Qatar Foundation Annual Research Conference Proceedings Volume 2016 Issue 1

Industrial revolution, a consequence of the rapid economic growth, has contributed to ever increasing demand for energy and has resulted in about 40% rise in the atmospheric concentration of carbon dioxide, from 280 ppm in 1750 to 400 ppm in 2015. Abundant use of fossil fuels has become a cause of concern due to their adverse effects on the environment, particularly related to the emission of carbon dioxide (CO2), a major contributor of GHG. In this context, CO2 capture and is storage or transformation gained significance in the recent research scenario. Various matured CO2 capture technologies such as amine based capture, needs high energy input, especially in desorption process and are also not sustainable in nature. Alternatively, carbonic anhydrase (CA) proved to be more efficient in capturing CO2 at faster rate and also needs less energy input for desorption process. However, utilization of the captured CO2 is more important rather than its capture, to close the carbon cycle and recycle it. In this direction, bioelectrochemical system (BES) is presenting an exciting opportunity with a possibility of simultaneous CO2 capture and biotransformation to value-added products in a sustainable way. Both microbes and enzymes were studied as catalyst in BES, though the application of enzymes is less foreseen. Present study demonstrates the biotransformation of CO2 to ethanol using a cascade of dehydrogenases [formate dehydrogenase (FateDH), formaldehyde dehydrogenase (FaldDH) and alcohol dehydrogenase (AlcDH)] together on the electrode of BES. Further to that, carbonic anhydrase (CA) was also included in the cascade and found that the product yield increased by 15% contributing to ethanol production rate of ∼0.6 kg/m³/h along with current density of ∼2 A/m². When the FaldDH was excluded from the cascade also, there is no reduction in productivity of ethanol. It was surprising to get ethanol instead of methanol but based on literature, it is also possible for the production of ethanol directly from formic acid, which is economically more viable.

Characterizing the content and understanding the distribution of organic carbon in sediments is a key element for the exploration and the production of new or revisited petroleum prospects.

Developed by Total, the LIPS has a set of unique features:

∘ it is poorly destructive: indeed, the laser impact affects only 1 mm³ of material,

∘ it generates very large datasets / big data (typically 10,000 data points and more for 100 meters of core). Statistical treatment on such data sets provide more significant and more representative description than discrete and low resolution sampling. This opens completely new perspectives to understand organic matter deposition and distribution. Thus, descriptive and inductive statistics may be used to infer laws and to detect:

  - trends, behaviors and dependencies,

  - relationships with lithology, rock type, Milankowitch cycles …

∘ it provides high resolution data allowing more accurate location and a better quantitative evaluation of the organic carbon in cores.

The LIPS equipment currently installed in Doha (Fig. 1) addresses typical issues in the Middle East.

Figure 1: LIPS equipment installed in TRC-Q, Doha, Qatar

The high resolution data acquisition allows exhaustive location of permeability barriers in carbonate reservoirs also known by petroleum engineers as tar mats. It also contributes to the identification of all the sweet spots in source rocks layers for non conventional plays in exploration and development. As such it is a tool contributing significantly to the economical exploitation of shales gases and shale oils.

“Milanković-type“ climate cycles are due to variation of Earth rotation. They are known to control fluctuation of sedimentary organic carbon. The data presented in Fig. 2 indicate that the resolution of LIPS data is high enough to highlight the climate change induced variations of organic carbon in the Jordan oil shale play. It also shows the added value of the LIPS in comparison with the conventional Rock Eval data.

Figure 2: High resolution LIPS data (1/cm) highlights the climate induced variations of organic carbon in the Jordan oil shale

In light of successful results obtained for GCC issues, new developments involving local staff are expected in Doha with the support of Total's Headquarter. Indeed, specific applications to carbonate reservoirs and resources are underway, for instance:

∘ new methods for performing quantitative analysis of bitumen forming tarmat in carbonate reservoirs. Middle East is the ideal trial field, since all tarmat configurations and formation pathways exist in these countries,

∘ new and simple devices for specific compound detection (e.g. CO2, organo-sulfur compounds...). The goal is to make a distinction between fossil organic carbon, tarmat, heavy oil and oil. Automatic measurement High resolution correlation between TOC and of residual permeability may be performed,

∘ hyphenated techniques from the coupling of the LIPS with on-line spectroscopic detection technologies (e.g. isotope ratios mass spectrometer).

The LIPS is a real breakthrough in terms of both its technological originality and its unique ability to characterize carbon deposits.

Aquatic ecosystems across the globe are under significant threat, suffering from various forms of anthropogenic disturbances, which is greatly impacting global biodiversity, economy and human health. Reliable monitoring of species is crucial for data-driven management actions in this context, but remains a challenge owing to non-standardized and selective methods relaying on physical identification of species by visual surveys and counting of individuals. However, traditional monitoring techniques remain problematic due to difficulties associated with correct identification of cryptic species or juvenile life stages, These traditional methods depend on practical and taxonomic expertise, which is steadily declining. In an attempt to come up with new objective solutions for monitoring biodiversity, recent and ongoing studies in Qatari waters, uses and further develops novel environmental DNA (eDNA) methods for Monitoring aquatic biodiversity in the Gulf and elsewhere.

Previous studies have shown that diversity of rare and threatened European freshwater animals - representing amphibians, fish, mammals, insects and crustaceans - can be detected and quantified based on environmental DNA (eDNA) obtained directly from small water samples of lakes, ponds and streams (Thomsen et al. 2012a).

Subsequently, for the first time, we investigated the potential of using metabarcoding of eDNA obtained directly from seawater samples to account for marine fish and mammal biodiversity. We show that such marine eDNA can account for fish biodiversity using high-throughput sequencing. Promisingly, eDNA covered the fish diversity better than any of 9 methods, conventionally used in marine fish surveys. Additionally, we show that even short fish eDNA sequences in seawater degrades beyond detectable levels within days, in accordance with results obtained from freshwater eDNA (Thomsen et al. 2012b). Controlled mesocosm experiments have also shown that eDNA becomes undetectable within 2 weeks after removal of animals, indicating that eDNA traces are near contemporary with species presence. Our findings underpin the ubiquitous nature of eDNA traces in the environment and support the use of eDNA as a tool for monitoring rare, threatened and economically important species across a wide range of taxonomic groups.

A particularly interesting study focuses on the large whale shark aggregation at the Al Shaheen Oil Field, located in the offshore area called “Block 5”, in the NE of the Exclusive Economic Zone (EEZ) of Qatar. Maersk Oil Qatar is currently operating several oil and gas production platforms within this field, and also take active part in a large whale shark research project studying many aspect about the aggregation. Quantitative PCR (qPCR) and high-throughput sequencing of sea water from the area have successfully been employed to gain new information about the occurrence, abundance and biology of the aggregation. More specifically, data from 2013 and 2014 showed that whale shark eDNA concentrations follows visual observations of abundance, and that degradation of eDNA occur rapidly, supporting that the obtained genetic material is of local origin. Our findings confirm that seawater samples can contain key information on populations of oceanic species, and demonstrate a general potential of eDNA for studying populations of marine organisms.

Although further studies are needed to validate the eDNA approach under varying environmental conditions, our findings provide a strong proof-of-concept with great perspectives for future monitoring of aquatic biodiversity and resources in the Gulf.

References

Thomsen PF, Kielgast J, Iversen LL, Wiuf C, Rasmussen M, Gilbert MTP, Orlando L, Willerslev E (2012a). Monitoring Endangered Freshwater Biodiversity using Environmental DNA. Molecular Ecology 21, 2565–2573.

Thomsen PF, Kielgast J, Iversen LL, Møller PR, Rasmussen M, Willerslev E (2012b). Detection of a Diverse Marine Fish Fauna using Environmental DNA from Seawater Samples. PLOS ONE 7(8), e41732.

In the present work we examine how recent progress at our collaborating laboratories, over various solar thermochemical technologies, can be brought to bear on the advancement of renewable resource utilization in Qatar.

Specific examples of such technologies include solar water splitting for H2 production, solar CO2 splitting thermochemical energy storage in reduced metal oxides, solar cracking of CH4 for production of carbon nanoparticles and hydrogen, and production of metal nanoparticles to be employed as renewable fuel. Where feasible the potential of using locally sourced materials is stressed and particular examples are given (e.g. the use of Qatar's CaCO3). Enabling technologies over all scales (from the lab to the demonstration scale) include advanced instrumentation and testing platforms (e.g, solar simulators, solar furnaces, etc). Reactor concepts and system designs are formulated and analyzed and promising designs from the user's perspective are identified for advancing to the next level. Here we describe results and future directions from three such examples.

A low energy, zero-effluent system for clean water production, employing a concentrated solar thermal aquatic stream processing module is described. The projected specific electric energy consumption of the system does not exceed 1 kWh/m³, which in fact can be largely produced by the system itself. The system can exhibit an unprecedented (>99%) clean water recovery from any aquatic stream (seawater, brines, wastewater). At the same time the salt/solids content of the aquatic stream is separated in dry-form, thus being transformed from a waste-to-be-managed into a raw material ready for further commercial exploitation. The system is based on a modular design hence it is applicable over a range of scales, from standalone applications to large scale industrial water plants as well as an add-on to existing large scale producers and/or users of water, for further recovery of water and residual solids (salts, valuable metals from brine/wastewater effluents).

Production of hydrogen can be achieved via photo- and electro-chemical water splitting processes. In order for such processes to be feasible, they employ sacrificial electron donors which also bind oxygen molecule. Then, they have to be regenerated, via thermochemical reactions, and also release the oxygen. So the whole process operates in a cyclic mode, thus called water-splitting cycle. The use of solar energy for the realization of the thermochemical steps increases the overall solar-to-hydrogen efficiency. The Hybrid Sulfur Ammonia cycle, described here, uses ammonium sulfate as the sacrificial donor and a mixture of alkali-metal sulfates and pyrosulfates, which help to recover oxygen at lower temperatures and higher efficiency. We present the of thermal analysis experiments conducted for the calculation of the respective thermodynamic properties (heat capacity and enthalpy). In addition, with the use of advanced thermodynamic tools (FacTSAGE etc), and experimental thermal analysis, we completed the thermodynamic analysis, and selected the reaction temperatures in a range from 350°C to 900°C.

The crucial drawback of solar energy is its intermittent character. At the same time, pollution caused by the release of CO2, mainly in power plants and cement production, results in a series of problems such as global warming and poor air quality. Thermal Energy Storage (TES) can provide an escape route for both the aforementioned problems. TES can be used in order to store heat during periods of high solar irradiation and release it during the night or periods of low activity. Carbonate systems, such as calcite and dolomite, can be utilized for TES. In this study we focus on the reversible calcination/carbonation cycle of (CaMg)CO3, because it is a very strong candidate as a high efficiency thermochemical material. Its energy density is the highest among other materials. It can be found in vast quantities in Qatar, according to its geological formation, thus can be easily used as low cost/high added value material. Furthermore, it is a non-toxic and safe material with easy separation of the phases. In addition, the cycle involves CO2 capture during the discharge stage. This ends up in both energy release and greenhouse gases elimination. So far, we have characterized thermally, chemically and morphologically local raw surface carbonates. Results show that dolomitic powder, (CaMg)CO3 from Northern Qatar and subsurface rocks have an average capacity of 6 mmol CO2/g, but sintering deactivates material significantly after 20 cycles. Currently, we are designing a potential TES process coupled to cement production. In parallel, we are investigating experimentally the available methods to enhance the capacity of the raw material and improve its stability.

Present research contributes towards the solution of the Global Challenges that our societies face today, and in particular it provides access to safe and clean water and energy. These can be achieved with improved performance, energy efficiency and ease of usability.

Petroleum refining, not only consumes large quantities of water but also generates large quantities of wastewater. Large quantities of petroleum refinery wastewater are generated worldwide, approximately 3.5–5 m³ of wastewater generated per ton of crude oil processed. This wastewater is considered as a major source of environmental pollution. Various chemical and biologically based technologies have been developed for the treatment of petroleum refinery wastewater such as reverse osmosis, membrane filtration, electrocoagulation, anaerobic tank, anaerobic baffled reactor, aerated filter and bio-contact oxidation. In the last decade, biological treatment methods of petroleum refinery wastewater were developed because of the high cost of chemical treatment methods and these methods are also more environmental friendly.

In this study, we demonstrate for the first time that it is possible to remove salt from saltwater and generate electricity while using petroleum refinery wastewater as an anodic substrate in the three chamber microbial desalination cell (MDC). MDC insinuates a new method for treating petroleum refinery wastewater and concurrently salt removal from seawater with bioelectricity generation. MDC was developed from microbial fuel cell (MFCs) concept. In this device, desalination and wastewater treatment are conducted in one system. MDC has an enormous potential as a low-cost desalination process with wastewater treatment and other benefits. MDC is a new technique in which saltwater can be desalinated without using any external energy source. The exoelectrogenic-bacteria are used in MDC reactor to oxidize biodegradable substrate in the anodic chamber and transfer the produced electrons to the anode electrode.

In this study, petroleum refinery wastewater was treated in MDC using three different initial salt concentrations of 5 g/l, 20 g/L and real seawater in desalination chamber along with two separate catholyte (phosphate buffer solution and acidified water). All the three chamber MDC operations were carried out in batch mode. The maximum % COD removals of 71 and 64 were obtained using initial salt concentration of 20 g/L with MDC operated with acidified and phosphate buffer solution as catholyte respectively. The maximum desalination efficiency of 19.9% and 19.1 % were obtained in MDC operated with real seawater using PBS and acidified water as catholyte respectively. The scanning electron microscope images investigation confirmed the presence of microbial biofilm on the anode electrode and anion exchange membrane surface. The MDC performed better with acidified water compared to PBS as catholyte. The above obtained results demonstrated the feasibility of using MDC technologies to generate bioelectricity, seawater desalination and simultaneously treat complex petroleum refinery wastewater, although further studies are required to scale up and optimize the process. The MDCs are emerged as a self-energy driven device for wastewater treatment and seawater desalination at the lab scale. But still MDCs needs further research before it can be implemented at large scale. Acknowledgements: This work was made possible by NPRP grant # 6-289-2-125 from the Qatar National Research Fund (a member of Qatar Foundation). The statements made herein are solely the responsibility of the authors.

The availability of fresh water and energy is the key factor of the development of many countries particularly those of over-populated arid areas. Potable water supply shortage and recent technological development have led to wider application of conventional, and yet advanced saline/brackish water desalination plants. Today, desalination methods require large amounts of energy, which is costly both in environmental pollution and in money terms. This study defines the main economic parameters used in estimation of desalination costs and limitation of the stand-alone, small size SWRO plants powered by photovoltaic at the North West cost of Egypt. Moreover, techno-economic study is made to estimate the actual cost of m³/fresh water production on real field measurements. All cost estimations are based on the prevailing prices during 2012–2013. The average unit cost of desalted water with the desalination unit powered by photovoltaic battery is 9.3–5.6 LE/m³, which is very high, but when using the unit with battery, the cost is reduced to be between 2.3–1.7 LE/m³ by increase working hours to 24 hours. Economical strategies should be developed for more reduction in cost taking into account all phases from site selection and design to operation and maintenance and most importantly increasing the local manufacturing. Keywords: Production cost, Economic analysis, Stand-Alone, Reverse osmosis, photo voltaic, Desalination, Egypt.

The catalytic decomposition of methane (CDM) on suitable surfaces offers the prospect for lower or zero-carbon routes to energy using natural gas or methane derived via biomass options. The carbon from the decomposition could be stored (buried), used for specific applications or perhaps converted to electricity using carbon fuel cells, according to which the overall process is near-zero or low carbon dioxide producing in character. A large volume of work now describes the action of supported nickel in the CDM reaction. However, the basic ground rules governing activity, longevity (closely related to carbon yield) and carbon morphology as well as issues around practical reactor systems for the sustained catalytic action of solid catalysts remain to be developed. In nickel/titania systems the carbon type and yield are dependent on nickel loading levels, with lower Ni loadings favouring higher carbon yields per unit of Ni. The carbon yield per unit mass of catalyst in nickel-titania systems is largely independent of Ni loading. Carbon yields are greatly influenced by the nature of the catalytic solid. Addition of Cu or La can lead to unusually high carbon yields in excess of 2000 g/gNi, some of the highest ever reported. The nature of zeolite morphology in Cu-Ni systems also greatly influences the carbon yield and examples of this behaviour will be presented and discussed. Considerations of how to regenerate CDM catalysts, or slowing their deactivation in the first place are demanded if sustained practical CDM is to be achieved and some ideas on the issue may be developed from experiences with other methane decomposition systems, including non-catalytic approaches that have been pursued using concentrated solar energy, for example.

The ability of date palm tree to survive under adverse abiotic conditions renders it as an important fruit tree growing in hot and dry regions. Nevertheless, the optimal conditions for date palm growth and production are also suitable for fungal growth leading to major diseases such as black scorch. The aim of this work was to develop a genetic control of date palm to Thielaviopsis punctulata, the causal agent of black scorch, through understanding molecular interactions between the plant host and the pathogen. Genomics and bioinformatics tools were used to sequence, assembly and annotate the whole genome of the pathogen and to decipher the molecular mechanisms of date palm resistance to the pathogen. The whole fungal genome was assembled and functionally annotated with an estimated size of 28.1 Mb containing 5,480 predicted genes. Some of the annotated genes belong to toxin-related genes such as necrosis inducing protein (NPP1) and Cerato-platanin, reflecting a potential functional role of fungal toxins in inducing disease symptoms. On the host side, real-time PCR and RNA-Seq approaches were used to quantify the fungal infection and profile the genome expression of date palm in response to the pathogen infection in two cultivars at 1, 2, 3 and 4 day post infection (dpi). Results from real-time PCR showed that the fungal infection started early at one dpi and the highest level of infection was detected at three dpi for both cultivars. Results also showed that Khalas cultivar is less infected by the pathogen compare to Kinzy cultivar reflecting a degree of resistance in Khalas cultivar. Data from RNA-Seq is being analyzed to identify regulatory genes involved in resistance to black scorch disease. Information from the current study will lead to further understanding of the molecular interactions between T. punctulata and date palm, assisting in deriving effective genetic control strategies for black scorch disease.

Air pollution, global greenhouse gases (GHG), water pollution and water resources degradation are among the most serious environmental concerns that encounter the Qatar country. In nowadays, it is commonly known that the effects of environment degradation exceed its direct negative impacts on climate changes to cover its impacts on Human health, nation livelihood and cultural integrity. So, we advocate that understanding and determining factors explaining environmental degradation remain an important question of research. Moreover, by determining factors that explain environment degradation, policymakers, researchers and international institutions can help on recommending the adequate economic policies that can improve the environment quality and the live standing of inhabitants. In the empirical literature, the Environmental Kuznets Curve (EKC) is the most powerful tool used to investigate the relationship between environment degradation and some macroeconomics and financial variables. Following the EKC hypothesis, the relationship between economic growth and environment degradation is inverted-U shaped. From the economic perspective, this means that initially economic growth increases environment degradation and then declines it after a threshold point of income per capita. More specifically, at initial level of economic growth, an increase in income is linked with an increase in energy consumption that raises environment degradation. After reaching a critical level of income, the spending on environment protection is increased, and hence environment degradation tend to decrease. From an econometrical or statistical perspectives, the EKC hypothesis have been firstly tested using the basic EKC equation which relies the environment degradation proxy to the real GDP and to a nonlinear term of the real GDP (the squared real GDP). If the EKC hypothesis holds then the real GDP and the squared real GDP have respectively a positive and negative signs. This EKC hypothesis has been firstly introduced by Kuznets (1955) when examining the relationship between economic growth and income inequality which shows that this relationship is inverted U-shaped. Grossman and Krueger (1995) are the first to examine this relationship between environment degradation and economic growth in their seminal paper published on the Quarterly Journal of Economics. They found that this relationship is inverted U-shaped which validates the EKC hypothesis. Empirically, until now no consensus has been reached about the true nature of the relation between real GDP and environment degradation. Evidence for the EKC hypothesis is very mixed. Overall, the results seem to depend in many factors including the specification, the pollutants and the econometrics technique used. First, empirical studies show that the results in term of positive and negative relationships as well as in term of magnitude differ significantly for the same country depend on the specification studied, linear, quadratic or cubic. Moreover, the inclusion of other factors in the right hand of the regression such as urbanization, trade openness, financial development and political stability have a significant impact on the magnitude of the income per capita variables coefficients. Second, the results differ significantly following the environment degradation proxy used. For instance, Horvath (1997) and Holtz-Eakin and Selden (1995) suggest that the use of global pollutants leads to continuously rise the levels of environment degradation or to a high levels of income per capita turning point, see also Esteve and Tamarit (2011). Third, the results also seem to depend in the econometric approach employed. In this paper, we investigate the case of the Qatar economy for several reasons. First, Qatar 2030 vision has given a high importance to questions related to air pollution, climate change and their impacts on economic sustainability. Second, the rapid increase of economic growth of the Qatar economy in the last two decades has been accompanied with an increase in energy consumption, urbanization and international trade. These factors are among the most important factors largely used in theoretical and empirical literature to explain environment degradation. Third, following the world health organization (WHO), local air pollution levels in Qatar has frequently exceeded recommended levels and are more time higher than the international standards. In fact, compared to the WHO's standards for PM10 for the 24-hour average and for the annual average concentration of 50 ug/m³ and 20 ug/m³ the Qatar's national air quality standards are far from these values. For instance, the values for PM10 is around 150 ug/m³ for 24 hours average concentration and to 50 ug/m³ for the annual average concentration. The data set used in this paper consists on macroeconomics and financial data, including CO2 emissions, ecological foot print, real GDP per capita, energy use, urbanization, financial development and openness trade, to investigate the EKC hypothesis for the Qatar economy. All the dataset except the ecological foot print variable are collected from the world Bank's development indicators (WDI). The ecological footprint data is obtained from the National Footprint Accounts (NFAs) of the Global Footprint Network. This variable is employed as second proxy of environment quality measures. This data set used is a quarterly data and covers the period 1975Q1 to 2007Q4 for variables used for ecological footprint equation and covers the periods 1980Q1 to 2010Q4 for the CO2 emissions equations variables. This paper contributes to the empirical literature of the EKC hypothesis in many ways. First, to our knowledge this paper is the first to consider the case of the Qatar economy as a single country to test the EKC hypothesis as well as the different directions of causality between variables. Second, in addition to the CO2 emissions largely employed in the empirical literature, in this paper we employ also the ecological footprint as a new proxy of environmental degradation. Third, we use recent development of cointegration approach with structural breaks which is also rarely used for the case of EKC hypothesis. As tests of cointegration with shifts in the cointegration vector, we use the Gregory and Hansen (1996), Hatemi-J (2008) and to investigate the causal relationship between all variables using standard Granger causality tests. Fourth, to our knowledge this paper is the first study that uses Markov Switching Equilibrium Correction Model with shifts in both the intercept and the income per capita coefficient for the long run relationship between environment degradation and its key determinants. The empirical findings of this paper are useful for Qatari policymakers and especially for the ministry of environment of the Qatar government. Moreover, economic implications and economic policy are proposed and discussed. [1] P.O.Box: 2713-Doha-Qatar. Email: [email protected]. Office: (+974) 4403-7764(+974) 4403-7764, Fax: (+974) 4403-5081. 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In this study a decentralized combined cooling-heating-and-power (CCHP) plant fueled with liquefied natural gas (LNG) is integrated with photovoltaic (PV) technology to reduce fuel consumption and improve the economics of the CCHP plant. In their previous publications the authors have investigated the potential of an LNG-fueled CCHP at different configurations and system capacities, where the inclusion of PV technology was not investigated in detail. In this study the penetration of PV technology is analyzed in detail to reveal possible benefits. The modular nature of PV technology allows an opportunity for investigating power generation at different configurations. Additionally this combination shows a potential for reducing emissions and suggests a new concept of integrating an intermittent source of energy, such as solar energy. The proposed system is based on a realistic gas turbine cycle, integrated with a cooling plant and a district energy network. The detailed analysis of this study shows the thresholds of the proposed system to become an ideal candidate for distributed generation applications, especially in locations which are distant from centralized power plants. Therefore apart from reducing transmission and distribution losses, waste heat could be recovered effectively to generate heating, or cooling (absorption refrigeration technology). The system considers fueling with LNG, which is a safe and transportable fuel option. The simulation results show a potential for further investigation of the proposed system, since its performance results in significant thermodynamic and environmental improvements. The system can be operated in two modes: (a) winter operation, where recovered heat is distributed to the district energy network, (b) summer operation, where recovered heat is used to drive an absorption chiller-based cooling plant to generate cooling, which is also distributed to the district energy network. The average primary energy ratio of the proposed system is near 90%, which shows a potential for operation at high efficiencies. The cost analysis shows that the payback period is within a reasonable time frame; approximately 4 years. The system is modeled based on theoretical and experimental, including data from manufacturers’ datasheets and other assumptions. Each component and/or subsystem is modeled separately and coupled to every adjacent component, as described in the system configuration. All details, including specific assumptions are provided in the study. The values for all system input parameters are given, followed by a description of all subsystem and/or component models, i.e. CCHP plant, heat exchangers, cooling plant and district energy network. The cost model is described in detail, with all necessary cost functions and their input values, and also to allow a more realistic analysis of the feasibility potential of the proposed system a rigorous cost model is formulated. The main economic parameters evaluated are: projected total lifecycle cost (LCC), investment cost, operating cost and PP. The system model is validated using two commercially available gas turbines as reference cases, which include measured data from their respective manufacturer. Therefore the model input values correspond to the values taken from the references. The results of the model validation are given in detail in the study. The calculated error between the system simulation and the manufacturers’ data is low (0 to about 5%). Thereby, it can be assumed that the proposed system is modeled within an acceptable level of accuracy. The proposed CCHP system can be applied using different operational strategies, which may be based on either thermal energy (heating/cooling) or electricity demand. However to allow complete utilization of the generated thermal energy, the system must be based on a thermal energy-led operation. Therefore if it is assumed that the system operates at a constant, full power capacity (which also allows maximum net electrical efficiency), all generated thermal energy is delivered to buildings. The system is grid-interconnected to allow import/export of electricity, while the buildings are equipped with vapor-compression heat pumps, which will be operated the thermal energy supplied from the CCHP system is insufficient. The heat pumps are operated with electricity generated from the CCHP system. In the case of a CCHP system it is important to choose the set of consumers (buildings) that will allow an efficient matching of the generated vectors of energy with demand. The reason is that for example in the case of heating mode, high heat is required during the evening and early morning hours in households (due to high occupancy and low ambient temperature), while high heat demand occurs during daytime working hours in weekdays. A proposed small-scale, decentralized CCHP system is considered as alternative to conventional large-scale centralized, electricity-only generating power plants. The system is designed, modeled and analyzed in terms of thermodynamics, including cost analysis and exergy analysis. The results of the system model simulation show the potential of the proposed system in terms of efficiency. The system performs efficiently, with a PER of near 90%, and therefore the proposed system may become a significant candidate in the energy market, since fuel consumption and CO2 emissions can be reduced. The considered fuel is LNG, and with the proposed design approach of its regasification, the cooling energy can be used to cool the feed air before compression, which results to a net electrical efficiency of almost 2%, which is an attractive system modification for areas with prolonged summer-like weather conditions. Overall, when the proposed system is compared to an equivalent conventional system, results show significant improvement in CO2 emissions reduction (almost 40%) and primary energy savings (more than 40%). The exergy analysis shows that there is a potential for improvement of the exergetic efficiency through design modifications. Exergy destruction is higher in the combustor, the cooling plant and the heat exchangers responsible for recovering waste heat (i.e. HEx2 and HEx3). In the case of the cooling plant and the heat exchangers, the irreversibility is due to the conversion of high quality waste heat to low quality useful heating (or cooling). This is an unavoidable result due to the purpose of the proposed system, although exergetic efficiency could improve with the replacement of the double-effect absorption chiller with a triple-effect one. Also, theoretically, net electrical efficiency (and also exergetic efficiency) can be improved with the introduction of a combined cycle configuration, which is however a more complex and costly, and thereby an unfavorable option for distributed generation applications. The only possible and feasible modification for the current system design could be the optimization of the combustion process, by preheating the reactants or minimizing the use of excess air, although this could result in an impractical (or inflexible) system configuration.

Background & Objective: Air pollution is a major problem that has been recognised throughout the world for hundreds of years. In the middle ages, the burning of coal in cities released increasing amounts of smoke and sulphur dioxide to the atmosphere. In the late 18th century, the Industrial Revolution, beginning in the UK, led to escalation in pollutant emissions based around the use of coal by both homes and industry.Pollutant emissions continued to grow through the 19th and early 20th centuries leading to poor Air Quality (AQ). In more recent times, pollution from motor vehicles has become the most recognised AQ issue. Present pollution monitoring is revealing that if we don't act swiftly then vehicle pollution could harm our environment and reduce the quality of life for future generations. The number of cars, both in Qatar and in most countries around the world, is currently steadily increasing, and a speed up in technological development is required to combat the pollution problem. Poor AQ has negative effects on the environment and thus on our wellbeing. Air pollution from transport vehicles includes emissions of carbon monoxide, particulates, nitrogen oxides and dioxide, hydrocarbons and so on. Whilst much attention has been directed towards poor outdoors AQ we sometimes forget that we spend up to 90% of our time indoors. Consequently, keeping the air which we breathe at home clean is crucial, particularly for vulnerable people including babies, children, pregnant women and the unborn babies, the elderly, and those suffering from respiratory or allergic diseases such as asthma. Although in the majority of homes the indoor AQ (IAQ) is fairly good, CO, SO2, NO2 etc… are just some of the indoor air pollutants which can give cause for concern. The level of indoor air pollutants depends on factors such as outdoor air pollutants, construction materials and interior finishing, poorly-designed air conditioning and ventilation systems, and households and furniture (via outgassing from fabrics, paints, pets, etc.). Over-ventilation, as often thought, does not solve the problem. Nevertheless, this illusory solution is not adequate in the hot climate of the Gulf region as it leads to unacceptable levels in power demand. Sustaining economic and social growth is impossible without a holistic environmental vision that places environmental preservation for Qatar's future generations at the forefront. The QNV2030 aim to strike a balance between developmental needs (human, society, economy) and the protection of its natural environment, whether land, sea or air. Echoing international initiatives, Qatar has recently undertaken relentless intensive steps in an attempt to address the problem of AQ. The QNV2030 associated Qatar National Development Strategy 2011-2016 (QNDS 2011-2016), through a set of well-defined recommendations, stresses on the need to address the issues of environment and air pollution. To meet these needs, in this extended abstract we present SERENO (SEnsor and REceiver Node), a renewable energy-harvested sensor node that intelligently monitors air quality continuously without human intervention. This paper discusses the challenges of designing an autonomous system powered by ambient energy harvesting. Preliminary results demonstrate that, the presented platform could effectively report and trace air quality levels in a sort of set and forget scenario using a mesh network topology to cover as large as possible area deploying from tens to thousand nodes. Methods: The advances in low power electronics and in electrochemical sensors have enabled the development of low cost and power efficient air quality monitoring systems (dedicated to specific target gas and analysis) suitable for even stringent environments and disruptive locations, where air quality assessment is required without human intervention. Environmental energy harvesting technologies has been developed to maximize wireless sensor systems' lifetime and minimize energy consumption by adopting ultra-low power electronics (i.e. ultra-low power controller, low-power AO and CMOS switches). The use of virtually no-power consumed sensors (e.g. electrochemical sensors connected to signal conditioning electronics with supply current around 1 uA) coupled with wireless communication, working on the principle duty cycling (i.e. the device remains in low power SLEEP mode for almost 100% of the time) helps in maximizing the power efficiency and lifetime of the system. It makes the system operative only to perform designated tasks i.e. sensor warm-up, sampling, data processing and wireless data transmission or communication. The top view diagram of the renewable energy harvested system for air quality monitoring named SERENO is given below. Figure 1 shows the 6 sensors operative on the PCB. The general description of the proposed system is described below.

Fresh fruit and vegetables are an important part of a healthy diet as they are a significant source of vitamins and minerals. However, fresh fruits and vegetables can also be a source of toxic substances such as pesticides. Pesticides are a several and diverse group of chemical compounds, which applied to crops at various stages of cultivation and during production and post-harvest treatment of agricultural commodities. Recently, the government of Qatar has attempted to encourage agricultural production. Despite a noticeable increase in agricultural production in Qatar, however, this increase does not fulfill the need of residents in Qatar. Therefore, Qatar imports large amounts of food products from other countries which are large agricultural producers. The lack of information regarding pesticide residues in food in Qatar implies the necessity to determinate their concentrations in food items. Organochlorine pesticides (also known as chlorinated hydrocarbons) are primarily insecticides with relatively low mammalian toxicity, fat soluble and normally persistent in the environment. Many chlorinated hydrocarbons have the ability to accumulate inside the body due to their lipophilic nature. The study was aimed to examine the occurrence of organochlorine pesticides residues in some local and imported vegetables and fruits in Qatar, as a prelude to assess the risks related to their consumption. In order to achieve this aim, the following specific objectives were carried out: (i) determine the amount of 10 organochlorine pesticides (Heptachlor, aldrin, dieldrin, Endrin, a-chlordane, g-chlordane, endosulfane I, methoxychlor, α-BHC and β-BHC) in seven mostly consumed vegetables and fruits in Qatar using Gas chromatography-electron capture detector (GC-ECD), (ii) screen the residues of pesticides in these vegetables and fruits using scan mode of Gas chromatography- mass spectrometry (GC-MS), and (iii) perform statistical analyses to data obtained. A total of 127 samples of most 7 consumed fresh vegetables and fruit from local and import production were analyzed. The samples included: 26 samples of fruits and 101 samples of vegetables. Samples were extracted within 24 hours and stored at 4°C until the analysis. The simple random sampling and stratified random sampling were used as sampling procedures for collecting the vegetables and fruits. For all vegetables and fruits except strawberries, simple random sampling was used. For strawberries sampling, the stratified random sampling procedure was used. The EPA Method 8081 was chosen as a reference method for the preparation and extraction method with some modification. Additionally, the Dionex Application Note 332 “Accelerated solvent extraction of pesticide residues in food products”, 2012, was used as extraction method for vegetables and fruits. The fresh fruits and vegetables samples were collected from farms and market a day before extraction. Each sample was divided in to two groups: washed sample with water and unwashed sample. No sample digestion was needed prior to extraction. A clean-up procedure is usually carried out to remove co-extracted compounds that may cause interference in the chromatographic determination or be detrimental to the analytical instrumentation. Following extraction, 5 g of anhydrous sodium sulfate were added to the collection vial to adsorb co-extracted water. The vial was shaken for 15 s and the water-free extract was decanted into a clean vial. Two solid phase extraction techniques were used (Florisil and Silica Gel). The EPA method 3620C- Florisil Cleanup and Method 3630C- Silica Gel Cleanup were used as reference methods for cleaning the samples. All samples were cleaned up using 2 g Florisil Clean-Prep Cartridge. However, some interferants that are not removed by Florisil Cartridge would be removed by a second cleanup technique which was Silica Gel cleanup. For the Quality Control and Quality Assurance measures (QC/QA), the Limit of detection and limit of quantitation were calculated for all analytes. The LOD and LOQ were calculated using 10 samples of the lowest concentration of spike (10 ppb). The evaluation of the recoveries of studied pesticides were done by adding known concentration of an internal standard (Decachlorobiphenyl) to about 10% of total number of samples. The range from 93.6% to 106.6% was the percent recoveries in spiked samples. Residues of 10 OCPs (Heptachlor, aldrin, dieldrin, Endrin, a-chlordane, g-chlordane, endosulfane I, methoxychlor, α-BHC and β-BHC) were identified using GC/ECD. The GC/ECD analyses were performed on an Agilent 6890 N equipped with a splitless injector and a 7683 autoinjector. The analysis by GC/MS was carried out on an Agilent 7890A MSD 5973 equipped with a split/splitless Inlet and a 7683B autoinjector. Separations were conducted using an HP-1 30 m 0.25 mm 0.25 μm column for GC/ECD and Rxi-5SILMS 30 m 0.25 mm 0.25 μm column for the GC/MS. The GC/MS data were acquired and processed with a wiley7n.1 and NIST98 Libraries. The most frequently detected OCPs in the samples were heptachlor, g-chlordane and a-chlordane. Two statistical analysis tests were used to determine significance (pair-difference t-test and analysis of variance (ANOVA)). In most of the comparisons between the washed and unwashed samples, no-significant differences were observed (P > 0.05). Here, there is a dire require for controlling program for residues of pesticides in food products. Since florisil and silica were used for cleanup, heavy matrix interferences were observed in most of the samples, consisting primarily of fatty acids. Thus the detection and identification of trace levels of pesticides in this complex profile can be very time-consuming and laborious. The level of pesticide residues contamination may be considered a potential public health problem, since pesticides are characterized by various degrees of toxicity to non-target species, including human beings. The results underscore the need for regular monitoring of large samples to determine the pesticide residues, especially for the imported samples. This research can be implemented as a regular monitoring for the presence of OCPs in fruits and vegetables. Also the results of this research can be used as reference for future work. Future studies should consider the processing factors other than washing with tap water in order to account for the reduction or removal of pesticides such as: washing (with acetic acid, sodium chloride and soap) and peeling. Also as a recommendation, we need to look to other types of food that are sold in Qatar and may contain pesticides residues, such as grains and dates. Future studies also should look to the presence of other type of pesticides such as organophosphorous and carbamates compounds.

Fadwa El Mellouhi1, Akinlolu Akande2, Sergey Rashkeev1, Mohamed El-Amine Madjet1, Golib Berdiyorov2, Carlo Motta2, Stefano Sanvito2 and Sabre Kais1, Fahhad Alharbi1

1Qatar Environment and Energy Research Institute, Hamad Bin Khalifa University, Qatar Foundation, Doha, Qatar

2School of Physics and CRANN, Trinity College Dublin, Ireland

In the past four years, the solar cell field has experienced an unprecedented meteoritic emergence of a new family of solar cell technologies; namely, perovskites solar cells (PSC) using (CH3NH3)PbI3 as absorber. [1] However, two main challenges prevent deploying PSC technology: the presence of the toxic element lead (Pb) and their structural instability.

The CRANN-QEERI initiative for Solar Energy Harvesting Materials (CRAQSolar project) aims at establishing a new research protocol for the rational and rapid design of advanced materials for solar energy harvesting. This will drastically accelerate the time necessary for materials discovery and will allow us to produce a new generation of photovoltaic compounds displaying high efficiency, ease of manufacturability, longevity and low costs. Our research protocol is based on the rational design of new compounds by means of state-of-the-art high-throughput electronic structure theory, followed by synthesis, processing and characterization. In particular we will target both chemical synthesis and liquid phase processing, two protocols, which guarantee handling of materials at low temperature and low costs. The grand objective of CRAQSolar is that of revolutionizing such cycle and to provide a way for producing a significant pallet of new promising compounds for further optimization. In particular the project has two targets:

Objective 1: Developing new hybrid organic/inorganic perovskites (HOIPs) with robust solar harvesting efficiency but also useful thermal and mechanical stability. These should be synthesized/processed chemically and have mobility superior to their all-organic counterparts.

Objective 2: Developing a range of compounds made of 2D materials (such as MoS2, TiS2, GaS, etc.) with strong light absorption properties and long-living excitons. These will be processed from the liquid phase so that solar cells devices may be produced by ink-jet printing.

We conducted extensive density functional theory (DFT) calculations on the prototypical light absorbing perovskite, CH3NH3PbI3, in its cubic phase, by taking into consideration the experimentally reported evidence of the fast rotation of CH3NH3 at room temperature. This compound has the standard AMX3 perovskite structure, where the cation position, A, is taken by methyl-ammonium, CH3NH3.

Ground-state total energies and forces were computed using DFT calculations with the FHI-aims all-electron quantum chemistry code [2]. These were used to optimize the crystal geometry, without the use of constraints. The GGA in the Perdew-Burke-Ernzerhof (PBE) parameterization was employed. Long-range van der Waals interactions have been taken into account via the Tkatchenko and Scheffler (TS) scheme [3]. The reciprocal space integration was performed over an 8 × 8 × 8 Monkhorst-Pack grid after performing convergence tests on the energy and forces.

Our pioneering work for this class of material consisted of lifting the limitation imposed in previous studies on the orientation of the organic molecule. This means that we did not limit our analysis to CH3NH3 oriented along the (100) or the (111) direction, for which the high Oh symmetry is maintained, but we also explore cases where the symmetry was lowered. Our main conclusion was that such symmetry lowering has profound consequences on the electronic structure namely that the bandgap changes from direct to indirect depending on the orientation of the CH3NH3 group.[4] Crucially such symmetry-lowering configurations represent local minima in the free energy surface of the crystal and they are stabilized by van der Waals (vdW) interactions. These are the key ingredients not only for obtaining accurate lattice parameters but also for the internal geometry. Our calculations then return a picture of the CH3NH3PbI3 as a “dynamical” bandgap semiconductor, in which the exact position of the conduction band minimum depends on the particular spatial arrangement of the molecules. Importantly our results are robust against bandgap corrections and spin-orbit interaction, and deliver an absorption spectrum in good agreement with experimental data near absorption edge.

These preliminary studies suggest that better efficiency might be achieved by seeking novel molecules maybe combined with different halides in order to enhance the symmetry breaking in these compounds. Our finding thus offers a design strategy to increase the efficiency of hybrid halide perovskites. This also lays a foundation in screening and designing alternative nontoxic lead-free materials.

The two classes of compounds selected for CRAQSolar's exploration encompass some among the most promising materials for developing a solar energy harvesting technology. In particular, since both can be grown and processed chemically from the liquid phase, they offer the possibility of achieving high energy-conversion efficiency, while maintaining low fabrication costs. Furthermore, these are families of compounds comprising a vast number of members with highly tunable properties, so that they are the ideal platform for a large-scale search.

Our efforts to design lead free family of hybrid materials demonstrate that the design of hybrid materials containing organic cations might require careful considerations among them the size of the cell used during the screening process. Our strategy will be presented as well as some resulting promising compounds.

Acknowledgement

Computational resources are provided by research computing at Texas A&M University at Qatar and the Swiss Super Computing Center(CSCS). This work is supported by the Qatar National Research Fund (QNRF) through the National Priorities Research Program (NPRP 8-090-2-047)

References

[1] M. Peplow, “The perovskite revolution [news],” Spectrum, IEEE, vol. 51, no. 7, pp. 16–17, 2014.

[2] V. Blum, R. Gehrke, F. Hanke, P. Havu, V. Havu, X. Ren, K. Reuter and M. Scheffler, Ab initio molecular simulations with numeric atom-centered orbitals, Comp. Phys. Comm. 180, 2175 (2009).

[3] A. Tkatchenko and M. Scheffler, Accurate molecular van der Waals interactions from ground-state electron density and free-atom reference data, Phys. Rev. Lett. 102, 073005 (2009).

[4] C. Motta, F. El Mellouhi, S. Kais, N. Tabet, F. Alharbi, and S. Sanvito, Revealing the role of organic cations in hybrid halide perovskites CH3NH3PbI3, Nature Communications 6, Article number:7026 (2015) (doi:10.1038/ncomms8026)

Karst is ubiquitous on the peninsula of Qatar, including depressions, sinkholes, and caves. Faulting and fractures play a major role in the development of karst, where fluids find pathways through limestone and dissolve the host rock. The resulting fissures may grow larger as more surface water is funneled through to form cavities or karst. Sinkholes may also form, when cavern roofs collapse, and it is this last characteristic that is of concern to rapidly growing metropolitan areas, that expand in heretofore unexplored regions. Qatar has seen a recent boom in construction, including the planning and development of complete new sub-sections of metropolitan areas. Before planning and construction can commence, the development areas need to be investigated to determine their suitability for the planned project. Of particular concern are ubiquitous karst features that are prone to collapse, particularly when surface loading is increased due to the construction of new buildings. In this paper, we present the results of a study to demonstrate a variety of seismic techniques to detect the presence of a karst analog in form of a vertical water-collection shaft located on the campus of Qatar University, Doha, Qatar. Seismic waves are well suited for karst detection and characterization. Voids represent high-contrast seismic objects that exhibit strong responses due to incident seismic waves. However, the complex geometry of karst, including shape and size, makes their imaging nontrivial. While karst detection can be reduced to the simple problem of detecting an anomaly, karst characterization can be complicated by the 3D nature of the problem of unknown scale, where irregular surfaces can generate diffracted waves of different kind. In our current paper we build upon previous results (Gritto et al, 2015) and employ a variety of seismic techniques to demonstrate the detection and characterization of a vertical water collection shaft analyzing the phase, amplitude and spectral information of seismic waves that have been scattered by the object. The experiment consisted of seismic transmission and reflection surveys, using a 10 kg sledge hammer as a source and three-component 10 Hz geophones to record the data. We used the reduction in seismic wave amplitudes and the delay in phase arrival times in the geometrical shadow of the vertical shaft to independently detect and locate the object in space. Additionally, we use narrow band-pass filtered data combining two orthogonal transmission surveys to detect and locate the object. Our analysis showed that ambient noise recordings may generate data with sufficient signal-to-noise ratio to successfully detect and locate subsurface voids. This is a result of the low intrinsic attenuation of seismic waves by the limestone and dolomite rocks that are ubiquitous throughout Qatar. Being able to use ambient noise recordings would eliminate the need to employ active seismic sources that are time consuming and more expensive to operate.

Bimetallic catalyst shows distinct physical and chemical properties differ from its monometallic catalyst due to the high synergy between the monometals. Bimetals of transition metals shows different applications in the field of catalysis, batteries and solar energy conversion etc. CuCo bimetallic catalysts are excellent candidate for the applications in the field of heterogeneous catalysis, solid state sensor, energy storage devices, and lithium-ion batteries. With the increase in fuel cell application, need of H2 source also rises. H2 can be extracted from the hydrogen rich precursors of light alcohol such as methanol and ethanol that can be produced from corn stover, starch containing materials and other biomass byproducts. Ethanol is low toxic and easy handling renewable source for H2 production for fuel cell applications and the production of ethanol is environmentally sustainable. Transition metal possess high C-C cleavage bond which is an indispensable property in ethanol conversion. Steam reforming, partial oxidation, dehydrogenation and decomposition are the main routes for the hydrogen generation from ethanol. Out of these, decomposition technique is a low temperature process and suitable for small scale fuel cell applications e.g. charging cell phones, computers etc. We follow decomposition route for H2 production along with other necessary byproducts. Bimetallic CuCo catalyst shows good performance during ethanol decomposition for hydrogen production in the temperature range of 50°C-400°C. Various physical and chemical techniques (such as thermal method, precipitation methods, pyrolysis process, sonochemical method, polyol method, microwave irradiation, sol-gel process, combustion method etc.) have been reported for the synthesis of different morphological structures of bimetallic nanoparticles In this work we are following combustion synthesis method to prepare cobalt catalysts which have been reported to be active for ethanol-hydrogen production. This work focuses primarily on understanding the reaction mechanism leading to various products using in situ DRIFTS studies. Combustion synthesis was opted for synthesis due to various advantages such as low energy requirement, single step, fast and economic synthesis process as it does not require expensive equipment. In Solution Combustion Synthesis (SCS) the precursors were mixed to form a homogenous solution and heated it over the hotplate heater to initiate the combustion process which resulted in the synthesis of nanoparticles with uniform properties. Typically, it consist a redox reaction of the homogeneous mixture of metal nitrate (oxidizing agent) and oxygen containing fuels (reducing agent) such as glycine, urea, glucose, citric acid etc. The reaction between NH3 and HNO3 released during decomposition of glycine and metal nitrate respectively produces the energy required for single step combustion synthesis. At higher value of φ, the reactive medium generates H2 rich reducing environment to convert metal oxide to metallic form Bimetallic CuCo were synthesized from the aqueous solution of cobalt nitrate (Co(NO3)2·6H2O), copper nitrate (Cu(NO3)2·6H2O) and glycine (C2H5NO2) in solution combustion synthesis (SCS) method using a fuel to oxidizer ratio of φ 0.5, 1, 1.75 and 2.5. The amount of precursors was calculated based on the synthesis of 1.5 g product in the output. These precursors were mixed in 75 ml of water and stir continuously for 1 hr to form a homogenous mixture. The solution was heated over a hot plate heater until all the water got evaporated. Once it reaches the ignition temperature, the combustion reaction started locally at one point and then spread inside the beaker. The resulted powder was grinded using a mortar and pestle to get a uniform powder to be used for catalytic investigations. Synthesized particles were characterized using XRD, SEM and TEM. Ethanol decomposition over bimetallic CuCo were conducted using in situ diffuse reflectance infrared fourier transform spectroscopy (DRIFT) study under N2 flow at different temperatures (50, 100, 200, 300, 400°C). Temperature-time profile of CuCo shows an increase in combustion temperature with increase in fuel ratio with maximum temperature at φ =  1 (stoichiometric ratio) and after that it decreases. The XRD shows the presence of copper-cobalt component in their oxidized states. Theoretical studies shows increase in particle size with maximum flame temperature. Crystalline size calculation using Scherrer formula shows the same trend in particle size calculation as in Table 1. SEM of as-synthesized nanoparticles of cobalt oxide at different molar ratios from 0.5 to 2.5 in SCS mode shows the nanoparticles of high porosity that are randomly distributes as well as agglomerated. Mostly this high porosity is due to the escaping of excess gases during combustion process. Also the EDS results are in consistent with the XRD results showing higher amount of oxide in the synthesized CuCo compound. TEM image in Fig. 1 also shows agglomeration that is common in solution combustion mode with non-uniform sized particles. Copper-cobalt oxide synthesized using combustion technique has been reduced to pure nanocrystal by passing hydrogen in the reaction chamber at 300°C. An FTIR spectrum at 50 and 100°C shows the presence of adsorbed ethanol and ethoxy species over the reduced catalyst. IR band at 3669 cm^− 1 indicates the presence of OH from adsorbed ethanol on the catalyst surface. At higher temperature the molecularly adsorbed ethoxy species is converted into acetate species along with the presence of carbonate species. After increasing the temperature from 200°C the intensity CO2 band at 2335-2367 cm^− 1 is evident. At this temperature the acetate species are dehydrogenated to acetaldehyde and other intermediate species. Strong acetate band of 1760 cm^− 1 above 200°C could be due to the transformation of acetaldehyde formed by the dehydrogenation of ethanol to either ethyl acetate or acetic acid though the nucleophilic reaction of ethoxy or hydroxyl species with the surface aldehyde. The presence of IR band between 2830-2695 cm^− 1 shows the presence of aldehyde group in the decomposition reaction. At higher temperature, the presence of carbonate species is evident with the carbonate layer formation from SEM and TEM images. This carbon layer at higher temperature hinders the action of catalyst in ethanol decomposition reaction.

Acknowledgement

This publication was made possible by JSREP grant (JSREP-05-004-2-002) from the Qatar national research fund (a member of Qatar foundation). The statements made herein are solely the responsibility of the author(s). The authors also wish to acknowledge the technical services granted by Central Laboratory Unit (CLU) and Gas Processing Centre (GPC) at Qatar University along with QU internal grant (QUUG-CENG-CHE-14/15-9) to support this research

Energy-related activities are a major contributor of greenhouse gas (GHG) emissions. A growing body of knowledge clearly depicts the links between human activities and climate change. Over the last century the burning of fossil fuels such as coal and oil and other human activities has released carbon dioxide (CO2) emissions and other heat-trapping GHG emissions into the atmosphere and thus increased the concentration of atmospheric CO2 emissions. The main human activities that emit CO2 emissions are (1) the combustion of fossil fuels to generate electricity, accounting for about 37% of total U.S. CO2 emissions and 31% of total U.S. GHG emissions in 2013, (2) the combustion of fossil fuels such as gasoline and diesel to transport people and goods, accounting for about 31% of total U.S. CO2 emissions and 26% of total U.S. GHG emissions in 2013, and (3) industrial processes such as the production and consumption of minerals and chemicals, accounting for about 15% of total U.S. CO2 emissions and 12% of total U.S. GHG emissions in 2013. This is why the adoption of hybrid and all-electric vehicles (EVs) instead of conventional gasoline powered vehicles with renewable source of power has been identified as the most effective GHG emissions mitigation strategy. This strategy not only saves considerable amounts of transportation-related CO2, but also reduces the demand for electricity in buildings, which is mainly supplied by coal-fired generation. Since solar energy is the only source of renewable energy that can be applied at a small scale (e.g. directly to the roof decking or solar window), this paper focuses only on the mitigation strategies in which EVs are powered by solar energy. One reason mitigation strategies are having difficulty delivering the desired outcome sought by policy makers is that many factors that affect the success or scale of GHG emissions reductions are uncertain and complex. Vehicle's specification (e.g. battery capacity, weight, and optimal energy use), road type and driving behavior (e.g. average speed), and environmental conditions (e.g. temperature and sunlight) are among the many factors affecting either energy consumption or generation and characterized by a significant degree of uncertainty. Thus, urban community planners and policy makers are confounded with huge amounts of unknown parameters, in which they wish to find the best solution from all feasible solutions (e.g. the largest GHG emissions reduction that a mitigation strategy can achieve) in the presence of uncertainty. The objective of this paper is to develop a stochastic mathematical model for energy consumption and mitigation strategy analysis that maximizes GHG emissions reductions based on the current demand trend and market prices. In this model, we consider EV and solar system costs, as well as the human activities (e.g. time spent in the building, time spent driving, and distance traveled) and environmental impacts (e.g. temperature, humidity, and sunlight) under uncertain conditions. What makes this study different from previous energy management or GHG emissions mitigation research is its focus on small-scale energy system and its validation process. Although mitigation actions through large-scale changes in energy system (e.g. new renewable energy power plant) will undoubtedly result in the largest GHG emissions reductions, but they also require major changes in the generation part of the energy sector and definitely need more investment. One the other hand, small-scale GHG emissions mitigation actions (e.g. EVs powered by solar energy) can be accomplished by local communities and characterized by a short decision making cycle, need much less investment, and also eliminate electricity losses in transmission and distribution systems. These all make small-scale GHG emissions mitigation strategies more practical and feasible. Another principal problem with prior energy management or GHG emissions mitigation research is that optimization models have not been validated with real data. In contrast, the proposed optimization approach is validated by comparing the estimated values of the optimal decision and actual values as realizations of the uncertain elements become known. Problem Statement The use of hybrid or EVs alone does not necessarily reduce the transportation's GHG emissions and it depends on the energy source. A conventional gasoline powered vehicle with 30 miles per gallon (mpg) fuel efficiency emits about 0.65 pounds CO2 per mile driven. In contrast, an EV with an average energy use of 3 mile per kWh emits about 0.71 pounds CO2 per mile driven when coal-fired electricity is used, and it emits 0.40 pounds CO2 per mile driven when natural gas-fired electricity is used. In order to optimize the mitigation strategies in which EVs are powered by solar energy (EV + solar power strategy), both energy supply (electricity generation) and demand (electricity consumption) sides must be considered. Research Methodology There are three primary solar systems: off-grid, grid-tied, and hybrid. Off-grid solar systems feed the extra energy the solar panels produce into batteries, while grid-tied solar systems send excess power to the electrical grid. Both off-grid and grid-tied systems yield the same amount of CO2 emissions reduction when the solar panels produce enough power for charging EV's batteries. When the solar panels are not producing the power required for charging an EV (e.g. during cloudy weather or night), however, grid-tied systems use electricity from the grid but off-grid systems use electricity stored in batteries. Depending on the electrical grid energy source in this case, a mitigation strategy using grid-tied systems may add a significant amount of CO2 to the atmosphere. Hybrid solar systems offer the flexibility of using a battery backup and being connected to the grid. Therefore, the outcome of a mitigation strategy using hybrid systems depends largely on the power generation capacity of the solar system. The area of solar panels, the solar cell efficiency and temperature coefficient, irradiance of input light, and temperature are the main factors affecting the capacity of a solar system. In the present problem, the decisions variables are the type of EV, which determines the optimal EV's energy use, the capacity of the solar system in the case of grid-tied system as well as the solar system storage capacity in the case of off-grid and hybrid system. Under a pre-specified budget constraint, the objective is to find these decision variables in such way to maximize GHG emissions reductions. The present model starts the optimization process by identifying the energy source of electricity generation. The electrical grid energy source is determined by the electricity demand at time t, Load t, and the electric power plants generating capacity, PPCj. The time index t takes integer values between 1 and N, where N is the time horizon of the analysis and the units of time measurement are hours. For instance, Load30 indicates the electricity demand on day 2, 6 AM. Smaller time horizons for the analysis and the prediction require less computation efforts but they are less accurate. To obtain a perfect reference for the best possible GHG emissions mitigation strategy, we solve a stochastic optimization problem with a prediction horizon of 1 hour over a year, thus N is 1 ×  365 × 24 = 8760 hours. The power plant index j indicates the respective set of the renewable (j = 1), nuclear- (j = 2), natural-gas (j = 3), coal- (j = 4), and oil-fired (j = 5) power plant. Load t is a probabilistic variable because it is unknown at the time the decision should be made; however, PPCj is a deterministic variable and is known for the analysis region. It is assumed that the supply level is sufficient to meet peak demand. The CO2 emissions at time t are then calculated for each type of solar system. For a grid-tied system, the CO2 emissions (measured in lb or kg) are calculated which may be positive or negative. A Negative value indicates a reduction in the CO2 emissions. When an EV is charging at time t, the energy generated by solar panel will be used in transportation sector. However, when an EV is not charging, all the energy will be used in the building. For an off-grid system, the factor that can seriously affect the CO2 emissions is the solar battery's state of charge. This factor is a function of the solar system storage capacity, and the charging duration, which starts at the last prediction horizon, and ends at time t. Once the solar batteries are fully charged, the extra energy the solar panels produce will be used only in the building. Since off-grid solar systems are not connected to the electrical grid, the energy produced by the system can meet at most the building's demand (DB) and the rest is wasted. This happens when the solar batteries are fully charged and the system is producing more energy than building's load. In the off-grid system, the EV is charged using the electricity stored in batteries. When the energy required to fully charging the EV exceeds the electricity stored in batteries, the EV will be charging using both the batteries and the electrical grid. In contrast to an off-grid solar system, no extra power is wasted in hybrid systems because they can send excess power to the electrical grid. In order to reduce more GHG emissions, the energy generated by solar panel must preferably be used to charge EV's vehicle batteries. For a grid-tied system, this happens when the EV is charging right when the solar system is producing energy. Off-grid and hybrid solar systems offer the flexibility of using a battery backup to charge the EV even when the solar system is not producing enough energy, for example during cloudy weather or night. Thus, it is assumed that the power from the solar system is first used to charge the batteries and then excess power is used in the building or fed into the electrical grid. In order to estimate the electricity generated by solar system, the distributions of stochastic variables such as solar irradiance and temperature are obtained from the weather records over the last 20 years from 1994 to 2014. Also, a database of 46 solar panels from 15 manufacturers is used to obtain solar cell efficiency and temperature coefficient. The average efficiency of 15.86% and temperature coefficient of -0.44 %/°C are used in the analysis. In order to estimate the electricity demand at a given time, the distributions of hourly load are obtained from the operable electric generating plants with a combined rated capacity of 1 MW or more over the last 18 years from 1996 to 2014. The Energy Information Administration (EIA) was the primary sources of hourly load data. Results and Conclusions Results show that among three primary solar systems (i.e. off-grid, grid-tied, and hybrid), a hybrid system consists of 7 modules of solar panels with 6 kWh storage capacity was found to be the best solution. Hybrid solar systems overcome the disadvantage of off-grid solar systems by sending the excess power to the electrical grid and reduce more CO2 emissions than grid-tied solar systems by using the electricity stored in batteries in transportation sector instead of buildings. The presented model is also capable of estimating CO2 emissions reductions from mitigation strategies in which EVs are powered by solar energy. With this capability, urban community planners and policy makers will know how long it will take for their strategy to meet GHG emissions reduction targets. The stochastic optimization problem was solved with a prediction horizon of an hour over a month. Then, CO2 emissions reductions estimated by the presented stochastic model were compared with actual data collected on an hourly basis for the analysis period of one month (720 hours). The results showed an accuracy of about 4% when the EV is powered by a grid-tied or hybrid solar system. When applied to an EV + off-grid solar power strategy, the stochastic model estimated CO2 emissions reductions 11% lower than the actual reductions. Overall, the presented stochastic model had better performance than deterministic methods for different types of solar systems.

In the present architecture of the electric power grids, energy is generated in large-scale that is remotely located from consumers and transmitted using passive high-voltage transmission networks to substations. The electric power is then delivered to consumers via medium and low-voltage distribution systems. Line frequency transformers (LFTs) enable high-efficiency and long-distance power transmission by stepping up the voltage on the transmission side. On the distribution side, the voltage is stepped down for industrial, commercial, and residential consumers. Furthermore, the traditional electric power system is characterized by hierarchical control structures with minimal feedback, limited energy storage, and passive loads. In recent years, the electric power system has been facing increasing stress due to fundamental changes in demand growth, technology change, and consumer preference. There has been a paradigm shift from centralized generation and control to distributed generation, storage and local control; in particular, there has been a global growth of investments in Renewable Energy Sources (RES) such as wind and solar. These RES generate fluctuating electric power and therefore they require Energy Storage Systems (ESS) to enable a time-shift between energy production and consumption. The high penetration of RES and other Distributed Generation (DG) types such as fuel cells (FCs) and Micro-Turbines (MTs) impose significant challenges on the operation of power system and coordination of supply and demand in real time. At the same time, the power system will need to react to events for which it was not designed for. Microgrids (MGs), being controllable small scale power networks, have become popular in distributed systems by facilitating an effective and smooth integration of distributed energy resources, loads, and energy storage devices into existing power systems. They help reduce expenditure by reducing network congestion, line losses and line costs and thereby higher energy efficiency. Power electronics converters are used in microgrids to control the routing of electricity and also provide flexible distributed generation sources interfaces to the distribution network to ensure stable and secure operation of the grid. These power converters rely on the type of microgrid (AC or DC), as well as on other features of the devices (voltage levels, power flow direction, etc.). In addition, they usually include a transformer in order to obtain galvanic isolation. The solid state transformer (SST), which is also called Electronic Power Transformer (EPT), Active Power Electronics Transformer (APET) and Intelligent TRansformer (ITR), has been proposed to replace the traditional line frequency distribution transformers. The basic operation of the SST is first to change the 50Hz AC voltage to high frequency (normally in the range of several to tens of kilohertz), then this high frequency voltage is stepped up/down by a high frequency transformer with significantly decreased volume and weight, and finally shaped back into the desired 50Hz voltage to feed the load. The SST is a power electronics circuit that provides a flexible method for interfacing microgrids with the existing Medium-Voltage (MV) power distribution system. It achieves voltage transformation via a high-frequency isolated transformer, therefore the mass and volume of the system can be reduced. Current and voltage are independently controlled via power semiconductor devices which enables grid support functions not present in the traditional LFT, including voltage and power factor regulation, fault isolation and limitation, filtering harmonic, reactive power compensation, power flow control and voltage and load disturbance rejection. However, at the present time, the commercial success of SSTs has been limited. Efforts have been made to design and implement SSTs with satisfactory performance, as well as explore its use at the distribution system level. The SST can functionally replace the traditional LFT and some power electronics converters, thus indicating a potentially more integrated and compact system. Although the concept of the SST can be seen straight forward, its implementation is a challenge. The SST combines the high voltage, high power, and high frequency operation, which make its design and operation a real challenge. To implement the SST, different power devices can be combined with different circuit topologies in different configurations. In addition, different core materials and transformer structures may be considered to build the high frequency transformer with different phase connections. Furthermore, due to power rating limitation of the semiconductor devices and magnetic components, SST topologies may have several SST cells connected in series or in parallel. Numerous degrees of freedom for the SST modularization are available, which lead to a vast amount of possible arrangements depending on the different levels of modularization in the three modularization axes: degree of power conversion partitioning; degree of phase modularity and number of levels or series/parallel connected cells. Since the level of modularity in each of these different directions is independent, these three axes can be considered to be orthogonal to each other and each element represents a specific design with a certain degree of modularization in each of the axes. The SST can be used as an enabling tool for interfacing microgrids (AC and DC) to medium voltage distribution network. For a SST-based microgrid, the performance of the microgrid mainly depends on the control algorithms of the SSTs. Generally, there are three SST control levels: system level, equipment level, and switch level. For a well-designed SST, the equipment level and firing level control strategies are well defined. However, the system level control strategy can be changed to fit different applications. In order to operate a microgrid properly and reliably, SST- based power control strategies should be developed to accommodate the modes of operation: grid-connected mode and standalone mode. That is why, the development of a controller that manages active and reactive power flow between the DC microgrid, the AC microgrid and the main distribution network is one of the most important research topic for the SST. Furthermore, investigating the effect of grid faults on the stability and performance of the SST is another hot research topic in the same area. Also, the SST can be used in different applications, such as: oil and gas and electric transportation applications. To give an overview of the SST, this work will present a review of the different levels of modularization, all possible control algorithms for the different control levels. Furthermore, stability and reliability analysis for grid connected SST will be reviewed. Finally, all possible application of the SST will be presented.

Qatar peninsula is an arid country with limited water resources. With little rainfall of approximately 80 mm per year and no surface water, aquifers are the only source of natural water in Qatar. The groundwater aquifer receives around 50 million m³ per year as natural recharge, whereas annual groundwater abstraction is more than 220 million m³, mainly used for agriculture. Groundwater occurs in a form of fresh lenses mainly in the northern part of the country, sitting atop of brackish and saline groundwater. Seawater has progressively intruded inland over the last decades because of over-pumping. As a result, the water table has dramatically dropped to unprecedented levels and salinity increased, in addition to other adverse environmental impacts. Because of its karstic nature, Qatar aquifer is prone to different sources of adverse environmental impacts. The concept of aquifer vulnerability is based on the idea that some areas above an aquifer provide more resistant to contamination than others (Vrba and Zaporozec 1994). Mapping groundwater vulnerability using hydrogeological settings gives a clear understanding of natural variation from one point to another within an aquifer. Vulnerability mapping is a powerful tool that can be used for groundwater protection and land management. In this study, vulnerability map was created based on hydrogeological parameters, land use and natural groundwater quality. All maps have been prepared and manipulated within Geographical Information System (GIS). The final vulnerability map was obtained as a sum of different rated maps using Raster Calculator. Two different approaches were used to create vulnerability maps (a) DRASTIC approach, which depends on general hydrogeological settings, and (b) EPIK approach, which focuses on karst hydrogeology. DRASTIC approach uses seven rated maps of: depth to water table, recharge, aquifer media, soil media, topography, vadose zone and hydraulic conductivity to calculate a weighted index map of vulnerability (Aller et al., 1987). EPIK approach is based on (1) epikarst, (2) protection cover, (3) infiltration rate and (4) karstic network. Depth to water table varies from a few meters near the coast to tens of meters further inland and recharge occur mainly in the many land depressions that spread all over the country. These land depressions vary in diameter from a few meters to more than two kilometers. These depressions were formed as a result of land collapse due to cavities underneath. The cavities are the result of dissolution of limestone over thousands of years. In all cases, these depressions have a high weight in vulnerability assessment. Soil may provide some sort of aquifer protection depending on its type and thickness. The dominant soil in Qatar is lithosol, which is composed of rocky soil and provide no protection. Some loamy sand exists in farm lands, which is normally derived by rainfall runoff and provide some protection cover. Aquifer media comprises limestone with dolomite, chalk and clay of variable thicknesses. Three main layers of limestone occur in Qatar. These layers are from top to bottom (1) Dam and Dammam Formation, (2) Rus Formation and (3) Umm Alraduma Formation. Results of aquifer tests show aquifer is highly heterogeneous, which is typical in karst environment with high variation of hydraulic conductivity values. A thick layer of gypsum occurs within the middle layer of limestone (Rus) in the southern part of the country and has a great implication on water quality. This layer is soluble in water, which deteriorates the groundwater quality. All the previously discussed hydrogeological settings have been used to create vulnerability maps in Qatar. While DRASTIC laid more weight on coastal sediments, as they appear to be highly vulnerable in the final map, EPIK approach laid more weights on karst formations in the middle of the country. DRASTIC approach shows high vulnerability areas occur along the coastline and in land depressions Results of both approaches show the high vulnerable areas are those were land depressions occur.

Qatar seeks to generate 2% of its electricity from solar power by 2020 (Bryden et al., 2013, REN 2015), and 20% by either 2024 (PV Insider, 2014) or 2030 (REN, 2015). Since electricity is produced almost entirely from natural gas in Qatar, these renewable energy targets introduce the prospect of natural gas savings that can be made use to increase trade and/or reduce carbon emissions. Electricity production in Qatar has been growing at a very fast pace since the mid-nineties. An estimated 7.3 millions of tons of oil equivalent (Mtoe) of natural gas were used in 2013 to produce 34.7 terawatt-hours (TWh), double the amount in 2007 and over five times as compared to 1997 (Table 1).

Table 1: Electricity production with associate natural gas (NG) use in Qatar 1971–2013. Source for electricity data: http://www.iea.org. Gas usage calculated as the estimated average efficiency for power plants using natural gas in the US for the period 2003–2013 (40.84%) estimated by the U.S. Energy Information Administration (http://www.eia.gov/electricity/annual/html/epa_08_01.html). Year – TWh produced in Qatar – NG used (Mtoe)1971 0.285 0.0601972 0.358 0.0751973 0.380 0.0801974 0.413 0.0871975 0.513 0.1081976 0.717 0.1511977 0.835 0.1761978 1.196 0.2521979 1.877 0.3951980 2.351 0.4951981 2.700 0.5691982 2.998 0.6311983 3.194 0.6731984 3.507 0.7381985 3.918 0.8251986 4.249 0.8951987 4.329 0.9121988 4.592 0.9671989 4.624 0.9741990 4.818 1.0141991 4.643 0.9781992 5.153 1.0851993 5.522 1.1631994 5.815 1.2241995 5.976 1.2581996 6.575 1.3841997 6.869 1.4461998 8.122 1.7101999 8.584 1.8072000 9.134 1.9232001 9.951 2.0952002 10.940 2.3042003 12.012 2.5292004 13.233 2.7862005 14.396 3.0312006 17.080 3.5962007 19.462 4.0982008 21.616 4.5512009 24.158 5.0872010 28.144 5.9262011 30.730 6.4702012 34.787 7.3252013 34.668 7.300

Ten-year forward projections, with cap limits of 200 Mtoe on yearly natural gas production, indicate that electricity production will peak at 48.4 TWh in 2021, with an associated natural gas use of 10.2 Mtoe (Table 2). Cap limits on natural gas production are necessary to prevent early depletion of natural gas reserves in Qatar, which have been estimated at 138 year at current output rates (QNB 2015).

Table 2: Ten-year projections (2014–2024) for electricity production and associated natural gas (NG) use in Qatar (Sanfilippo & Pedersen, in preparation). These projections assume that yearly NG production will not grow beyond 200 Mtoe. Year – Energy production (TWh) – NG needed for energy production (Mtoe) 2013 34.67 7.32014* 32.55 6.92015* 23.30 4.92016* 24.48 5.22017* 23.06 4.92018* 31.96 6.72019* 43.97 9.32020* 48.04 10.12021* 48.41 10.22022* 47.97 10.12023* 45.96 9.72024* 43.61 9.2.

The foreseen use of solar power to generate of electricity could yield a natural gas surplus of 0.2 Mtoe in 2020 and up to 1.8 Mtoe by 2024 or 2030, to reach 3.9 Mtoe thereafter, assuming a PV market peak of 43% in electricity generation – over 3.35% of Qatar total natural gas exports in 2013. This surplus could be repurposed for natural gas trade, and countries in the Far East stand as the most natural trading partners. Exports to Japan, Korea & China accounted for 41% of Qatar's NG world trade in 2013 (http://www.iea.org). Japan and Korea have historically been some of the greatest importers of natural gas from Qatar, and China is quickly emerging as a strong trading partner due to its growing need for energy. China's share in Total Primary Energy Supply (TPES) worldwide has grown from 7% in 1971 to 22% in 2013 (http://www.iea.org). China is now the world largest energy consumer with a 5% lead over the United States, the country that topped the list with 29% share of the world TPES in 1971. China's natural gas imports from Qatar rose from 0.5 to 8.8 Mtoe in only 5 years, from 2009 to 2013. Moreover, China is quickly becoming a major trading partner for Qatar. For the period 2009–2014, the trade between the two nations grew at a Compound Annual Growth Rate (CAGR) of 35.38%, as compared to 28.92% for the period 2003–2008 (http://data.imf.org). Across the same periods, Qatar's trade shows a sharp CAGR decline with both Japan (2009–2014 CAGR: 12.6 vs. 2003–2008 CAGR: 25.37%) and Korea (2009–2014 CAGR: 33.12 vs. 2003–2008 CAGR: 22.1%). Considering these market trends, China appears the most likely candidate partner for additional natural gas trade from Qatar. While the recent turbulence in Asian markets signals a slowdown in China's economy, it is unlikely that China's position as the world largest energy consumer will change in the years to come. Moreover, foreign natural gas is playing an increasingly important role in Chinese energy market (Higashi 2009). Despite plans by the Chinese government to expand domestic production, the internal Chinese natural gas market remains unbalanced (Li et al., 2014). The development and implementation of a new strategic roadmap are needed to manage the local production, marketing and transportation of gas efficiently. These changes may take decades to come to fruition, during which reliance on natural gas imports is bound to grow. In terms of carbon emissions, the amount of CO2 equivalent to the prospected 3.9 Mtoe of natural gas replaced by solar energy (see above) is 9,053,724 US tons, assuming the IEA estimate that each million British thermal units (MBtu) of energy generated by natural gas generate 117 pounds of CO2 emissions (http://www.eia.gov/tools/faqs/faq.cfm?id = 73&t = 11).

References

Bryden, J. Riahi, l., Zissler, R., (2013). MENA: Renewables Status Report. United Arab Emirates Ministry of Foreign Affairs, REN 21. International Renewable Energy Agency (IRENA).

Higashi, N. (2009). Natural gas in China. IEA Energy Markets and Security Working Papers.

Li, Z., Zhang, Q., Farfan Reyes, S., Wang, Z., (2014) Natural Gas Development strategy modeling in China. 4th International Association for Energy Economics Asian Conference, Beijing, China, September 19–21, 2014.

PV Insider, (2014). PV in MENA: Turning Policy into Projects. Retrieved on Nov 1, 2015 from http://www.pv-insider.com/menasol/pdf/policyintoplants.pdf. QNB, (2015).

QNB Economic Commentary, 21 June, 2015. REN21, (2015).

Renewables 2015 Global Status Report. http://www.ren21.net/status-of-renewables/global-status-report/. Sanfilippo, A. & Pederson, L., (in preparation).

Impacts of PV Adoption in Qatar on Natural Gas Exports to the Far East. In Lester, L. & Efird, B. (eds.) Energy Relations and Policy Making in Asia: The benefits of mutual interdependence, Palgrave Macmillan.

Among the diverse catalytic processes, the heterogeneous catalytic CO oxidation is an important reaction for removal of small amounts of poisoning CO in fuel cell applications and environmental remediation. Therefore, there is a great need to develop highly active and stable nanocatalysts for catalytic CO oxidation at low temperature. Plasmonic nanocatalysts supported on reducible metal oxide such as CeO2 and TiO2 have been known for their superior catalytic activity at very low temperature but they are expensive and could suffer from particle agglomeration and sintering at high operating temperature (Veith, Lupini et al. 2009). Transition metals supported on reducible metal oxides are good substituents catalysts because of their low cost and wide-use along with activities per unit surface area similar to those of noble metal catalysts. They been shown to possess high oxygen release capacity at high range of temperature and have been shown as good candidate materials for oxygen storage and to provide oxygen for combustion and oxidation reaction at high temperature. (Royer and Duprez 2011; Hedayati, Azad et al. 2012; Song, Liu et al. 2013). In particular, supported CuO nanostructures have received a great deal of attention as non-expensive and non-plasmonic catalysts for oxidation reaction. (Caputo, Lisi et al. 2007; Hornes, Hungria et al. 2009; Royer and Duprez 2011; In, Vaughn et al. 2012; Komarneni, Shan et al. 2012; Chen, Xu et al. 2015; Fang, Xing et al. 2015; Kim and Liu 2015) In this study, we have developed a highly stable and active CuO-TiO2 nanocatalyst that can catalyze the CO oxidation at low temperature window between 80–200°C. The CuO-TiO2 nanocatalysts were prepared by the hydrothermal synthesis of TiO2 nanotubes followed by the deposition precipitation of CuO nanoparticles in alkaline conditions. We first prepared the TiO2 nanotube support by the hydrothermal treatment of TiO2 spherical particles in strong alkaline solution at 140°C. We then synthesized a series of CuO-TiO2 catalysts by deposition precipitation at constant pH, with sodium carbonate as the alkali precipitating agent and different loading ratios of Cu to TiO2 between 2% and 30 wt.%. We studied the morphological and structural properties of prepared nanocatalysts using standard physical techniques including SEM, EDX, TEM, TGA, XRD and XPS in order to understand the structure-property relationship and to optimize their catalytic activity. We carried out multiple catalytic CO oxidation cycles in a continuous flow fixed-bed reactor at low temperature range (25–300°C) and studied the catalytic activity of the different CuO-TiO2 nanocatalysts and their stability under stream. We also studied the effect of shape of the TiO2 support and the effect of the mole ratio of CuO loading on the CO conversion rates. The catalytic activity of the single counterparts of CuO and TiO2 were measured for comparison. The experimental results revealed that the CuO nanoparticles supported on TiO2 nanostructures exhibited higher activity and enhanced CO conversion rates at lower temperature, compared to un-supported CuO nanoparticles. The increased activity at lower activation temperature is probably due to the increased degree of dispersion of the active CuO phase on the TiO2 support as concluded from the EDX mapping study. Moreover, the results showed that the correlation between the catalytic activity of CuO-TiO2 nanocatalysts and both the shape and crystalline phase of the TiO2 support. The CuO supported on TiO2 nanotubes demonstarted enhanced CO conversion rates at lower temperature compared to that supported on TiO2 nanospheres. In all samples the CuO-TiO2 nanocatalysts calcined at 400°C exhibited the anatase phase of the TiO2 nanotubes support and demonstrated higher activity. The results also showed that increasing the Cu to Ti ratio could lower the activation temperature needed for CO to CO2 conversion probably due to the enhanced synergetic effect of the two mixed metal oxides. In addition, the XPS study of the CuO-TiO2 composite oxide structure indicated high degree of oxygen deficiency in CuO-TiO2 nanocatalysts with higher Cu to TiO2 loading and this could result in CO oxidation rates. The prepared CuO-TiO2 nanocatalyst demonstrated a high stability for CO oxidation for test periods of up to 5 h under stream at 200°C. The prepared CuO-TiO2 nanocatalysts could have potential applications in hydrogen purification in fuel cell systems and for CO removal in carbon dioxide lasers and in air quality industries.

References

Caputo, T., L. Lisi, et al. (2007). “Kinetics of the Preferential Oxidation of CO over CuO/CeO2 Catalysts in H2-Rich Gases.” Industrial & Engineering Chemistry Research 46(21): 6793–6800.

Chen, G., Q. Xu, et al. (2015). “Facile and Mild Strategy to Construct Mesoporous CeO2-CuO Nanorods with Enhanced Catalytic Activity toward CO Oxidation.” ACS Applied Materials & Interfaces 7(42): 23538–23544.

Fang, B., Y. Xing, et al. (2015). “Hierarchical CuO-TiO2 Hollow Microspheres for Highly Efficient Photodriven Reduction of CO2 to CH4.” ACS Sustainable Chemistry & Engineering 3(10): 2381–2388.

Hedayati, A., A.-M. Azad, et al. (2012). “Evaluation of Novel Ceria-Supported Metal Oxides As Oxygen Carriers for Chemical-Looping Combustion.” Industrial & Engineering Chemistry Research 51(39): 12796–12806.

Hornes, A., A. B. Hungria, et al. (2009). “Inverse CeO2/CuO Catalyst As an Alternative to Classical Direct Configurations for Preferential Oxidation of CO in Hydrogen-Rich Stream.” Journal of the American Chemical Society 132(1): 34–35.

In, S.-I., D. D. Vaughn, et al. (2012). “Hybrid CuO-TiO2 − xNx Hollow Nanocubes for Photocatalytic Conversion of CO2 into Methane under Solar Irradiation.” Angewandte Chemie International Edition 51(16): 3915–3918.

Kim, H. Y. and P. Liu (2015). “Complex Catalytic Behaviors of CuTiOx Mixed-Oxide during CO Oxidation.” The Journal of Physical Chemistry C 119(40): 22985–22991.

Komarneni, M., J. Shan, et al. (2012). “Adsorption Dynamics of CO on Silica Supported CuOx Clusters: Utilizing Electron Beam Lithography To Study Methanol Synthesis Model Systems.” The Journal of Physical Chemistry C 116(9): 5792–5801.

Royer, S. and D. Duprez (2011). “Catalytic Oxidation of Carbon Monoxide over Transition Metal Oxides.” ChemCatChem 3(1): 24–65.

Song, Q., W. Liu, et al. (2013). “A high performance oxygen storage material for chemical looping processes with CO2 capture.” Energy & Environmental Science 6(1): 288–298.

Veith, G. M., A. R. Lupini, et al. (2009). “Thermal stability and catalytic activity of gold nanoparticles supported on silica.” Journal of Catalysis 262(1): 92–101.

The current study is a laboratory investigation to estimate the levels of activity concentrations of Naturally Occurring Radioactive Materials (NORM) in groundwater in the Dukhan area in the State of Qatar. The primary radionuclide associated with clear gamma-ray decay signatures of concern in NORM wastes is 226Ra (from the 238U decay series) and its decay progenies 214Pb and 214Bi. Previous studies which were conducted on radioactivity concentration in soil in the State of Qatar have shown elevated levels of enhanced radioactivity in the area, North-West Dukhan, known for its oil fields. With the original aim of investigating the correlation between the underlying geological background and any measured elevation in the activity concentration of 226Ra, an anomalously high value of 226Ra activity had been observed for a number of measured samples in our earlier work, in this particular area and in particular. The weighted mean value of the activity concentrations of 226Ra in one of the samples was found to be around approximately a factor of 10 higher than the accepted worldwide average value of 35 Bq/kg. Our first study reported a value of about 201.9 ± 1.5Stat. ± 13Syst. Bq/kg for 226Ra in one sample,¹ while our further and focused (smaller grids) investigation in the latest work determined a measured value for 226Ra of about 342.00 ±  1.9Stat. ± 25Syst. Bq/kg in a sample taken from the same locality.² This is significantly higher than all the other investigated soil samples in the current and previous work and was likely to be in a heterogeneous distribution. This was found to be attributed to the weak correlation between the levels of activity concentration of 226Ra and the type of soil in this area implying that the increased 226Ra concentration arises from discharging co-produced water directly to land surface in this area. A preliminary study on the level of natural radionuclides in eight groundwater samples for this specific area using five cutting edge techniques in the national and collaborating laboratories will be presented. About half of those samples were collected from Dukhan farms where the groundwater was used for irrigation. Measurements for 222Rn concentrations in groundwater will be conducted using Rad-7 and a Liquid Scintillator Counter (LSC) at the Physics Department, Faculty of Sciences, Princess Nora Bint Abdul Rahman University, KSA. The activity concentration of 210Po and 210Pb will also be analyzed using alpha spectrometry and LSC at the National Physical Laboratory, UK. Gamma measurements using Low-level HPGe Detector will focus on activity concentration levels of 228, 226Ra and their decay progenies 214Bi, 214Pb, 228Ac, 212Pb and 208Tl and they will be conducted at the Radiation Measurements Laboratory, Ministry of Environment, Qatar. A general chemical analysis using ICP-MS will be conducted at the laboratory of Qatar Environment and Energy Research Institute (QEERI) in order to support the radiological analysis in the project. The results of this study will be essential to further clarify the reasons behind this elevation in this area. In addition, it will help in characterizing the areas of concern and explore the beneficial use and the suitable and feasible treatment options of the co-produced water and positively contributing to the water security target.

References

1. Al-Sulaiti, H., Regan P. H., Bradley D. A., Malain D., et al., A preliminary report on the determination of natural radioactivity levels of the State of Qatar using high-resolution gamma-ray spectrometry. Nuclear Instruments and Methods in Physics Research Section A: Accelerators, Spectrometers, Detectors and Associated Equipment (NIM-A), 2010. 619(1–3): p. 427–431.

2. Huda Al-Sulaiti, Tabassum Nasir, K.S. AlMugren, et al., Determination of the Natural Radioactivity Levels in North West of Dukhan, Qatar Using High-Resolution Gamma-ray Spectrometry, Proceedings of the 8th International Topical Meeting on Industrial Radiation and Radioisotope Measurement Applications (IRRMA-8) Applied Radiation and Isotopes, July 2012, Volume 70, Issue 7, p. 1344–1350.

Abstract Background: The plant growth and production rely on the supporting favorable environmental conditions throughout its growing stages. In harsh environmental conditions such as in Qatar, agricultural growth is limited by water availability, salinity and drought, leading to low yield. In soil, there are different kinds of microbiota including fungi, bacteria, actinomycetes, algae as well as various types of plant species. Fungi are important components of the soil microbiota. For example, soil-borne fungi cause a significant yield loss for many vegetable and fruit crops in Qatar including tomatoes, cucumbers, legumes, limes, strawberries and others. Several recent studies have demonstrated that the adaptation of plants to severe environmental conditions is attributed to genetic abilities of their associated microbes. For example, all plants in natural ecosystems are thought to be symbiotic with mycorrhizal and/or endophytic fungi reflecting fitness benefits conferred by fungi that contribute to or are responsible for plant adaptation to stress. In Qatar, there are many plant species that can survive under adverse abiotic conditions of salinity and drought rendering them as rich resources for structuring their associated microbes. Objectives: The aims of this study were to: (i) investigate the effect of different ecosystems on the structure and distribution of soil-borne fungi; (ii) inspect the ability of plant-associated microbes to tolerate harsh environmental conditions; and (iii) examine the effectiveness of isolated fungi as potential biological control agents. The ultimate goal of this study is to improve the sustainable agriculture in Qatar through the implementation of plant-associated microbes for biological control of important diseases and enhance plant tolerance to abiotic stress. Materials and Methods-Isolation of plant associated microbes: Samples from plant rhizosphere and soil were collected from four different plant species grown under different ecosystems in Qatar. Qatar University Farm (Al-Zubara Area, Qatar) exemplifies the agricultural ecosystem; in addition to six private farms represent different ecosystems. Four plant species were considered in this study namely Launae capitata, Lycium shawii, Ziziphus lotus and Zygophyllum qatarense (Tetraena qatarense). Samples from plant rhizosphere and soil were collected in January. Soil-borne fungi were isolated from the rhizosphere and soil using direct plate method. About 0.5 g of homogenized soil sample was plated on melted potato dextrose agar supplemented with Rose Bengal. Plates were incubated at 25°C for 3–7 days and colonies with different morphological characters were isolated and purified. Fungal isolates were identified morphologically using light microscopy. DNA was extracted using QIAGEN kit for molecular analysis. Effect of abiotic stress on the growth of Trichoderma spp.: different concentrations of sodium chloride (NaCl) were used to induce salinity stress. NaCl concentrations include 0 (control), 10 mM, 50 mM, 100 mM, 250 mM, 500 mM, 1 M, 1.25 M, 1.5 M, 1.75 M, 2 M, 2.25 M, 2.5 M, 2.75 M and 3 M. Fifty ml of potato dextrose broth medium, with different salt level, was inoculated with five mm disc of Trichoderma spp. Poly Ethylene Glycol (PEG) was used to induce drought effect on Trichoderma spp. Different percentages of PEG were performed including 0% (control), 10%, 20%, 30%, 40%, 50%, 60%, 70%, 80%, 90% and 100%. In 100 ml conical flask; 50 ml of PDB medium with different percentages of PEG was inoculated with five mm disc of Trichoderma spp. The antagonistic effect of the fungal isolates was tested using the direct opposition method. Antagonistic test was performed between Trichoderma spp. which has an effective biocontrol activity towards many soil-borne pathogenic fungi and Ceratocystis radicicola (Thielaviopsis paradoxa), which causes many diseases in date palm trees. The test was performed in dual culture on PDA medium. Five mm disc of each fungus was placed at peripheral end (five cm between each other) of Petri plate. The plates were incubated at 25°C for 7 days. Three replicates were considered. Results: Tthirty-nine of fungal genera were isolated from the plant rhizosphere and soil. Results showed that the most dominant genus was Aspergillus niger (48.5%) followed by Rhizopus spp. (26.8%). Other fungal communities were also detected such as Aspergillus vesicolory, Aspergillus sydowii, Aspergillus wentii, Fusarium oxysporum, Penicillia oxalicum, and Rhizoctonia solani. Results also showed that Aspergillus terreus is associated with rhizosphere of plant species growing in harsh conditions. However, plants grown under agricultural conditions showed a biodiversity in their associated-fungal species, the most common fungi are Fusarium sp. and Trichoderma sp., which were isolated from rhizosphere of Launaea capitata and Ziziphus lotus grown in harsh conditions. In vitro, Trichoderma spp. was able to grow in high concentrations of salt (2 M) and PEG (80%) reflecting a high adaptation of plant associated microbes to both salinity and drought stresses. Results from the antagonistic test showed that Trichoderma spp. caused a remarkable growth inhibition of C. radicicola the causal agent of many diseases in date palm trees. Conclusion: Data obtained from the current study will lead to the initiation of a Qatari fungal culture collection, which will help conserve the biodiversity and could be essential for future studies. Additionally, plant-associated microbes isolated from different ecosystems can further be used for biological control of important plant diseases and enhancing plant tolerance to abiotic stress. Altogether, results from the current study suggest a prospective implementation of plant-associated microbes for a sustainable agriculture in Qatar.

Municipal solid waste management is one of the major challenges facing Qatar with more than 2.5 million tons of municipal solid waste each year, a very high waste generation rate in a country with small land mass. Solid waste in Qatar consists mostly of organic materials (60%) with the remaining made up of recyclables, such as glass, metals and plastics. Qatar's ambitious development strategy targets environmental sustainability and invests in research on key grand challenges including water/food security. Fortunately both can be addressed through value-added conversion of solid organic waste into biochars. Solid municipal wastes such as newspaper, cardboard, woodchips and plant residues from landscaping can be converted to biochar for mitigation of their environmental impact and value-addition. On the other hand, agricultural soils have significant deficiencies in a range of essential trace elements and macronutrients and often exhibit low water holding capacity. These deficiencies impact both the yield and the nutritional quality of edible crops with direct consequences cost-effectiveness and human health. Fortunately, these challenges can be advantageously addressed by production of biochars from organic sources such as mixed organic solid waste from municipalities as well as agricultural and landscaping operations. The landfill and composting of these solid municipal wastes generate greenhouse gases that contribute to climate changes. Biochars prepared from solid municipal wastes can greatly benefit the carbon content of soil. Additionally, biochar may interact with fertilizers to deliver indirect improvements in plant growth and reduce the emission of greenhouse gases from native organic matter. Biochars can also be custom-designed to increase/decrease native soil pH to bring it closer to the optimum range for microbial and plant growth. These applications give solid organic municipal wastes promising potential as precursors for value-added biochars with varied physicochemical characteristics allowing them to be used not only as an alternative to bio-waste management and greenhouse gas mitigation but also as means to improve depleted soil. We hypothesize that soil deficiencies in soil can be remedied by the application of biochars that are custom-designed to possess the right physicochemical characteristics suitable to improve soil fertility. The aim of this study was to: (1) produce biochars from mixed solid organic waste for use in soil quality enhancement, (2) investigate the effect of biochar addition to soil on plant germination and growth and (3) evaluate the potential of biochars in mitigating green house gas (GHGs) emissions. Select solid organic municipal wastes (newspaper, cardboard, woodchips and landscaping residues) were used as a precursor for biochar preparation. A blend of 25% of each precursor was used and pyrolyzed at 700°C for 2 hrs under N2 gas at a flow rate of 0.1 mL min^− 1 using a Lindberg box programmable furnace equipped with an air-tight retort. Soil fertility parameters such as pH, water retention and macro and micronutrients were analyzed. Fine sandy clay loam soil from the Ap horizon (0-15 cm deep) was amended with biochar at the rate of 2% (w/w). To test the germination rate in soils, with and without biochars (produced from municipal solid waste precursors of 25% blend of four types of waste materials), hybrid savoyed spinach seeds were sown in germination trays (3 seeds/well) for two weeks in climate controlled greenhouse settings. Trays were watered twice daily to maintain moisture level between 10 and 12 percent. The percentage of seed germination was calculated and the plant growth measured as dry biomass. Incubation experiments were conducted to measure GHGs production in sealed glass vials containing soil with and without biochar or raw materials from which this biochar was produced. Greenhouse gases emission differential between the biochars and their corresponding raw feedstocks in treated soil was used as indicator of GHGs emission by biochars during the incubation period Biochars prepared from blends produced at 700°C pyrolysis temperatures and used at 2% application rate to soil showed higher pH (6.8), increased water retention, and high K and NO3-N content. The net effect of these changes in soil properties positively impacted both seed germination and biomass yield of the plants (up to two folds in soil amended with biochars). At the same time, conversion of solid organic wastes into biochar enabled 14% reduction in GHGs emission compared to the solid waste precursors, as indicated by lower CO2 emission. Biochar amendment in soil significantly reduced the CO2 emission (14%), which would otherwise have increased greenhouse gas due to solid waste decomposition in soil. This differential is mainly due to respiration controlled by microbes. Soil amended with biochar closely followed the trend of soil treatment signifying no additional contribution to CO2 efflux. The increase in CO2 efflux seen in feedstock-amended soil can be attributed to the decomposition of feedstock during the time incubation period. In summary, biochars from mixed solid organic wastes at 2% carbon to soil ratio improved seed germination, increased plant biomass yield, and reduced GHGs emission compared to precursors. To reach the maximum benefits, pyrolysis conditions and feedstock selection are critical steps to produce biochars with desirable properties for specific soil amendment. From the present study, it is clear that constituents of municipal solid organic wastes hold promising potential as inexpensive precursor for value-added biochar manufacturing with varied and customizable physicochemical characteristics that would be beneficial in soil amendments while alleviating the problem of solid waste disposal and contributing to mitigation of GHGs. Further studies are need needed to confirm the reported advantages in natural field settings.

The Northeastern Qatari coast is comprised of diverse and sensitive flora and fauna such as seagrass meadows, turtles, algae, and coral reefs/patches that tolerate harsh environmental conditions. In the near future, this area may see a rise in anthropogenic activity in the form of coastal development projects, which will add to the existing natural stresses, such as high temperature, high salinity and low rates of precipitation. Therefore, there is a need to characterize the area and assess the potential impacts that these anthropogenic activities may have on the region. Eco-hydrological models are theoretical, mathematical representations of natural systems, made to help understand their functionalities under physical forcing. Site-specific data, hydrodynamic models, and ecological and physical phenomena are combined to build a functional ecosystem model that mimics real environments. These models can then be used to predict the impacts of anthropogenic and natural stressors on real systems. There are two main types of Eco-hydrological models: analytic and computational. Analytic models are usually less complex since they have an analytical solutions, and are used to represent simple or abstract systems with well-known behaviors. Alternatively, computational models are considered to be more ecologically sensible, as they can be used to solve complex systems that require the use of numerical techniques. The results of the computational model can vary between different numerical techniques or modeling software, resulting in uncertainty and variability that should be estimated. Given the complex nature of the environmental system in the Northeastern Qatari coast, numerical solutions using modeling software are developed to establish an adequate representation. There are three main modeling programs that have been used for the development of Ecological Response Models in Qatar (SWAN, GEMSS, and TELEMAC-2D). GEMSS provides a set of hydrodynamic, transportation and water quality modules allowing for the development of an integrated Eco-hydrological model according to the needs of each modeling application, which makes it the most appropriate software to use in this study. The aim of this study is to develop hydrodynamic and sediment transport models for a stretch of the Jabal Fuwairat Coastline in Qatar, using GEMSS and bathymetric LIDAR data processed with ArcGIS. The hydrodynamic model (HDM), which will be calibrated and tested using field data, simulates the spatial and temporal dynamics of the water, while the sediment transport model (STM) identifies, under present or simulated scenarios, the fate of the suspended sediments in the studied coastal zone. The STM provides data about sediment typologies, suspended particulate matter and currents that are near the seafloor (shear stress). The developed models will be tested using potential scenarios of future anthropogenic activities forecasted to take place in the area. The results will show the effects on water and sediment behavior, and provide a scientific basis for key stakeholders to make decisions with respect to the management of the considered coastal zone. It also provides a tool/framework that can be utilized in future hydrodynamic studies along other areas of the Qatari coastal zone. Furthermore, the outcomes are fundamental to developing a complete and accurate Eco-hydrological model. Keywords: Hydrodynamic Model, Sediment Transport Model, Anthropogenic stressors, coastal dynamics, GEMSS, ArcMap, LIDAR.