The loss of carbon dioxide from activated perbenzoate anions in the gas phase : Unimolecular rearrangement via epoxidation of the benzene ring

The unimolecular reactivities of a range of perbenzoate anions (X-C6H5CO3-), including the perbenzoate anion itself (X=H), nitroperbenzoates (X=para-, meta-, ortho-NO2), and methoxyperbenzoates (X=para-, meta-OCH3) were investigated in the gas phase by electrospray ionization tandem mass spectrometry. The collision-induced dissociation mass spectra of these compounds reveal product ions consistent with a major loss of carbon dioxide requiring unimolecular rearrangement of the perbenzoate anion prior to fragmentation. Isotopic labeling of the perbenzoate anion supports rearrangement via an initial nucleophilic aromatic substitution at the ortho carbon of the benzene ring, while data from substituted perbenzoates indicate that nucleophilic attack at the ipso carbon can be induced in the presence of electron-withdrawing moieties at the ortho and para positions. Electronic structure calculations carried out at the B3LYP/6311++G(d,p) level of theory reveal two competing reaction pathways for decarboxylation of perbenzoate anions via initial nucleophilic substitution at the ortho and ipso positions, respectively. Somewhat surprisingly, however, the computational data indicate that the reaction proceeds in both instances via epoxidation of the benzene ring with decarboxylation resulting-at least initially-in the formation of oxepin or benzene oxide anions rather than the energetically favored phenoxide anion. As such, this novel rearrangement of perbenzoate anions provides an intriguing new pathway for epoxidation of the usually inert benzene ring.

Coal seam gas water : potential hazards and exposure pathways in Queensland

The extraction of coal seam gas (CSG) produces large volumes of potentially contaminated water. It has raised concerns about the environmental health impacts of the co-produced CSG water. In this paper, we review CSG water contaminants and their potential health effects in the context of exposure pathways in Queensland’s CSG basins. The hazardous substances associated with CSG water in Queensland include fluoride, boron, lead and benzene. The exposure pathways for CSG water are: (1) water used for municipal purposes, (2) recreational water activities in rivers, (3) occupational exposures, (4) water extracted from contaminated aquifers, and; (5) indirect exposure through the food chain. We recommend mapping of exposure pathways into communities in CSG regions to determine the potentially exposed populations in Queensland. Future efforts to monitor chemicals of concern and consolidate them into a central database will build the necessary capability to undertake a much needed environmental health impact assessment.

The importance of use and end-of-life phases to the life cycle greenhouse gas (GHG) emissions of concrete : a review

Global climate change is one of the most significant environmental impacts at the moment. One central issue for the building and construction industry to address global climate change is the development of credible carbon labelling schemes for building materials. Various carbon labelling schemes have been developed for concrete due to its high contribution to global greenhouse gas (GHG) emissions. However, as most carbon labelling schemes adopt cradle-to-gate as system boundary, the credibility of the eco-label information may not be satisfactory because recent studies show that the use and end-of-life phases can have a significant impact on the life cycle GHG emissions of concrete in terms of carbonation, maintenance and rehabilitation, other indirect emissions, and recycling activities. A comprehensive review on the life cycle assessment of concrete is presented to holistically examine the importance of use and end-of-life phases to the life cycle GHG quantification of concrete. The recent published ISO 14067: Carbon footprint of products – requirements and guidelines for quantification and communication also mandates the use of cradle-to-grave to provide publicly available eco-label information when the use and end-of-life phases of concrete can be appropriately simulated. With the support of Building Information Modelling (BIM) and other simulation technologies, the contribution of use and end-of-life phases to the life cycle GHG emissions of concrete should not be overlooked in future studies.

The impact of a congestion charging exemption on the demand for new low‐emission vehicles

Numerous initiatives have been employed around the world in order to address rising greenhouse gas (GHG) emissions originating from the transport sector. These measures include: travel demand management (congestion‐charging), increased fuel taxes, alternative fuel subsidies and low‐emission vehicle (LEV) rebates. Incentivizing the purchase of LEVs has been one of the more prevalent approaches in attempting to tackle this global issue. LEVs, whilst having the advantage of lower emissions and, in some cases, more efficient fuel consumption, also bring the downsides of increased purchase cost, reduced convenience of vehicle fuelling, and operational uncertainty. To stimulate demand in the face of these challenges, various incentive‐based policies, such as toll exemptions, have been used by national and local governments to encourage the purchase of these types of vehicles. In order to address rising GHG emissions in Stockholm, and in line with the Swedish Government’s ambition to operate a fossil free fleet by 2030, a number of policies were implemented targeting the transport sector. Foremost amongst these was the combination of a congestion charge – initiated to discourage emissions‐intensive travel – and an exemption from this charge for some LEVs, established to encourage a transition towards a ‘green’ vehicle fleet. Although both policies shared the aim of reducing GHG emissions, the exemption for LEVs carried the risk of diminishing the effectiveness of the congestion charging scheme. As the number of vehicle owners choosing to transition to an eligible LEV increased, the congestion‐reduction effectiveness of the charging scheme weakened. In fact, policy makers quickly recognized this potential issue and consequently phased out the LEV exemption less than 18 months after its introduction (1). Several studies have investigated the demand for LEVs through stated‐preference (SP) surveys across multiple countries, including: Denmark (2), Germany (3, 4), UK (5), Canada (6), USA (7, 8) and Australia (9). Although each of these studies differed in approach, all involved SP surveys where differing characteristics between various types of vehicles, including LEVs, were presented to respondents and these respondents in turn made hypothetical decisions about which vehicle they would be most likely to purchase. Although these studies revealed a number of interesting findings in regards to the potential demand for LEVs, they relied on SP data. In contrast, this paper employs an approach where LEV choice is modelled by taking a retrospective view and by using revealed preference (RP) data. By examining the revealed preferences of vehicle owners in Stockholm, this study overcomes one of the principal limitations of SP data, namely that stated preferences may not in fact reflect individuals’ actual choices, such as when cost, time, and inconvenience factors are real rather than hypothetical. This paper’s RP approach involves modelling the characteristics of individuals who purchased new LEVs, whilst estimating the effect of the congestion charging exemption upon choice probabilities and subsequent aggregate demand. The paper contributes to the current literature by examining the effectiveness of a toll exemption under revealed preference conditions, and by assessing the total effect of the policy based on key indicators for policy makers, including: vehicle owner home location, commuting patterns, number of children, age, gender and income. Extended Abstract Submission for Kuhmo Nectar Conference 2014 2 The two main research questions motivating this study were:  Which individuals chose to purchase a new LEV in Stockholm in 2008?; and,  How did the congestion charging exemption affect the aggregate demand for new LEVs in Stockholm in 2008? In order to answer these research questions the analysis was split into two stages. Firstly, a multinomial logit (MNL) model was used to identify which demographic characteristics were most significantly related to the purchase of an LEV over a conventional vehicle. The three most significant variables were found to be: intra‐cordon residency (positive); commuting across the cordon (positive); and distance of residence from the cordon (negative). In order to estimate the effect of the exemption policy on vehicle purchase choice, the model included variables to control for geographic differences in preferences, based on the location of the vehicle owners’ homes and workplaces in relation to the congestion‐charging cordon boundary. These variables included one indicator representing commutes across the cordon and another indicator representing intra‐cordon residency. The effect of the exemption policy on the probability of purchasing LEVs was estimated in the second stage of the analysis by focusing on the groups of vehicle owners that were most likely to have been affected by the policy i.e. those commuting across the cordon boundary (in both directions). Given the inclusion of the indicator variable representing commutes across the cordon, it is assumed that the estimated coefficient of this variable captures the effect of the exemption policy on the utility of choosing to purchase an exempt LEV for these two groups of vehicle owners. The intra‐cordon residency indicator variable also controls for differences between the two groups, based upon direction of travel across the cordon boundary. A counter‐hypothesis to this assumption is that the coefficient of the variable representing commuting across the cordon boundary instead only captures geo‐demographic differences that lead to variations in LEV ownership across the different groups of vehicle owners in relation to the cordon boundary. In order to address this counter‐hypothesis, an additional analysis was performed on data from a city with a similar geodemographic pattern to Stockholm, Gothenburg ‐ Sweden’s second largest city. The results of this analysis provided evidence to support the argument that the coefficient of the variable representing commutes across the cordon was capturing the effect of the exemption policy. Based upon this framework, the predicted vehicle type shares were calculated using the estimated coefficients of the MNL model and compared with predicted vehicle type shares from a simulated scenario where the exemption policy was inactive. This simulated scenario was constructed by setting the coefficient for the variable representing commutes across the cordon boundary to zero for all observations to remove the utility benefit of the exemption policy. Overall, the procedure of this second stage of the analysis led to results showing that the exemption had a substantial effect upon the probability of purchasing and aggregate demand for exempt LEVs in Stockholm during 2008. By making use of unique evidence of revealed preferences of LEV owners, this study identifies the common characteristics of new LEV owners and estimates the effect of Stockholm's congestion charging exemption upon the demand for new LEVs during 2008. It was found that the variables that had the greatest effect upon the choice of purchasing an exempt LEV included intra‐cordon residency (positive), distance of home from the cordon (negative), and commuting across the cordon (positive). It was also determined that owners under the age of 30 years preferred non‐exempt LEVs (low CO2 LEVs), whilst those over the age of 30 years preferred electric vehicles. In terms of electric vehicles, it was apparent that those individuals living within the city had the highest propensity towards purchasing this vehicle type. A negative relationship between choosing an electric vehicle and the distance of an individuals’ residency from the cordon was also evident. Overall, the congestion charging exemption was found to have increased the share of exempt LEVs in Stockholm by 1.9%, with, as expected, a much stronger effect on those commuting across the boundary, with those living inside the cordon having a 13.1% increase, and those owners living outside the cordon having a 5.0% increase. This increase in demand corresponded to an additional 538 (+/‐ 93; 95% C.I.) new exempt LEVs purchased in Stockholm during 2008 (out of a total of 5 427; 9.9%). Policy makers can take note that an incentive‐based policy can increase the demand for LEVs and appears to be an appropriate approach to adopt when attempting to reduce transport emissions through encouraging a transition towards a ‘green’ vehicle fleet.

Resilience and opportunity : regions and the roll-out of Australia's greenhouse gas abatement programs. A manual for Queensland's NRM regions

Voluntary and compliance markets for forest carbon and other (emission avoidance and biosequestration) activities are growing internationally and across Australia. Queensland and its Natural Resource Management (NRM) regions have an opportunity to take a variety of actions to help guide these markets to secure multiple landscape benefits and to build landscape resilience in the face of climate change. As the national arrangements for offsets within Australia’s Clean Energy Package (CEP) and emissions trading environment emerge, Queensland’s regions can prepare themselves and their landholding communities to take advantage of these opportunities to deliver improved climate resilience in their regional landscapes.

Plasma-produced phase-pure cuprous oxide nanowires for methane gas sensing

Phase-selective synthesis of copper oxide nanowires is warranted by several applications, yet it remains challenging because of the narrow windows of the suitable temperature and precursor gas composition in thermal processes. Here, we report on the room-temperature synthesis of small-diameter, large-area, uniform, and phase-pure Cu2O nanowires by exposing copper films to a custom-designed low-pressure, thermally non-equilibrium, high-density (typically, the electron number density is in the range of 10 11-1013cm-3) inductively coupled plasmas. The mechanism of the plasma-enabled phase selectivity is proposed. The gas sensors based on the synthesized Cu2O nanowires feature fast response and recovery for the low-temperature (∼140°C) detection of methane gas in comparison with polycrystalline Cu2O thin film-based gas sensors. Specifically, at a methane concentration of 4%, the response and the recovery times of the Cu2O nanowire-based gas sensors are 125 and 147s, respectively. The Cu2O nanowire-based gas sensors have a potential for applications in the environmental monitoring, chemical industry, mining industry, and several other emerging areas.

Effect of atmospheric gas plasmas on cancer cell signaling

Cancer is one of the most life-threatening diseases with many forms still regarded as incurable. The conventional cancer treatments have unwanted side effects such as the death of normal cells. A therapy that can accurately target and effectively kill tumor cells could address the inadequacies of the available therapies. Atmospheric gas plasmas (AGP) that are able to specifically kill cancerous cells offer a promising alternative approach compared to conventional therapies. AGP have been shown to exploit tumor-specific genetic defects and a recent trial in mice has confirmed its antitumor effects. The mechanism by which the AGP act on tumor cells but not normal cells is not fully understood. A review of the current literature suggests that reactive oxygen species (ROS) generated by AGP induce death of cancer cells by impairing the function of intracellular regulatory factors. The majority of cancer cells are defective in tumor suppressors that interfere normal cell growth pathways. It appears that pro-oncogene or tumor suppressor-dependent regulation of antioxidant/or ROS signaling pathways may be involved in AGP-induced cancer cell death. The toxic effects of ROS are mitigated by normal cells by adjustment of their metabolic pathways. On the other hand, tumor cells are mostly defective in several regulatory signaling pathways which lead to the loss of metabolic balance within the cells and consequently, the regulation of cell growth. This review article evaluates the impact of AGP on the activation of cellular signaling and its importance for exploring mechanisms for safe and efficient anticancer therapies.

Atmospheric gas plasma–induced ROS production activates TNF-ASK1 pathway for the induction of melanoma cancer cell apoptosis

Atmospheric gas plasmas (AGPs) are able to selectively induce apoptosis in cancer cells, offering a promising alternative to conventional therapies that have unwanted side effects such as drug resistance and toxicity. However, the mechanism of AGP-induced cancer cell death is unknown. In this study, AGP is shown to up-regulate intracellular reactive oxygen species (ROS) levels and induce apoptosis in melanoma but not normal melanocyte cells. By screening genes involved in apoptosis, we identify tumor necrosis factor (TNF)-family members as the most differentially expressed cellular genes upon AGP treatment of melanoma cells. TNF receptor 1 (TNFR1) antagonist-neutralizing antibody specifically inhibits AGP-induced apoptosis signal, regulating apoptosis signal-regulating kinase 1 (ASK1) activity and subsequent ASK1-dependent apoptosis. Treatment of cells with intracellular ROS scavenger N-acetyl-l-cysteine also inhibits AGP-induced activation of ASK1, as well as apoptosis. Moreover, depletion of intracellular ASK1 reduces the level of AGP-induced oxidative stress and apoptosis. The evidence for TNF-signaling dependence of ASK1-mediated apoptosis suggests possible mechanisms for AGP activation and regulation of apoptosis-signaling pathways in tumor cells.

Feather-like He plasma plumes in surrounding N2 gas

Effects of surrounding gases on the propagation of room-temperature atmospheric-pressure plasma jets are reported. A highly unusual feather-like plasma plume is observed only when N2 is used as surrounding gas. The He concentration on the axis at the starting point of the feather-like plume is ∼0.85 of the maximum value and is independent on the He flow rates. High-speed optical imaging reveals that dim diffuse plasmas emerge just behind the bright head of the plasma bullet at the starting point of the feather-like plume. These results help tailoring surface exposure in emerging applications of plasma jets in medicine and nanotechnology.

Vertical graphene gas- and bio-sensors via catalyst-free, reactive plasma reforming of natural honey

A rapid reforming of natural honey exposed to reactive low-temperature Ar + H2 plasmas produced high-quality, ultra-thin vertical graphenes, without any metal catalyst or external heating. This transformation is only possible in the plasma and fails in similar thermal processes. The process is energy-efficient, environmentally benign, and is much cheaper than common synthesis methods based on purified hydrocarbon precursors. The graphenes retain the essential minerals of natural honey, feature reactive open edges and reliable gas- and bio-sensing performance.

Deterministic control of structural and optical properties of plasma-grown vertical graphene nanosheet networks via nitrogen gas variation

The effect of nitrogen on the growth of vertically oriented graphene nanosheets on catalyst-free silicon and glass substrates in a plasma-assisted process is studied. Different concentrations of nitrogen were found to act as versatile control knobs that could be used to tailor the length, number density and structural properties of the nanosheets. Nanosheets with different structural characteristics exhibit markedly different optical properties. The nanosheet samples were treated with a bovine serum albumin protein solution to investigate the effects of this variation on the optical properties for biosensing through confocal micro-Raman spectroscopy and UV-Vis spectrophotometry. © 2012 Optical Society of America.

Nanowire sensor response to reactive gas environment

The response of an originally developed catalytic sensor with a Nb2 O5 nanowire array at its outer surface to the varying density of O atoms is experimentally and numerically studied. This technique can be used to measure one order of magnitude lower densities of O atoms and achieve a stable linear response in a significantly broader pressure range compared to conventional catalytic probes with a flat surface. The nanostructured outer surface also acts as a thermal barrier against sensor overheating. This approach is generic and can be used for reactive species detection in other reactive gas environments.

Effect of gas pressure on electron field emission from carbon nanotube forests

This article quantifies the effect of the operating pressure of the H 2 + C 2H 4 gas mixture on the current density and threshold voltage of the electron emission from dense forests of multiwalled carbon nanotubes synthesized using thermal catalytic Chemical Vapor Deposition under near atmospheric pressure process conditions. The results suggest that in the pressure range of interest 400-700 Torr the field emission properties can be substantially improved by operating the process at lower gas pressures when the nanostructure aspect ratios are higher. The obtained threshold voltage ∼1.75 V/μm and the emission current densities ∼10 mA/cm 2 offer competitive advantages compared with the results reported by other authors. Copyright

Effect of input power and gas pressure on the roughening and selective etching of SiO2/Si surfaces in reactive plasmas

We report on the application low-temperature plasmas for roughening Si surfaces which is becoming increasingly important for a number of applications ranging from Si quantum dots to cell and protein attachment for devices such as "laboratory on a chip" and sensors. It is a requirement that Si surface roughening is scalable and is a single-step process. It is shown that the removal of naturally forming SiO2 can be used to assist in the roughening of the surface using a low-temperature plasma-based etching approach, similar to the commonly used in semiconductor micromanufacturing. It is demonstrated that the selectivity of SiO2 /Si etching can be easily controlled by tuning the plasma power, working gas pressure, and other discharge parameters. The achieved selectivity ranges from 0.4 to 25.2 thus providing an effective means for the control of surface roughness of Si during the oxide layer removal, which is required for many advance applications in bio- and nanotechnology.

Performance and gaseous and particle emissions from a liquefied petroleum gas (LPG) fumigated compression ignition engine

In this study, an LPG fumigation system was fitted to a Euro III compression ignition (CI) engine to explore its impact on performance, and gaseous and particulate emissions. LPG was introduced to the intake air stream (as a secondary fuel) by using a low pressure fuel injector situated upstream of the turbocharger. LPG substitutions were test mode dependent, but varied in the range of 14-29% by energy. The engine was tested over a 5 point test cycle using ultra low sulphur diesel (ULSD), and a low and high LPG substitution at each test mode. The results show that LPG fumigation coerces the combustion into pre-mixed mode, as increases in the peak combustion pressure (and the rate of pressure rise) were observed in most tests. The emissions results show decreases in nitric oxide (NO) and particulate matter (PM2.5) emissions; however, very significant increases in carbon monoxide (CO) and hydrocarbon (HC) emissions were observed. A more detailed investigation of the particulate emissions showed that the number of particles emitted was reduced with LPG fumigation at all test settings – apart from mode 6 of the ECE R49 test cycle. Furthermore, the particles emitted generally had a slightly larger median diameter with LPG fumigation, and had a smaller semi-volatile fraction relative to ULSD. Overall, the results show that with some modifications, LPG fumigation systems could be used to extend ULSD supplies without adversely impacting on engine performance and emissions.