Spatiotemporal modelling in estimation of nitrous oxide emissions from soil

Nitrous oxide is a major greenhouse gas emission. The aim of this research was to develop and apply statistical models to characterize the complex spatial and temporal variation in nitrous oxide emissions from soils under different land use conditions. This is critical when developing site-specific management plans to reduce nitrous oxide emissions. These studies can improve predictions and increase our understanding of environmental factors that influence nitrous oxide emissions. They also help to identify areas for future research, which can further improve the prediction of nitrous oxide in practice.

Proposed REDD+ project for the Sundarbans : legal and institutional issues

Sundarbans, a Ramsar and World Heritage site, is the largest single block of tidal halophytic mangrove forest in the world covering parts of Bangladesh and India. Natural mangroves were very common along the entire coast of Bangladesh. However, all other natural mangrove forests, including the Chakaria Sundarbans with 21,000 hectares of mangrove, have been cleared for shrimp cultivation. Against this backdrop, the Forest Department of Bangladesh has developed project design documents for a project called ‘Collaborative REDD+ Improved Forest Management (IFM) Sundarbans Project’ (CRISP) to save the only remaining natural mangrove forest of the country. This project, involving conservation of 412,000 ha of natural mangrove forests, is expected to generate, over a 30-year period, a total emissions reduction of about 6.4 million tons of CO2. However, the successful implementation of this project involves a number of critical legal and institutional issues. It may involve complex legal issues such as forest ownership, forest use rights, rights of local people and carbon rights. It may also involve institutional reforms. Ensuring good governance of the proposed project is very vital considering the failure of the Asian Development Bank (ADB) funded and Bangladesh Forest Department managed ‘Sundarbans Biodiversity Conservation Project’. Considering this previous experience, this paper suggests that a comprehensive legal and institutional review and reform is needed for the successful implementation of the proposed CRISP project. This paper argues that without ensuring local people’s rights and their participation, no project can be successful in the Sundarbans. Moreover, corruption of local and international officials may be a serious hurdle in the successful implementation of the project.

An in situ high pressure FT-IR study of CO2/H2 interactions with model ZnO/SiO2, Cu/SiO2 and Cu/ZnO/SiO2 methanol synthesis catalysts

In situ FT-IR spectroscopy allows the methanol synthesis reaction to be investigated under actual industrial conditions of 503 K and 10 MPa. On Cu/SiO2 catalyst formate species were initially formed which were subsequently hydrogenated to methanol. During the reaction a steady state concentration of formate species persisted on the copper. Additionally, a small quantity of gaseous methane was produced. In contrast, the reaction of CO2 and H2 on ZnO/SiO2 catalyst only resulted in the formation of zinc formate species: no methanol was detected. The interaction of CO2 and H2 with Cu/ZnO/SiO2 catalyst gave formate species on both copper and zinc oxide. Methanol was again formed by the hydrogenation of copper formate species. Steady-state concentrations of copper formate existed under actual industrial reaction conditions, and copper formate is the pivotal intermediate for methanol synthesis. Collation of these results with previous data on copper-based methanol synthesis catalysts allowed the formulation of a reaction mechanism

Infrared study of CO, CO2, H2 and H2O interactions on potassium-promoted reduced and oxidised silica-supported copper catalysts

FTIR spectra are reported of CO, CO2, H2 and H2O on silica-supported potassium, copper and potassium-copper catalysts. Adsorption of CO on a potassium/silica catalyst resulted in the formation of complexed CO moieties. Whereas exposure of CO2 to the same catalyst produced bands ascribed to CO2 -, bidentate carbonate and complexed CO species. Fully oxidised copper/silica surfaces gave bands due to CO on CuO and isolated Cu2+ cations on silica. Addition of potassium to this catalyst removed a peak attributed to CO adsorption on isolated Cu2+ cations and red-shifted the maximum ascribed to CO adsorbed on CuO. For a reduced copper/silica catalyst bands due to adsorbed CO on both high and low index planes were red-shifted by 10 cm-1 in the presence of potassium, although the strength of the Cu - CO bond did not appear to be increased concomitantly. An explanation in terms of an electrostatic effect between potassium and adsorbed CO is forwarded. A small maximum at ca. 1510 cm-1 for the reduced catalyst increased substantially upon exposing CO to a reoxidised promoted catalyst. Correspondingly, CO2 adsorption allowed the identification of two distinct carboxylate species, one of which was located at an interfacial site between copper and potassium oxide. Carboxylate species reacted with hydrogen at 295 K, on a reduced copper surface, to produce predominantly unidentate formate on potassium. In contrast no interaction was detected on a reoxidised copper catalyst at 295 K until a fraction of the copper surface was in a reduced state. Furthermore the interaction of polar water molecules with carboxylate species resulted in a perturbation of this structure which gave lower C----O stretching frequencies.

A combined temperature-programmed reaction spectroscopy and Fourier-transform infrared spectroscopy study of CO2/H2 and CO/CO2/H2 interactions with model ZnO/SiO2, Cu/SiO2 and Cu/ZnO/SiO2 methanol-synthesis catalysts

The reaction of CO2 and H2 with ZnO/SiO2 catalyst at 295 K gave predominantly hydrogencarbonate on zinc oxide and a small quantity of formate was evolved after heating at 393 K. Elevation of the reaction temperature to 503 K enhanced the rate of formation of zinc formate species. Significantly these formate species decomposed at 573 K almost entirely to CO2 and H2. Even after exposure of CO2-H2 or CO-CO2-H2 mixtures to highly defected ZnO/SiO2 catalyst, the formate species produced still decomposed to give CO2 and H2. It was concluded that carboxylate species which were formed at oxygen anion vacancies on polar Zn planes were not significantly hydrogenated to formate. Consequently it was proposed that the non-polar planes on zinc oxide contained sites which were specific for the synthesis of methanol. The interaction of CO2 and H2 with reduced Cu/ZnO/SiO2 catalyst at 393 K gave copper formate species in addition to substantial quantities of formate created at interfacial sites between copper and zinc oxide. It was deduced that interfacial formate species were produced from the hydrogenation of interfacial bidentate carbonate structures. The relevance of interfacial formate species in the methanol synthesis reaction is discussed. Experiments concerning the reaction of CO2-H2 with physical mixtures of Cu/SiO2 and ZnO/SiO2 gave results which were simply characteristic of the individual components. By careful consideration of previous data a detailed proposal regarding the role of spillover hydrogen is outlined. Admission of CO to a gaseous CO2-H2 feedstock resulted in a considerably diminished amount of formate species on copper. This was ascribed to a combination of over-reduction of the surface and site-blockage.

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.

A fourier-transform infrared study of CO2 and CO2/H2 interactions with caesium-doped copper catalysts

FTIR spectra are reported of CO2 and COi/Hi on a silica-supported caesium-doped copper catalyst. Adsorption of COj on a "caesium"/silica surface resulted in the formation of COj and complexed CO species. Exposure of CO2 to' a caesium-doped reduced copper catalyst produced not only these species but also two forms of adsorbed carboxylate giving bands at 1550, 1510, 1365 and 1345 cm"1. Reaction of carboxylate species with hydrogen at 388 K gave formate species on copper and caesium oxide in addition to methoxy groups associated with caesium oxide. Methoxy species were not detected on undoped copper catalyst suggesting that caesium may be a promoter for the methanol synthesis reaction. Methanol decomposition on a caesium-doped copper catalyst produced a small number of formate species on copper and caesium oxide. Methoxy groups on caesium oxide decomposed to CO and U.2, and subsequent reaction between CO and adsorbed oxygen resulted in carboxylate formation. Methoxy species located at interfacial sites appeared to exhibit unusual adsorption properties.

Driver perceptions of the benefits of reducing their driving speed on safety, emissions, and stress and road rage

The existing literature shows driving speed significantly affects levels of safety, emissions, and stress in driving. In addition, drivers who feel tense when driving have been found to drive more slowly than others. These findings were mostly obtained from crash data analyses or field studies, and less is known regarding driver perceptions of the extent to which reducing their driving speed would improve road safety, reduce their car’s emissions, and reduce stress and road rage. This paper uses ordered probit regression models to analyse responses from 3538 Queensland drivers who completed an online RACQ survey. Drivers most strongly agreed that reducing their driving speed would improve road safety, less strongly agreed that reducing their driving speed would reduce their car’s emissions and least strongly agreed that reducing their driving speed would reduce stress and road rage. Younger drivers less strongly agreed that these benefits would occur than older drivers. Drivers of automatic cars and those who are bicycle commuters agreed more to these benefits than other drivers. Female drivers agreed more strongly than males on improving safety and reducing stress and road rage. Type of fuel used, engine size, driving experience, and distance driven per week were also found to be associated with driver perceptions, although these were not found to be significant in all of the regression models. The findings from this study may help in developing targeted training or educational measures to improve drivers’ willingness to reduce their driving speed.

A flexible Bayesian model for describing temporal variability of N2O emissions from an Australian pasture

Soil-based emissions of nitrous oxide (N2O), a well-known greenhouse gas, have been associated with changes in soil water-filled pore space (WFPS) and soil temperature in many previous studies. However, it is acknowledged that the environment-N2O relationship is complex and still relatively poorly unknown. In this article, we employed a Bayesian model selection approach (Reversible jump Markov chain Monte Carlo) to develop a data-informed model of the relationship between daily N2O emissions and daily WFPS and soil temperature measurements between March 2007 and February 2009 from a soil under pasture in Queensland, Australia, taking seasonal factors and time-lagged effects into account. The model indicates a very strong relationship between a hybrid seasonal structure and daily N2O emission, with the latter substantially increased in summer. Given the other variables in the model, daily soil WFPS, lagged by a week, had a negative influence on daily N2O; there was evidence of a nonlinear positive relationship between daily soil WFPS and daily N2O emission; and daily soil temperature tended to have a linear positive relationship with daily N2O emission when daily soil temperature was above a threshold of approximately 19°C. We suggest that this flexible Bayesian modeling approach could facilitate greater understanding of the shape of the covariate-N2O flux relation and detection of effect thresholds in the natural temporal variation of environmental variables on N2O emission.

Biodiesel with controlled physicochemical properties, a means to further reduce diesel engine particle emissions

The issue of particle emissions from diesel engines is still a matter of concern due its deleterious effects both on human health and environment(Ristovski et al., 2012). Recently, International Agency for Research on Cancer (IARC) inclusion of diesel engine exhaust particles as carcinogenic to human health added a new margin on it. Apart from the use of after treatment technology, biodiesel is also considered as potential way to reduce particle emission alongside with other emissions(Xue, Grift, & Hansen, 2011). Global biodiesel production is still reasonably small compared to its counterpart fossil diesel, but even this small amount comes from a wide variety of feed stocks. Contrary to fossil diesel, the important physicochemical properties of biodiesel vary among different feed stocks(Hoekman, Broch, Robbins, Ceniceros, & Natarajan, 2012).

Sulfur resistant emissions catalyst

A catalyst comprising one or more complex oxides having a nominal compn. as set out in formula (1): AxB1-y-zMyPzOn (1) wherein A is selected from one or more group III elements including the lanthanide elements or one or more divalent or monovalent cations; B is selected from one or more elements with at. no. 22 to 24, 40 to 42 and 72 to 75; M is selected from one or more elements with at. no. 25 to 30; P is selected from one or more elements with at. no. 44 to 50 and 76 to 83; x is defined as a no. where 0

Continuous remote emissions monitoring – the lynchpin for air quality management

Diesel particulate matter (DPM), in particular, has been likened in a somewhat inflammatory manner to be the ‘next asbestos’. From the business change perspective, there are three areas holding the industry back from fully engaging with the issue: 1. There is no real feedback loop in any operational sense to assess the impact of investment or application of controls to manage diesel emissions. 2. DPM are getting ever smaller and more numerous, but there is no practical way of measuring them to regulate them in the field. Mass, the current basis of regulation, is becoming less and less relevant. 3. Diesel emissions management is generally wholly viewed as a cost, yet there are significant areas of benefit available from good management. This paper discusses a feedback approach to address these three areas to move the industry forward. The six main areas of benefit from providing a feedback loop by continuously monitoring diesel emissions have been identified: 1. Condition-based maintenance. Emissions change instantaneously if engine condition changes. 2. Operator performance. An operator can use a lot more fuel for little incremental work output through poor technique or discipline. 3. Vehicle utilisation. Operating hours achieved and ratios of idling to under power affect the proportion of emissions produced with no economic value. 4. Fuel efficiency. This allows visibility into other contributing configuration and environmental factors for the vehicle. 5. Emission rates. This allows scope to directly address the required ratio of ventilation to diesel emissions. 6. Total carbon emissions - for NGER-type reporting requirements, calculating the emissions individually from each vehicle rather than just reporting on fuel delivered to a site.

Climate change and IMO technical and operational measures for reduction of emissions of greenhouse gas from ships

According to a study conducted by the International Maritime organisation (IMO) shipping sector is responsible for 3.3% of the global Greenhouse Gas (GHG) emissions. The 1997 Kyoto Protocol calls upon states to pursue limitation or reduction of emissions of GHG from marine bunker fuels working through the IMO. In 2011, 14 years after the adoption of the Kyoto Protocol, the Marine Environment Protection Committee (MEPC) of the IMO has adopted mandatory energy efficiency measures for international shipping which can be treated as the first ever mandatory global GHG reduction instrument for an international industry. The MEPC approved an amendment of Annex VI of the 1973 International Convention for the Prevention of Pollution from Ships (MARPOL 73/78) to introduce a mandatory Energy Efficiency Design Index (EEDI) for new ships and the Ship Energy Efficiency Management Plan (SEEMP) for all ships. Considering the growth projections of human population and world trade the technical and operational measures may not be able to reduce the amount of GHG emissions from international shipping in a satisfactory level. Therefore, the IMO is considering to introduce market-based mechanisms that may serve two purposes including providing a fiscal incentive for the maritime industry to invest in more energy efficient manner and off-setting of growing ship emissions. Some leading developing countries already voiced their serious reservations on the newly adopted IMO regulations stating that by imposing the same obligation on all countries, irrespective of their economic status, this amendment has rejected the Principle of Common but Differentiated Responsibility (the CBDR Principle), which has always been the cornerstone of international climate change law discourses. They also claimed that negotiation for a market based mechanism should not be continued without a clear commitment from the developed counters for promotion of technical co-operation and transfer of technology relating to the improvement of energy efficiency of ships. Against this backdrop, this article explores the challenges for the developing counters in the implementation of already adopted technical and operational measures.

REDD+ and mangroves : a study on Sundarbans

Sundarbans, a Ramsar and World Heritage site, is the largest single block of tidal halophytic mangrove forest in the world covering parts of Bangladesh and India. Natural mangroves were very common along the entire coast of Bangladesh. However, all other natural mangrove forests, including the Chakaria Sundarbans with 21,000 hectares of mangrove, have been cleared for shrimp cultivation. Against this backdrop, the Forest Department of Bangladesh has developed project design documents for a project called ‘Collaborative REDD+ Improved Forest Management (IFM) Sundarbans Project’ (CRISP) to save the only remaining natural mangrove forest of the country. This project, involving conservation of 412,000 ha of natural mangrove forests, is expected to generate, over a 30-year period, a total emissions reduction of about 6.4 million tons of CO2. However, the successful implementation of this project involves a number of critical legal and institutional issues. It may involve complex legal issues such as forest ownership, forest use rights, rights of local people and carbon rights. It may also involve institutional reforms. Ensuring good governance of the proposed project is very vital considering the failure of the Asian Development Bank (ADB) funded and Bangladesh Forest Department managed ‘Sundarbans Biodiversity Conservation Project’. Considering this previous experience, this paper suggests that a comprehensive legal and institutional review and reform is needed for the successful implementation of the proposed CRISP project. This paper argues that without ensuring local people’s rights and their participation, no project can be successful in the Sundarbans. Moreover, corruption of local and international officials may be a serious hurdle in the successful implementation of the project.

Spatial prediction of N2O emissions in pasture : a Bayesian model averaging analysis

Nitrous oxide (N2O) is one of the greenhouse gases that can contribute to global warming. Spatial variability of N2O can lead to large uncertainties in prediction. However, previous studies have often ignored the spatial dependency to quantify the N2O - environmental factors relationships. Few researches have examined the impacts of various spatial correlation structures (e.g. independence, distance-based and neighbourhood based) on spatial prediction of N2O emissions. This study aimed to assess the impact of three spatial correlation structures on spatial predictions and calibrate the spatial prediction using Bayesian model averaging (BMA) based on replicated, irregular point-referenced data. The data were measured in 17 chambers randomly placed across a 271 m(2) field between October 2007 and September 2008 in the southeast of Australia. We used a Bayesian geostatistical model and a Bayesian spatial conditional autoregressive (CAR) model to investigate and accommodate spatial dependency, and to estimate the effects of environmental variables on N2O emissions across the study site. We compared these with a Bayesian regression model with independent errors. The three approaches resulted in different derived maps of spatial prediction of N2O emissions. We found that incorporating spatial dependency in the model not only substantially improved predictions of N2O emission from soil, but also better quantified uncertainties of soil parameters in the study. The hybrid model structure obtained by BMA improved the accuracy of spatial prediction of N2O emissions across this study region.