Modelling photochemical production of fine particulates in a toluene/NOx/water vapour system

This work investigates the computer modelling of the photochemical formation of smog products such as ozone and aerosol, in a system containing toluene, NOx and water vapour. In particular, the problem of modelling this process in the Commonwealth Scientific and Industrial Research Organization (CSIRO) smog chambers, which utilize outdoor exposure, is addressed. The primary requirement for such modelling is a knowledge of the photolytic rate coefficients. Photolytic rate coefficients of species other than N02 are often related to JNo2 (rate coefficient for the photolysis ofN02) by a simple factor, but for outdoor chambers, this method is prone to error as the diurnal profiles may not be similar in shape. Three methods for the calculation of diurnal JNo2 are investigated. The most suitable method for incorporation into a general model, is found to be one which determines the photolytic rate coefficients for N02, as well as several other species, from actinic flux, absorption cross section and quantum yields. A computer model was developed, based on this method, to calculate in-chamber photolysis rate coefficients for the CSIRO smog chambers, in which ex-chamber rate coefficients are adjusted by accounting for variation in light intensity by transmittance through the Teflon walls, albedo from the chamber floor and radiation attenuation due to clouds. The photochemical formation of secondary aerosol is investigated in a series of toluene-NOx experiments, which were performed in the CSIRO smog chambers. Three stages of aerosol formation, in plots of total particulate volume versus time, are identified: a delay period in which no significant mass of aerosol is formed, a regime of rapid aerosol formation (regime 1) and a second regime of slowed aerosol formation (regime 2). Two models are presented which were developed from the experimental data. One model is empirically based on observations of discrete stages of aerosol formation and readily allows aerosol growth profiles to be calculated. The second model is based on an adaptation of published toluene photooxidation mechanisms and provides some chemical information about the oxidation products. Both models compare favorably against the experimental data. The gross effects of precursor concentrations (toluene, NOx and H20) and ambient conditions (temperature, photolysis rate) on the formation of secondary aerosol are also investigated, primarily using the mechanism model. An increase in [NOx]o results in increased delay time, rate of aerosol formation in regime 1 and volume of aerosol formed in regime 1. This is due to increased formation of dinitrocresol and furanone products. An increase in toluene results in a decrease in the delay time and an increase in the rate of aerosol formation in regime 1, due to enhanced reactivity from the toluene products, such as the radicals from the photolysis of benzaldehyde. Water vapor has very little effect on the formation of aerosol volume, except that rates are slightly increased due to more OH radicals from reaction with 0(1D) from ozone photolysis. Increased temperature results in increased volume of aerosol formed in regime 1 (increased dinitrocresol formation), while increased photolysis rate results in increased rate of aerosol formation in regime 1. Both the rate and volume of aerosol formed in regime 2 are increased by increased temperature or photolysis rate. Both models indicate that the yield of secondary particulates from hydrocarbons (mass concentration aerosol formed/mass concentration hydrocarbon precursor) is proportional to the ratio [NOx]0/[hydrocarbon]0

Volcanic stratigraphy, alteration zoning, and vein paragenesis of the Sascha-Pelligrini low-sulphidation epithermal system, Santa Cruz, Argentina

The Sascha-Pelligrini low-sulphidation epithermal system is located on the western edge of the Deseado Massif, Santa Cruz Province, Argentina. Outcrop sampling has returned values of up to 160g/t gold and 796g/t silver, with Mirasol Resources and Coeur D.Alene Mines currently exploring the property. Detailed mapping of the volcanic stratigraphy has defined three units that comprise the middle Jurassic Chon Aike Formation and two units that comprise the upper Jurassic La Matilde Formation. The Chon Aike Formation consists of rhyodacite ignimbrites and tuffs, with the La Matilde Formation including rhyolite ash and lithic tuffs. The volcanic sequence is intruded by a large flow-banded rhyolite dome, with small, spatially restricted granodiorite dykes and sills cropping out across the study area. ASTER multispectral mineral mapping, combined with PIMA (Portable Infrared Mineral Analyser) and XRD (X-ray diffraction) analysis defines an alteration pattern that zones from laumontite-montmorillonite, to illite-pyritechlorite, followed by a quartz-illite-smectite-pyrite-adularia vein selvage. Supergene kaolinite and steam-heated acid-sulphate kaolinite-alunite-opal alteration horizons crop out along the Sascha Vein trend and Pelligrini respectively. Paragenetically, epithermal veining varies from chalcedonic to saccharoidal with minor bladed textures, colloform/crustiform-banded with visible electrum and acanthite, crustiform-banded grey chalcedonic to jasperoidal with fine pyrite, and crystalline comb quartz. Geothermometry of mineralised veins constrains formation temperatures from 174.8 to 205.1¡ÆC and correlates with the stability field for the interstratified illite-smectite vein selvage. Vein morphology, mineralogy and associated alteration are controlled by host rock rheology, permeability, and depth of the palaeo-water table. Mineralisation within ginguro banded veins resulted from fluctuating fluid pH associated with selenide-rich magmatic pulses, pressure release boiling and wall-rock silicate buffering. The study of the Sascha-Pelligrini epithermal system will form the basis for a deposit-specific model helping to clarify the current understanding of epithermal deposits, and may serve as a template for exploration of similar epithermal deposits throughout Santa Cruz.

Alteration of the foetal skin's response to Lipopolysaccharide (LPS) following Ureplasma Parvum exposure

Early preterm birth (<32 weeks) is associated with in utero infection and inflammation. We used an ovine model of in utero infection to ask if exposure to Ureaplasma serovar 3 (UP) modulated the response of the fetal skin to LPS.

Electrochemical and photochemical routes to semiconducting transition metal-tetracyanoquinodimethane coordination polymers

TCNQ·− radical anions (TCNQ = 7,7,8,8,-tetracyanoquinodimethane) form a wide range of semiconducting coordination polymers when coordinated to transition metals. Some such as CuTCNQ and AgTCNQ exhibit molecular switching and memory storage properties; others have intriguing magnetic properties and for example may behave as molecular magnets at low temperature. In this review, the electro- and photo-chemical synthesis and characterization of this important class of material is reviewed. In particular, the electrochemistry and the redox properties of TCNQ derivatives of coordination polymers based on Cu, Ag, Mn, Fe, Co, Ni, Zn and Cd transition metals are surveyed, with an emphasis on the mechanistic aspects of their electrochemical formation via nucleation–growth processes. Given that TCNQ is an extremely good electron acceptor, readily forming TCNQ•− and TCNQ2-, electrochemical reduction of TCNQ in the presence of a transition metal ion provides an ideal method for synthesis of metal-TCNQ materials by electrocrystallization from organic solvents and ionic liquids or solid-solid transformation using TCNQ modified electrodes from aqueous media containing transition metal electrolytes. The significance of the reversible formal potential (E0f) in these studies is discussed. The coupling of electrocrystallisation on electrode surfaces and microscopic characterization of the electrodeposited materials reveals a wide range of morphologies and phases which strongly influence their properties and applications. Since TCNQ also can be photo-reduced in the presence of suitable electron donors, analogous photochemical approaches to the synthesis of TCNQ-transition metal derivatives are available. The advantages of electrochemical and photochemical methods of synthesis relative to chemical synthesis are outlined.

An analysis for the causes of accidents of repair, maintenance, alteration and addition works in Hong Kong

This study unveils causes of accidents in repair, maintenance, alteration and addition (RMAA) work. RMAA work is playing an increasingly important role in developed societies, including Hong Kong. Safety problems associated with RMAA work in Hong Kong has reached an alarming level. In view of rapid expansion of the RMAA sector and rising proportion of accidents in the construction industry, there is a pressing need to investigate causes of RMAA accidents. Structured interviews were conducted with RMAA contractors to explore causes of accidents in the RMAA sector. A two-round Delphi method with 13 safety experts was subsequently employed to verify the interview findings and rank the relative degree of importance for various causes of accidents. Accidents happen in RMAA work due to intersection of reasons. One of the root causes of accidents in RMAA works is low safety awareness of RMAA workers; however, wider organizational and industrial factors are not negligible. This study sheds light on why accidents happen in the RMAA sector. Only when the factors leading to accidents are identified can effective measures be made.

Safety management in repair, maintenance, minor alteration, and addition works : knowledge management perspective

Safety of repair, maintenance, alteration, and addition (RMAA) works have long been neglected because RMAAworks are often minute and only last for a short period of time. With rising importance of the RMAA sector in many developed societies, safety of RMAA works has begun to draw attention. Many RMAA contracting companies are small- and medium-sized enterprises (SMEs) that do not have comprehensive safety management systems. Existing safety legislation and regulations for new construction sites are not fully applicable to RMAAworks. Instead of relying on explicit and well-established safety systems, tacit safety knowledge plays an extremely important role in RMAA projects. To improve safety of RMAAworks, safety knowledge should be better managed. However, safety knowledge is difficult to capture in RMAA works. This study aims to examine safety management practices of RMAA contracting companies to see how safety knowledge of RMAA projects is managed. Findings show that RMAA contracting companies undertaking large-scale RMAA projects have more initiatives of safety management. Safety management of small-scale RMAA works relies heavily on the motivation of site supervisors and self-regulation of workers. Better tacit knowledge management improves safety performance. To enhance safety capability of RMAA contracting companies, a knowledge sharing culture should be cultivated. The government should provide assistance to SMEs to implement proper safety management practices in small-sized projects. Potentials of applying computer software technology in RMAA projects to capture, store, and retrieve safety information should be explored. Employees should be motivated to share safety knowledge by giving proper recognition to those who are willing to share.

Safety climate and injury occurrence of repair, maintenance, minor alteration and addition works : a comparison of workers, supervisors and managers

Purpose The repair, maintenance, minor alteration and addition (RMAA) sector has been expanding in many developed cities. Safety problems of the RMAA sector have attracted the attention of many governments. This study has the objectives of comparing the level of safety climate of workers, supervisors and managers in the RMAA sector; and explaining/ predicting the impact of safety climate on injury occurrence of workers, supervisors and managers. Design/methodology/approach A questionnaire survey was administered to RMAA contracting companies in Hong Kong. Findings When comparing the safety climate perception of workers, supervisors and managers in the RMAA sector, the supervisors group had the lowest mean safety climate score. Results showed that a positive workforce safety attitude and acceptance of safety rules and regulations reduced the workers’ likelihood of having injuries. A reasonable production schedule led to a lower probability of supervisors being injured. Management commitment and effective safety management reduced the probability of managers being injured. Originality/value This study revealed variations of safety climate at the different levels in the organizational hierarchy and their varying influence on safety performance of the RMAA sector. Safety of RMAA works could be improved by promulgating specific safety measures at the different hierarchy levels.

Fatalities of repair, maintenance, minor alteration, and addition works in Hong Kong

This study examines fatalities of repair, maintenance, minor alteration, and addition (RMAA) works which occurred in Hong Kong between January 2000 and October 2011. A total of 119 RMAA fatalities were recorded. Particular emphasis was placed on fall from height accidents as they accounted for the vast majority of RMAA fatal accidents for the period. A cluster analysis was conducted on fall from height fatal cases. The cluster analysis clearly identified three groups of fall from height fatalities: (1) bamboo scaffolders aged between 25 and 34 who fell from external wall/facade in the beginning of weekdays; (2) miscellaneous workers aged between 45 and 54 who fell from other/unknown places in the end of weekdays; and (3) manual labour aged between 35 and 44 who fell at floor level/from floor openings in weekends. Unsafe process and improper procedures were the main unsafe condition leading to fatalities whereas safety belt not properly used was the main unsafe action leading to fatalities. Specific safety interventions were recommended for each of these groups to help avoid these fatalities.

Relationships between safety climate and safety performance of building repair, maintenance, minor alteration, and addition (RMAA) works

The importance of repair, maintenance, minor alteration, and addition (RMAA) works is increasing in many built societies. When the volume of RMAA works increases, the occurrence of RMAA accidents also increases. Safety of RMAA works deserves more attention; however, research in this important topic remains limited. Safety climate is considered a key factor that influences safety performance. The present study aims to determine the relationships between safety climate and safety performance of RMAA works, thereby offering recommendations on improving RMAA safety. Questionnaires were dispatched to private property management companies, maintenance sections of quasi-government developers and their subcontractors, RMAA sections of general contractors, small RMAA contractors, building services contractors and trade unions in Hong Kong. In total, data from 396 questionnaires were collected from RMAA workers. The sample was divided into two equal-sized sub-samples. On the first sub-sample SEM was used to test the model, which was validated on the second sub-sample. The model revealed a significant negative relationship between RMAA safety climate and incidence of self-reported near misses and injuries, and significant positive relationships between RMAA safety climate and safety participation and safety compliance respectively. Higher RMAA safety climate was positively associated with a lower incidence of self-reported near misses and injuries and higher levels of safety participation and safety compliance.

Determining safety climate factors in the repair, maintenance, minor alteration, and addition sector of Hong Kong

The accident record of the repair, maintenance, minor alteration, and addition (RMAA) sector has been alarmingly high; however, research in the RMAA sector remains limited. Unsafe behavior is considered one of the key causes of accidents. Thus, the organizational factors that influence individual safety behavior at work continue to be the focus of many studies. The safety climate, which reflects the true priority of safety in an organization, has drawn much attention. Safety climate measurement helps to identify areas for safety improvement. The current study aims to identify safety climate factors in the RMAA sector. A questionnaire survey was conducted in the RMAA sector in Hong Kong. Data were randomly split into the calibration and the validation samples. The RMAA safety climate factors were determined by exploratory factor analysis on the calibration sample. Three safety climate factors of the RMAA works were identified: (1) management commitment to occupational health and safety (OHS) and employee involvement, (2) application of safety rules and work practices, and; (3) responsibility for health and safety. Confirmatory factor analysis (CFA) was then conducted on the validation sample. The CFA model showed satisfactory goodness of fit, reliability, and validity. The suggested RMAA safety climate factors can be utilized by construction industry practitioners in developed economies to measure the safety climate of their RMAA projects, thereby enhancing the safety of RMAA works.

Strategies for improving safety performance of repair, maintenance, minor alteration and addition (RMAA) works

Purpose Managing and maintaining infrastructure assets are one of the indispensible tasks for many government agencies to preserve the nations' economic viability and social welfare. To reduce the expenditures over the life-cycle of an infrastructure asset and extend the period for which the asset performs effectively, proper repair and maintenance are essential. While repair, maintenance, minor alteration and addition (RMAA) sector is expanding in many developed cities, occurrences of fatalities and injuries in this sector are also soaring. The purposes of this paper are to identify and then evaluate the various strategies for improving the safety performance of RMAA works. Design/methodology/approach Semi-structured interviews and two rounds of Delphi survey were conducted for data collection. Findings Raising safety awareness of RMAA workers and selecting contractors with a good record of safety performance are the two most important strategies to improve the safety performance in this sector. Technology innovations and a pay-for-safety scheme are regarded as the two least important strategies. Originality/value The paper highlights possible ways to enhance safety of the rather under-explored RMAA sector in the construction industry.

A game theoretical approach to construction safety in the Repair, Maintenance, Alteration and Addition (RMAA) sector

Safety has long been a problem in the construction industry. Repair, maintenance, alteration and addition (RMAA) sector has emerged to play an important role in the construction industry. It accounted for 53% of the total construction market in Hong Kong in 2007. Safety performance of the RMAA words has been alarming. Statistics indicate that the percentage of fatal industrial accidents arising from RMAA work in Hong Kong was over 56% in 2006 while the remaining 44% was from new works. Effective safety measures to address the safety problems and improve safety performance of the RMAA sector are urgently needed. Unsafe behaviour has been attributed to one of the major causes of accidents. Traditional cost-benefit analysis of workers' safety behaviour seems to be inadequate. This paper proposes to adopt a game theoretical approach to analyse safety behaviour of RMAA workers. Game theory is concerned with the decision-making process in situations where outcomes depend upon choices made by one or more players. A game theoretical model between contractor and worker has been proffered. Mathematical analysis of this game model has been done and implications of the analysis have been discussed.

Interface control of surface photochemical reactivity in ultrathin epitaxial ferroelectric films

Asymmetrical electrical boundary conditions in (001)-oriented Pb(Zr 0.2TiO0.8)O3 (PZT) epitaxial ultrathin ferroelectric films are exploited to control surface photochemical reactivity determined by the sign of the surface polarization charge. It is shown that the preferential orientation of polarization in the as-grown PZT layer can be manipulated by choosing an appropriate type of bottom electrode material. PZT films deposited on the SrRuO3 electrodes exhibit preferential upward polarization (C) whilst the same films grown on the (La,Sr)CoO 3-electrodes are polarized downward (C-). Photochemical activity of the PZT surfaces with different surface polarization charges has been tested by studying deposition of silver nanoparticles from AgNO3 solution under UV irradiation. PZT surfaces with preferential C orientation possess a more active surface for metal reduction than their C- counterparts, evidenced by large differences in the concentration of deposited silver nanoparticles. This effect is attributed to band bending at the bottom interface which varies depending on the difference in work functions of PZT and electrode materials.

The effects of low degree alteration on Sm-Nd and U-Pb isotope systematics in Eoarchean basalts from the Doolena Gap and Warralong Greenstone belts, Pilbara Craton, Western Australia

This research led to the discovery of one of the best preserved remnants of the Earth's surficial environment 3.47 billion years ago. These ancient volcanic and sedimentary rocks contain original minerals and textures that are rare in rocks of this age. The research concentrated on chemical analysis of volcanic rocks to differentiate secondary alteration from the primary magmatic signature. This study contributes to our understanding of melting processes and geochemical reservoirs in the early Earth, which is vital for forward modelling of Earth's geodynamic evolution.