Microbial reductive transformation of pentachloronitrobenzene under methanogenic conditions

The reductive transformation of pentachloronitrobenzene (PCNB), an organochlorine fungicide, was investigated with a mixed, methanogenic culture developed from a contaminated estuarine sediment. Batch assays performed with this enrichment culture resulted in the biotransformation of PCNB to pentachloroaniline (PCA), which was then sequentially dechlorinated as follows: PCA --> 2,3,4,5- and 2,3,5,6-tetrachloroaniline (TeCA) --> 2,4,5- and 2,3,5-trichloroaniline (TrCA) --> 2,4-, 2,5-, and 3,5-dichloroaniline (DCA) --> 3- and 4-chloroaniline (CA) (low levels). Glucose fermentation, methanogenesis, and dechlorination were not inhibited at an initial PCNB concentration up to 40 microM, which is 27 times higher than its aqueous solubility. The addition of 25 mM 2-bromoethanesulfonate (BES) to the PCNB-amended culture resulted in the complete inhibition of methanogenesis, but the biotransformation of PCNB to PCA and its sequential dechlorination pathway were not affected. The addition of sodium azide (200 mg/L) to the PCNB-amended culture resulted in complete inhibition of methanogenesis, but did not inhibit the transformation of PCNB to PCA; however, PCA dechlorination was not observed. PCNB was also abiotically transformed to PCA in autoclaved culture media but at much lower rates as compared to the biotic assays. In contrast, the rate of PCNB to PCA transformation in autoclaved culture controls was similar to the rates observed in the azide-amended culture and the active enrichment culture, indicating that biotically derived reductants facilitated the observed transformation of PCNB to PCA. Dechlorination of PCA was not observed in any of the abiotic controls. These findings have significant environmental implications in terms of the fate and transport of PCNB, PCA, and its dechlorination products in subsurface systems.     

Adsorption of organophosphates into microporous and mesoporous NaX zeolites and subsequent chemistry

Due to the neurotoxicity of organophosphate (OP) pesticides and nerve agents synthesized as military or terror agents, their safe destruction and disposal is of considerable current importance. A representative OP, trimethyl phosphate (TMP), was adsorbed onto NaX zeolite, two mesoporous modifications, and a low-silica X zeolite. The nucleophilic chemical reactions of TMP with the zeolites were investigated by solid-state 13C and 31P nuclear magnetic resonance (NMR) and the solvent extracts by 1H, 13C, and 31P NMR. Nucleophilic substitution and subsequent hydrolysis reaction schemes are proposed. All of the zeolites have similar TMP decomposition yields, supporting the hypothesis that slow or incomplete diffusion of TMP in the microporous zeolite regions limits TMP decomposition.     

Infrastructure,automation and model-based operation strategy in a stand-alone hydrolytic solar-hydrogen production unit

An autonomous power system that exploits solar energy for the production of hydrogen through water electrolysis is fully assessed in terms of system implementation and optimal operating strategy. A 10 kW_p photovoltaic array supplies energy to a PEM electrolyzer rated at 6.9 kW_p. In order to maintain a smooth operation regardless of the inherent weather fluctuations, a 1000 Ah/24 V lead–acid accumulator stores energy excess and provides it when needed. The monitoring and control of the system is implemented through a Supervisory Control and Data Acquisition system (SCADA), while the interactions between electrical and chemical subsystems are addressed by a complete automation infrastructure. The mathematical models of each subsystem are validated based on real operational data and a model-based power management strategy is proposed and assessed through a parameter sensitivity analysis. Further on, an off-line optimization framework is evaluated regarding the optimal operation of the system in two diverse, but representative time periods. The optimal parameters are identified and their effect on hydrogen production and accumulator utilization is reported.     

Individual Particle Morphology and Acidity

The morphological characterization of particles during the Pittsburgh Air Quality Study (PAQS) suggests that particle shape and physical state depends on their acidity. The aerosol shape parameters measured by Computer-Controlled Scanning Electron Microscopy (CCSEM) are statistically different in periods when atmospheric particles are neutral and when they are acidic. High concentrations of particles smaller than 500 nm with high sulfur content and liquid appearance or signs of a previous liquid state before partial or total recrystallization are present on filters collected in days with high aerosol acidity. By contrast, in winter and summer periods in which the aerosol was neutral, the shape parameter values are similar and suggest that the particles have been dried out. These direct observations support the hypothesis that during summer acidic periods in the Eastern United States the particles may contain some water even at low relative humidity both in the atmosphere and on filters.     

Diffusion-Limited Versus Quasi-Equilibrium Aerosol Growth

Condensation of gas-phase material onto particulate matter is the predominant route by which atmospheric aerosols evolve. The traditional approach to representing formation of secondary organic aerosols (SOAs) is to assume instantaneous partitioning equilibrium of semivolatile organic compounds between gas and particle phases. Growth occurs as the vapor concentration of the species increases owing to gas-phase chemistry. The fundamental mathematical basis of such a condensation growth mechanism (quasi-equilibrium growth) has been lacking. Analytical solutions for the evolution of an organic aerosol size distribution undergoing quasi-equilibrium growth and irreversible diffusion-limited growth are obtained for open and closed systems. The quasi-equilibrium growth emerges as a limiting case for semivolatile species condensation when the rate of change of the ambient vapor concentration is slow compared with the rate of establishment of local gas-aerosol equilibrium. The results suggest that the growth mechanism in a particular situation might be inferred from the characteristics of the evolving size distribution. In certain conditions, a bimodal size distribution can occur during the condensation of a single species on an initially unimodal distribution.

Copyright 2012 American Association for Aerosol Research     

Local and Regional Secondary Organic Aerosol: Insights from a Year of Semi-Continuous Carbon Measurements at Pittsburgh

We present Scanning Mobility CCN Analysis (SMCA) as a novel method for obtaining rapid measurements of size-resolved cloud condensation nuclei (CCN) distributions and activation kinetics. SMCA involves sampling the monodisperse outlet stream of a Differential Mobility Analyzer (DMA) operated in scanning voltage mode concurrently with CCN and condensation particle counters. By applying the same inversion algorithm as used for obtaining size distributions with a scanning mobility particle sizer (SMPS), CCN concentration and activated droplet size are obtained as a function of mobility size over the timescale of an SMPS scan (typically 60–120 s). Methods to account for multiple charging, particle non-sphericity, and limited counting statistics are presented. SMCA is demonstrated using commercial SMPS and CFSTGC instruments with the manufacturer-provided control software. The method is evaluated for activation of both laboratory aerosol and ambient aerosol obtained during the 2004 NEAQS-ITCT2k4 field campaign. It is shown that SMCA reproduces the results obtained with a DMA operating in voltage “stepping” mode.     

Prediction of Coating Properties of Thermally Sprayed WC–Co on Complex Geometries

This work outlines the development of an analytical software tool that enables the prediction of various coating properties on any given sprayable geometry. The prediction is achieved by analyzing the input computer-aided design geometry and by correlating the resulting kinematic conditions with experimental measurements. The results of the developed tool have been validated experimentally using HVOF-sprayed WC-17Co coatings. Specifically, coating thickness, microhardness, WC vol.% and specific sliding wear rate are examined and their values are predicted for the case of the external spray of a rotor-like model.     

Protection of volatile esters and terpenes during storage of a white wine and a model wine medium by a mixture of N-acetyl-cysteine and caffeic acid

A mixture of N-acetyl-cysteine + caffeic acid, at 10 + 30 mg/L respectively, was tested as inhibitor of the decrease of volatile esters and terpenes during storage of Debina white wine. Moreover, the inhibition of the decrease of isoamyl acetate, ethyl hexanoate and linalool in a model wine medium by the mixture, at 1.25 + 3.75 to 10 + 30 mg/L, was tested. Several volatiles, such as isoamyl acetate, ethyl hexanoate, ethyl octanoate, ethyl decanoate and linalool, decreased during wine storage. The mixture of N-acetyl-cysteine + caffeic acid restricted the decrease of these volatiles to a large extent. In the model medium, the mixture inhibited the decrease of the three volatiles in a dose dependent manner. It was active at any concentration tested. The present results indicate that mixture of N-acetyl-cysteine + caffeic acid, containing each compound at low concentration, may be taken into account as an effective inhibitor of the disappearance of volatile aroma in wines.     

Improvement of oleuropein extractability by optimising steam blanching process as pre-treatment of olive leaf extraction via response surface methodology

Impact of steam, hot water blanching and UV-C irradiation as pre-treatments on extraction of oleuropein and related biophenols from olive leaves (OLs), was investigated. Moreover, particle size effect of olive leaves and steam blanching duration were selected as independent variables to optimise steam blanching process in terms of oleuropein content (OC) and antioxidant activity (AC) of ethanolic extracts, by using response surface methodology. Optimum conditions for OC and AC were 10 min steam blanching of 20–11 and 3–1 mm olive leaf fraction, respectively. Depending on the extraction procedure, at optimum conditions of steaming the results indicate that steam blanching of OL prior to extraction can significantly increase oleuropein yield from 25 to 35 times compared to non-steam blanched sample, whereas the antioxidant activity increased from 4 to 13 times. No significant UV-C effect was observed in OC and AC, while hot water blanched samples showed significantly higher oleuropein yields and antioxidant activity compared to untreated samples.     

Unveiling the underlying relationships over a network for monitoring purposes

Nowadays traffic monitoring and analysis tools provide poor information about traffic volume without giving any clear view of what the hidden rules and relationships that govern these flows are. Since the majority of flows is generated by services (web browsing, email, p2p) and most of these applications are dependent on many network assets (servers and databases) we should discover the underlying relationships of every application. We present a technique that discovers the hidden relationships among components of a network that consist of parts of specific applications. From time information and flow attributes, such as IP addresses and service ports, our method using a novel hybrid genetic algorithm produces a small set of fuzzy rules that can reveal the underlying relationships over a network without any guidance. These dependencies build a service graph which can become a useful tool for fault localization, monitoring service performance, designing changes and anomaly detection. Copyright © 2009 John Wiley & Sons, Ltd.