A density functional theory study of CO2 and N2 adsorption on aluminium nitride single walled nanotubes

Strong binding of isolated carbon dioxide (CO2) on aluminium nitride (AlN) single walled nanotubes is verified using two different functionals. Two optimized configurations corresponding to physisorption and chemisorption are linked by a low energy barrier, such that the chemisorbed state is accessible and thermodynamically favored at low temperatures. In contrast, N2 is found only to form a physisorbed complex with the AlN nanotube, suggesting the potential application of aluminium nitride based materials for CO2 fixation. The effect of nanotube diameter on gas adsorption properties is also discussed. The diameter is found to have an important effect on the chemisorption of CO2, but has little effect on the physisorption of either CO2 or N2.

Carbon dioxide reforming of methane to produce synthesis gas over metal-supported catalysts: State of the art

Carbon dioxide reforming of methane produces synthesis gas with a low hydrogen to carbon monoxide ratio, which is desirable for many industrial synthesis processes. This reaction also has very important environmental implications since both methane and carbon dioxide contribute to the greenhouse effect. Converting these gases into a valuable feedstock may significantly reduce the atmospheric emissions of CO2 and CH4. In this paper, we present a comprehensive review on the thermodynamics, catalyst selection and activity, reaction mechanism, and kinetics of this important reaction. Recently, research has centered on the development of catalysts and the feasible applications of this reaction in industry. Group VIII metals supported on oxides are found to be effective for this reason. However, carbon deposition causing catalyst deactivation is the major problem inhibiting the industrial application of the CO2/CH4 reaction. Ni-based catalysts impregnated on certain supports show carbon-free operation and thus attract much attention. To develop an effective catalyst for CO2 reforming of CH4 and accelerate the commercial application of the reaction, the following are identified to be the most important areas for future work: (1) selection of metal and support and studying the effect of their interaction on catalyst activity; (2) the effect of different promoter on catalyst activity; (3) the reaction mechanism and kinetics; and (4) pilot reactor performance and scale-up operation.

Influence of nitrogen fertiliser application and timing on greenhouse gas emissions from a lychee (Litchi chinensis) orchard in humid subtropical Australia

Nitrous oxide emissions from intensive, fertilised agricultural systems have been identified as significant contributors to both Australia's and the global greenhouse gas (GHG) budget. This is expected to increase as rates of agriculture intensification and land use change accelerate to support population growth and food production. Limited data exists on N2O trace gas fluxes from subtropical or tropical tree cropping soils critical for the development of effective mitigation strategies.This study aimed to quantify GHG emissions over two consecutive years (March 2007 to March 2009) from a 30 year (lychee) orchard in the humid subtropical region of Australia. GHG fluxes were measured using a combination of high temporal resolution automated sampling and manually sampled chambers. No fertiliser was added to the plots during the 2007 measurement season. A split application of nitrogen fertiliser (urea) was added at the rate of 265kgNha-1 during the autumn and spring of 2008. Emissions of N2O were influenced by rainfall events and seasonal temperatures during 2007 and the fertilisation events in 2008. Annual N2O emissions from the lychee canopy increased from 1.7kgN2O-Nha-1yr-1 for 2007, to 7.6kgN2O-Nha-1yr-1 following fertiliser application in 2008. This represented an emission factor of 1.56%, corrected for background emissions. The timing of the split application was found to be critical to N2O emissions, with over twice as much lost following an application in spring (2.44%) compared to autumn (EF: 1.10%). This research suggests that avoiding fertiliser application during the hot and moist spring/summer period can reduce N2O losses without compromising yields.

Fuel consumption and gas emissions of an automatic transmission vehicle following simple eco-driving instructions on urban roads

Following eco-driving instructions can reduce fuel consumption between 5 to 20% on urban roads with manual cars. The majority of Australian cars have an automatic transmission gear-box. It is therefore of interest to verify whether current eco-driving instructions are e cient for such vehicles. In this pilot study, participants (N=13) drove an instrumented vehicle (Toyota Camry 2007) with an automatic transmission. Fuel consumption of the participants was compared before and after they received simple eco-driving instructions. Participants drove the same vehicle on the same urban route under similar tra c conditions. We found that participants drove at similar speeds during their baseline and eco-friendly drives, and reduced the level of their accelerations and decelerations during eco-driving. Fuel consumption decreased for the complete drive by 7%, but not on the motorway and inclined sections of the study. Gas emissions were estimated with the VT-micro model, and emissions of the studied pollutants (CO2, CO, NOX and HC) were reduced, but no di erence was observed for CO2 on the motorway and inclined sections. The di erence for the complete lap is 3% for CO2. We have found evidence showing that simple eco-driving instructions are e cient in the case of automatic transmission in an urban environment, but towards the lowest values of the spectrum of fuel consumption reduction from the di erent eco-driving studies.

Design and flight testing of an integrated solar powered UAV and WSN for remote gas sensing

This paper describes a generic and integrated solar powered remote Unmanned Air Vehicles (UAV) and Wireless Sensor Network (WSN) gas sensing system. The system uses a generic gas sensing system for CH4 and CO2 concentrations using metal oxide (MoX) and non-dispersive infrared sensors, and a new solar cell encapsulation method to power the UASs as well as a data management platform to store, analyse and share the information with operators and external users. The system was successfully field tested at ground and low altitudes, collecting, storing and transmitting data in real time to a central node for analysis and 3D mapping. The system can be used in a wide range of outdoor applications, especially in agriculture, bushfires, mining studies, opening the way to a ubiquitous low cost environmental monitoring. A video of the bench and flight test performed can be seen in the following link https://www.youtube.com/watch?v=Bwas7stYIxQ.

IMO technical and operational measures for reduction of emissions of greenhouse gas from ships : perspectives of Asian countries

International shipping is responsible for about 2.7% of the global emissions of CO2. In the absence of proper action, emissions from the maritime sector may grow by 150% to 250% by 2050, in comparison with the level of emissions in 2007. Against this backdrop, the International Maritime Organisation has introduced a mandatory Energy Efficiency Design Index (EEDI) for new ships and the Ship Energy Efficiency Management Plan (SEEMP) for all ships. Some Asian countries have voiced serious reservations about the newly adopted IMO regulations. They have suggested that imposing the same obligations on all countries, irrespective of their economic status, is a serious departure from the Principle of Common but Differentiated Responsibility, which has always been the cornerstone of international climate change law discourse. Against this backdrop, this article presents a brief overview of the technical and operational measures from the perspective of Asian countries.

Carbon dioxide capture and gas separation on B80 fullerene

Exploring advanced materials for efficient capture and separation of CO2 is important for CO2 reduction and fuel purification. In this study, we have carried out first-principles density functional theory calculations to investigate CO2, N2, CH4, and H2 adsorption on the amphoteric regioselective B80 fullerene. Based on our calculations, we find that CO2 molecules form strong interactions with the basic sites of the B80 by Lewis acid–base interactions, while there are only weak bindings between the other three gases (N2, CH4, and H2) and the B80 adsorbent. The study also provides insight into the reaction mechanism of capture and separation of CO2 using the electron deficient B80 fullerene.

The collision induced loss of carbon monoxide from deprotonated benzyl benzoate in the gas phase. An anionic 1,2-Wittig type rearrangement

The ion PhCO2--CHPh, upon collision activation, undergoes competitive losses of CO and CO2 of which the former process produces the base peak of the spectrum. Product ion and substituent effect (Hammett) studies indicate that PhCO2--CHPh cyclises to a deprotonated hydroxydiphenyloxirane which ring opens to PhCOCH(O-)Ph. This anion then undergoes an anionic 1,2-Wittig type rearrangement {through [PhCO- (PhCHO)]} to form Ph2CHO- and CO. The mechanism of the 1,2-rearrangement has been probed by an ab initio study [at MP4(SDTQ)/6-31++G(d,p) level] of the model system HCOCH2O- →; MeO- + CO The analogous system RCO2--CHPh (R = alkyl) similarly loses CO, and the migratory aptitudes of the alkyl R groups in this reaction are Bu′ > Me > Et ∼Pri). This trend correlates with the order of anion basicities (i.e. the order of ΔG○acid values of RH), supporting the operation of an anion migration process. The loss of CO2 from PhCO2--CHPh yields Ph2CH- as the anionic product: several mechanistic scenarios are possible, one of which involves an initial ipso nucleophilic substitution.

Concerted HO2 elimination from alpha-Aminoalkylperoxyl free radicals : Experimental and theoretical evidence from the gas phase NH2 center dot CHCO2- + O-2 reaction

We have investigated the gas-phase reaction of the alpha-aminoacetate (glycyl) radical anion (NH2(sic)CHCO2-) with O-2 using ion trap mass spectrometry, quantum chemistry, and statistical reaction rate theory. This radical is found to undergo a remarkably rapid reaction with O-2 to form the hydroperoxyl radical (HO2(sic)) and an even-electron imine (NHCHCO2-), with experiments and master equation simulations revealing that reaction proceeds at the ion molecule collision rate. This reaction is facilitated by a low-energy concerted HO2(sic) elimination mechanism in the NH2CH(OO(sic))CO2- peroxyl radical. These findings can explain the widely observed free-radical-mediated oxidation of simple amino acids to amides plus alpha-keto acids (their imine hydrolysis products). This work also suggests that imines will be the main intermediates in the atmospheric oxidation of primary and secondary amines, including amine carbon capture solvents such as 2-aminoethanol (commonly known as monoethanolamine, or MEA), in a process that avoids the ozone-promoting conversion of (sic)NO to (sic)NO2 commonly encountered in peroxyl radical chemistry.

Development of gas sensing technology for ground and airborne applications powered by solar energy : methodology and experimental results

Monitoring gases for environmental, industrial and agricultural fields is a demanding task that requires long periods of observation, large quantity of sensors, data management, high temporal and spatial resolution, long term stability, recalibration procedures, computational resources, and energy availability. Wireless Sensor Networks (WSNs) and Unmanned Aerial Vehicles (UAVs) are currently representing the best alternative to monitor large, remote, and difficult access areas, as these technologies have the possibility of carrying specialised gas sensing systems, and offer the possibility of geo-located and time stamp samples. However, these technologies are not fully functional for scientific and commercial applications as their development and availability is limited by a number of factors: the cost of sensors required to cover large areas, their stability over long periods, their power consumption, and the weight of the system to be used on small UAVs. Energy availability is a serious challenge when WSN are deployed in remote areas with difficult access to the grid, while small UAVs are limited by the energy in their reservoir tank or batteries. Another important challenge is the management of data produced by the sensor nodes, requiring large amount of resources to be stored, analysed and displayed after long periods of operation. In response to these challenges, this research proposes the following solutions aiming to improve the availability and development of these technologies for gas sensing monitoring: first, the integration of WSNs and UAVs for environmental gas sensing in order to monitor large volumes at ground and aerial levels with a minimum of sensor nodes for an effective 3D monitoring; second, the use of solar energy as a main power source to allow continuous monitoring; and lastly, the creation of a data management platform to store, analyse and share the information with operators and external users. The principal outcomes of this research are the creation of a gas sensing system suitable for monitoring any kind of gas, which has been installed and tested on CH4 and CO2 in a sensor network (WSN) and on a UAV. The use of the same gas sensing system in a WSN and a UAV reduces significantly the complexity and cost of the application as it allows: a) the standardisation of the signal acquisition and data processing, thereby reducing the required computational resources; b) the standardisation of calibration and operational procedures, reducing systematic errors and complexity; c) the reduction of the weight and energy consumption, leading to an improved power management and weight balance in the case of UAVs; d) the simplification of the sensor node architecture, which is easily replicated in all the nodes. I evaluated two different sensor modules by laboratory, bench, and field tests: a non-dispersive infrared module (NDIR) and a metal-oxide resistive nano-sensor module (MOX nano-sensor). The tests revealed advantages and disadvantages of the two modules when used for static nodes at the ground level and mobile nodes on-board a UAV. Commercial NDIR modules for CO2 have been successfully tested and evaluated in the WSN and on board of the UAV. Their advantage is the precision and stability, but their application is limited to a few gases. The advantages of the MOX nano-sensors are the small size, low weight, low power consumption and their sensitivity to a broad range of gases. However, selectivity is still a concern that needs to be addressed with further studies. An electronic board to interface sensors in a large range of resistivity was successfully designed, created and adapted to operate on ground nodes and on-board UAV. The WSN and UAV created were powered with solar energy in order to facilitate outdoor deployment, data collection and continuous monitoring over large and remote volumes. The gas sensing, solar power, transmission and data management systems of the WSN and UAV were fully evaluated by laboratory, bench and field testing. The methodology created to design, developed, integrate and test these systems was extensively described and experimentally validated. The sampling and transmission capabilities of the WSN and UAV were successfully tested in an emulated mission involving the detection and measurement of CO2 concentrations in a field coming from a contaminant source; the data collected during the mission was transmitted in real time to a central node for data analysis and 3D mapping of the target gas. The major outcome of this research is the accomplishment of the first flight mission, never reported before in the literature, of a solar powered UAV equipped with a CO2 sensing system in conjunction with a network of ground sensor nodes for an effective 3D monitoring of the target gas. A data management platform was created using an external internet server, which manages, stores, and shares the data collected in two web pages, showing statistics and static graph images for internal and external users as requested. The system was bench tested with real data produced by the sensor nodes and the architecture of the platform was widely described and illustrated in order to provide guidance and support on how to replicate the system. In conclusion, the overall results of the project provide guidance on how to create a gas sensing system integrating WSNs and UAVs, how to power the system with solar energy and manage the data produced by the sensor nodes. This system can be used in a wide range of outdoor applications, especially in agriculture, bushfires, mining studies, zoology, and botanical studies opening the way to an ubiquitous low cost environmental monitoring, which may help to decrease our carbon footprint and to improve the health of the planet.

Greenhouse gas emissions from sub-tropical agricultural soils after addition of organic by-products

As the cost of mineral fertilisers increases globally, organic soil amendments (OAs) from agricultural sources are increasingly being used as substitutes for nitrogen. However, the impact of OAs on the production of greenhouse gases (CO2 and N2O) is not well understood. A 60-day laboratory incubation experiment was conducted to investigate the impacts of applying OAs (equivalent to 296 kg N ha−1 on average) on N2O and CO2 emissions and soil properties of clay and sandy loam soils from sugar cane production. The experiment included 6 treatments, one being an un-amended (UN) control with addition of five OAs being raw mill mud (MM), composted mill mud (CM), high N compost (HC), rice husk biochar (RB), and raw mill mud plus rice husk biochar (MB). These OAs were incubated at 60, 75 and 90% water-filled pore space (WFPS) at 25°C with urea (equivalent to 200 kg N ha−1) added to the soils thirty days after the incubation commenced. Results showed WFPS did not influence CO2 emissions over the 60 days but the magnitude of emissions as a proportion of C applied was RB < CM < MB < HC CO2 and N2O emissions as a function of the dry matter and C/N ratio of the OAs, WFPS, and the soil CEC. Application of RB reduced N2O emissions by as much as 42-64% depending on WFPS. The reductions in both CO2 and N2O emissions after application of RB were due to a reduced bioavailability of C and not immobilisation of N. These findings show that the effect of OAs on soil GHG emissions can vary substantially depending on their chemical properties. OAs with a high availability of labile C and N can lead to elevated emissions of CO2 and N2O, while rice husk biochar showed potential in reducing overall soil GHG emissions.

Evolved gas analysis of coal-derived pyrite/marcasite

The products evolved during the thermal decomposition of the coal-derived pyrite/marcasite were studied using simultaneous thermogravimetry coupled with Fourier-transform infrared spectroscopy and mass spectrometry (TG-FTIR–MS) technique. The main gases and volatile products released during the thermal decomposition of the coal-derived pyrite/marcasite are water (H2O), carbon dioxide (CO2), and sulfur dioxide (SO2). The results showed that the evolved products obtained were mainly divided into two processes: (1) the main evolved product H2O is mainly released at below 300 °C; (2) under the temperature of 450–650 °C, the main evolved products are SO2 and small amount of CO2. It is worth mentioning that SO3 was not observed as a product as no peak was observed in the m/z = 80 curve. The chemical substance SO2 is present as the main gaseous product in the thermal decomposition for the sample. The coal-derived pyrite/marcasite is different from mineral pyrite in thermal decomposition temperature. The mass spectrometric analysis results are in good agreement with the infrared spectroscopic analysis of the evolved gases. These results give the evidence on the thermal decomposition products and make all explanations have the sufficient evidence. Therefore, TG–MS–IR is a powerful tool for the investigation of gas evolution from the thermal decomposition of materials.

Modelling CO2 adsorption and separation on experimentally-realized B40 fullerene

Searching for efficient solid sorbents for CO2 adsorption and separation is important for developing emergent carbon reduction and natural gas purification technology. This work, for the first time, has investigated the adsorption of CO2 on newly experimentally realized cage-like B40 fullerene (Zhai et al., 2014) based on density functional theory calculations. We find that the adsorption of CO2 on B40 fullerene involves a relatively large energy barrier (1.21 eV), however this can be greatly decreased to 0.35 eV by introducing an extra electron. A practical way to realize negatively charged B40 fullerene is then proposed by encapsulating a Li atom into the B40 fullerene (Li@B40). Li@B40 is found to be highly stable and can significantly enhance both the thermodynamics and kinetics of CO2 adsorption, while the adsorptions of N2, CH4 and H2 on the Li@B40 fullerene remain weak in comparison. Since B40 fullerene has been successfully synthesized in a most recent experiment, our results highlight a new promising material for CO2 capture and separation for future experimental validation.

A life cycle assessment approach to quantifying greenhouse gas emissions from land-use change for beef production in eastern Australia

In life cycle assessment studies, greenhouse gas (GHG) emissions from direct land-use change have been estimated to make a significant contribution to the global warming potential of agricultural products. However, these estimates have a high uncertainty due to the complexity of data requirements and difficulty in attribution of land-use change. This paper presents estimates of GHG emissions from direct land-use change from native woodland to grazing land for two beef production regions in eastern Australia, which were the subject of a multi-impact life cycle assessment study for premium beef production. Spatially- and temporally consistent datasets were derived for areas of forest cover and biomass carbon stocks using published remotely sensed tree-cover data and regionally applicable allometric equations consistent with Australia's national GHG inventory report. Standard life cycle assessment methodology was used to estimate GHG emissions and removals from direct land-use change attributed to beef production. For the northern-central New South Wales region of Australia estimates ranged from a net emission of 0.03 t CO2-e ha-1 year-1 to net removal of 0.12 t CO2-e ha-1 year-1 using low and high scenarios, respectively, for sequestration in regrowing forests. For the same period (1990-2010), the study region in southern-central Queensland was estimated to have net emissions from land-use change in the range of 0.45-0.25 t CO2-e ha-1 year-1. The difference between regions reflects continuation of higher rates of deforestation in Queensland until strict regulation in 2006 whereas native vegetation protection laws were introduced earlier in New South Wales. On the basis of liveweight produced at the farm-gate, emissions from direct land-use change for 1990-2010 were comparable in magnitude to those from other on-farm sources, which were dominated by enteric methane. However, calculation of land-use change impacts for the Queensland region for a period starting 2006, gave a range from net emissions of 0.11 t CO2-e ha-1 year-1 to net removals of 0.07 t CO2-e ha-1 year-1. This study demonstrated a method for deriving spatially- and temporally consistent datasets to improve estimates for direct land-use change impacts in life cycle assessment. It identified areas of uncertainty, including rates of sequestration in woody regrowth and impacts of land-use change on soil carbon stocks in grazed woodlands, but also showed the potential for direct land-use change to represent a net sink for GHG.

Mathematical modelling of gas production and compositional shift of a CSG (coal seam gas) field: Local model development

In this work we discuss the development of a mathematical model to predict the shift in gas composition observed over time from a producing CSG (coal seam gas) well, and investigate the effect that physical properties of the coal seam have on gas production. A detailed (local) one-dimensional, two-scale mathematical model of a coal seam has been developed. The model describes the competitive adsorption and desorption of three gas species (CH4, CO2 and N2) within a microscopic, porous coal matrix structure. The (diffusive) flux of these gases between the coal matrices (microscale) and a cleat network (macroscale) is accounted for in the model. The cleat network is modelled as a one-dimensional, volume averaged, porous domain that extends radially from a central well. Diffusive and advective transport of the gases occurs within the cleat network, which also contains liquid water that can be advectively transported. The water and gas phases are assumed to be immiscible. The driving force for the advection in the gas and liquid phases is taken to be a pressure gradient with capillarity also accounted for. In addition, the relative permeabilities of the water and gas phases are considered as functions of the degree of water saturation.