieved with runs lasting as long as 2 h. All carbon dioxide samples contained measurable quantities of naphthalene and the measured mass transfer coefficients were as high as 4.6×10^?4 s^?1.     

Implications of variable fluid resistance caused by start-up flow in microfluidic networks

Electrical circuit analogies are often used to design microfluidic systems because they simplify device design, providing simple relationships between fluid flow rate, driving forces, and channel dimensions. However, such approximations often significantly overestimate flow rates in situations where start-up energy losses from establishing kinetic head are similar in magnitude to the energy required to overcome viscous shear stresses, as is often the case within complex microfluidic networks. These reduced flows can be more accurately predicted within an electrical analogy framework that accounts for the nonlinear flow resistance generated on the transient regime of start-up flow. In this work, standard flow resistance expressions are modified to account for such effects, and the onset of nonlinear resistance is predicted by a dimensionless parameter, $\xi = Re\frac{D}{L},$ which is dependent on the Reynolds number and the channel length. As a demonstration, variable fluid resistance is shown to dramatically affect the flow performance of common microfluidic units such as T-junctions and serpentine channels, and the change in performance is accurately predicted. Experimental and theoretical analysis of T-junctions further shows that variable flow resistance causes the ratio of flows through the junction to converge toward unity with respect to an increasing total flow rate. In addition, serpentine channels are shown to exaggerate these start-up effects, owing to compounded energetic demand associated with changing a flow’s direction. As a result, serpentine channels cause the ratio of flow rates exiting a T-junction to diverge from unity with respect to an increasing flow rate.     

An engineering study of the film embossing process

A mathematical model of the dynamics and heat transfer of the film embossing process has been developed. The thermal analysis around the preheat roll is determined from an unsteady, two-dimensional heat conduction equation along with appropriate boundary conditions by neglecting the curvature of the preheat roll and choosing a Lagrangian reference frame. The heat transfer occurring between the preheat roll and the embossing rolls is based on a one-dimensional analysis, including both convective and radiative effects. The deformation occurring in the nip region is analyzed for two different situations. For the case where the surface features are small in comparison with the film thickness, a modified one-dimennsional calendering analysis is given, accounting for the irregular geometry of the embossing roll surface. For the case where the polymer does not make complete contact with the surface of the engraved channel, the local deformation is determined by means of a simple one-dimensional cavity filling model. The required pressure distribution is determined by means of a simple one-dimensional cavity filling model, The required pressure distribution is determined by means of a conventional calendering analysis. The analysis for the case of a Newtonian and power-law model is presented in detail. The model yields qualitatively correct results and is computationally simple.     

A model for studying LCAT reaction: In vitro cholesterol esterification in pig ovarian follicular fluid

Phosphatidylcholine acyltransferase (lecithin:cholesterol acyltransferase or LCAT; EC 2.3.1.43) activity was found to be present in pig ovarian follicular fluid (POFF), in addition to pig serum (PS). The cholesterol esterification rate in both POFF and PS is linear with incubation time up to 2 hr. The mean absolute rate of POFF-cholesterol esterification was 8.1±0.4 nmoles per ml per hr approximately one-fourth of that in PS. However, the fractional rate (percent of labeled cholesterol esterified per hr) of POFF-cholesterol esterification was similar to that observed in PS. There was little variation of absolute rate of cholesterol esterification in the fluid obtained from different sizes of follicles. Fatty acid or triacylglycerol did not participate in the reaction of cholesterol esterification in POFF. No appreciable change in enzymatic activity was found from storing POFF at 4 C for periods of time up to 24 hr or at −70 C up to 2 months, but activity was lost thereafter. On the other hand, PS showed a much longer period of stability (5 days at 4 C and 9 months at −70 C). A discrepancy between the fatty acid composition of cholesteryl esters formed by the LCAT reaction and the fatty acid composition at the C-2 position of phosphatidylcholine led us to propose a two-step mechanism for the LCAT reaction. It is concluded that the LCAT of POFF, as well as that of plasma, is specific for individual fatty acids rather than for the fatty acid composition of phosphatidylcholine. The fatty acid concentration of lysophosphatidylcholine decreased during prolonged incubation times (6 to 21 hr) suggesting that the increased lysophosphatidylcholine formed as a product of the LCAT reaction may be reused as substrate for the LCAT reaction or for hydrolysis by lysophosphatidylcholine hydrolase. Presented at the AOCS Meeting, New York, May 1977.     

Ventilation of a dead-end duct having a porous barrier

Analytic expressions for the flow and pressure in a dead-end duct which has loss of fluid through a porous wall are developed. The presence of an obstruction or auxiliary fan at the end of the duct is included. In either case there is a maximum permissible length of duct. As the duct length approaches this maximum, the main supply fan power and flow increase dramatically. There is no recirculation within the duct when there is an obstruction at the end of the duct. If an auxiliary fan is used, there is always recirculation. However the use of an auxiliary fan can yield major savings in total power requirements.     

Effects of Al:Si and (Al + Na):Si ratios on the properties of the international simple glass,part II: Structure

High-alumina containing high-level waste (HLW) will be vitrified at the Waste Treatment Plant at the Hanford Site. The resulting glasses, high in alumina, will have distinct composition-structure-property (C-S-P) relationships compared to previously studied HLW glasses. These C-S-P relationships determine the processability and product durability of glasses and therefore must be understood. The main purpose of this study is to understand the detailed structural changes caused by Al:Si and (Al + Na):Si substitutions in a simplified nuclear waste model glass (ISG, international simple glass) by combining experimental structural characterizations and molecular dynamics (MD) simulations. The structures of these two series of glasses were characterized by neutron total scattering and ²⁷Al, ²³Na, ²⁹Si, and ¹¹B solid-state nuclear magnetic resonance (NMR) spectroscopy. Additionally, MD simulations were used to generate atomistic structural models of the borosilicate glasses and simulation results were validated by the experimental structural data. Short-range (eg, bond distance, coordination number, etc) and medium-range (eg, oxygen speciation, network connectivity, polyhedral linkages) structural features of the borosilicate glasses were systematically investigated as a function of the degree of substitution. The results show that bond distance and coordination number of the cation-oxygen pairs are relatively insensitive to Al:Si and (Al + Na):Si substitutions with the exception of the B-O pair. Additionally, the Al:Si substitution results in an increase in tri-bridging oxygen species, whereas (Al + Na):Si substitution creates nonbridging oxygen species. Charge compensator preferences were found for Si-[NBO] (Na⁺), ^[3]B-[NBO] (Na⁺), ^[4]B (mostly Ca²⁺), ^[4]Al (nearly equally split Na⁺ and Ca²⁺), and ^[6]Zr (mostly Ca²⁺). The network former-BO-network former linkages preferences were also tabulated; Si-O-Al and Al-O-Al were preferred at the expense of lower Si-O-^[3]B and ^[3]B-O-^[3]B linkages. These results provide insights on the structural origins of property changes such as glass-transition temperature caused by the substitutions, providing a basis for future improvements of theoretical and computer simulation models.     

Development of Habitat Suitability Criteria and In‐Stream Habitat Assessment for the Benthic Cyanobacteria Phormidium

Global demand for freshwater has led to unprecedented levels of water abstraction from riverine systems. This has resulted in large alterations in natural river flows. The deleterious impacts of reduced flows on fish and macroinvertebrate abundances have been thoroughly investigated; in contrast, there is a limited understanding of the potential for changes in the abundance of nuisance benthic algal/cyanobacterial blooms. In New Zealand, Phormidium sp. blooms are common in numerous rivers during summer low flows. In this study, an in‐stream habitat assessment is used to examine the relationship between Phormidium habitat availability and reducing flows. Over 650 observations of Phormidium mats, from seven sites (Hutt River, lower North Island, New Zealand), were used to construct habitat suitability curves for depth, velocity and substrate. Preference curves were fitted using both the ‘forage ratio’ and ‘quantile regression’ methods. Phormidium growth, observed at all seven sites, increased significantly from upstream (uppermost site, 5.2% mat cover) to downstream (63.5%). The habitat suitability curves revealed Phormidium had a large tolerance to velocity, depth and substrate type. Consequently, decreases in flow had only negligible effects on available Phormidium habitat. During periods of stable flow, Phormidium abundance positively correlated with increased nitrogen concentrations, potentially explaining the large variation in Phormidium cover from upstream to downstream. Quantile regression generated habitat suitability criteria were a more accurate predictor of available Phormidium habitat than the forage ratio criteria. Copyright © 2013 John Wiley & Sons, Ltd.