Grouping the criteria by pondering categories (PC)
\\n\\n
Released this past November, the list is based on data collected from the Web of Science and highlights some of the world’s most influential scientific minds by naming the researchers whose publications over the previous decade have included a high number of Highly Cited Papers placing them among the top 1% most-cited.
\\n\\nWe wish to congratulate all of the researchers named and especially our authors on this amazing accomplishment! We are happy and proud to share in their success!
\\n"}]',published:!0,mainMedia:null},components:[{type:"htmlEditorComponent",content:'IntechOpen is proud to announce that 179 of our authors have made the Clarivate™ Highly Cited Researchers List for 2020, ranking them among the top 1% most-cited.
\n\nThroughout the years, the list has named a total of 252 IntechOpen authors as Highly Cited. Of those researchers, 69 have been featured on the list multiple times.
\n\n\n\nReleased this past November, the list is based on data collected from the Web of Science and highlights some of the world’s most influential scientific minds by naming the researchers whose publications over the previous decade have included a high number of Highly Cited Papers placing them among the top 1% most-cited.
\n\nWe wish to congratulate all of the researchers named and especially our authors on this amazing accomplishment! We are happy and proud to share in their success!
\n'}],latestNews:[{slug:"stanford-university-identifies-top-2-scientists-over-1-000-are-intechopen-authors-and-editors-20210122",title:"Stanford University Identifies Top 2% Scientists, Over 1,000 are IntechOpen Authors and Editors"},{slug:"intechopen-authors-included-in-the-highly-cited-researchers-list-for-2020-20210121",title:"IntechOpen Authors Included in the Highly Cited Researchers List for 2020"},{slug:"intechopen-maintains-position-as-the-world-s-largest-oa-book-publisher-20201218",title:"IntechOpen Maintains Position as the World’s Largest OA Book Publisher"},{slug:"all-intechopen-books-available-on-perlego-20201215",title:"All IntechOpen Books Available on Perlego"},{slug:"oiv-awards-recognizes-intechopen-s-editors-20201127",title:"OIV Awards Recognizes IntechOpen's Editors"},{slug:"intechopen-joins-crossref-s-initiative-for-open-abstracts-i4oa-to-boost-the-discovery-of-research-20201005",title:"IntechOpen joins Crossref's Initiative for Open Abstracts (I4OA) to Boost the Discovery of Research"},{slug:"intechopen-hits-milestone-5-000-open-access-books-published-20200908",title:"IntechOpen hits milestone: 5,000 Open Access books published!"},{slug:"intechopen-books-hosted-on-the-mathworks-book-program-20200819",title:"IntechOpen Books Hosted on the MathWorks Book Program"}]},book:{item:{type:"book",id:"5437",leadTitle:null,fullTitle:"Developments in Near-Infrared Spectroscopy",title:"Developments in Near-Infrared Spectroscopy",subtitle:null,reviewType:"peer-reviewed",abstract:"Over the past few decades, exciting developments have taken place in the field of near-infrared spectroscopy (NIRS). 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Eissa’s publications have 349 total citation cited by 291 documents in Scopus and he has H-index= 10 from 1995 at (1st of January, 2015)\n• http://www.scopus.com/authid/detail.url?authorId=35581693900\nGOOGLE SCHOLAR CITATIONS\n• M.M. Eissa’s publications on Google Scholar Citation is 520 and H-index=12\nCitation Indices = 520 h-index = 12\nhttp://scholar.google.com/citations?hl=en&user=5useqg4AAAAJ\nProf. Moustafa Mohammed Eissa (Digital Protection, Smart Grid, Wide Area Monitoring and Application, Grid Modeling and assessment, Smart Grid based on GIS) (www.helwan-ntra.com)\nProf. at Faculty of Engineering-Helwan University-Cairo-EGYPT\n\nM. M. Eissa (M’96–SM’01) was born in Helwan, Cairo, Egypt, on May 17, 1963. He received the B.Sc. and M.Sc. degrees in electrical engineering from Helwan University, Cairo, in 1986 and 1992, respectively, and the Ph.D. degree from the Research Institute for Measurements and Computing Techniques. Hungarian Academy of Science Budapest, Hungary, in 1997 (PhD Study is cooperated with Duisburg University-Institute of Electrical Engineering-GERMANY). Currently, he is a Professor with Helwan University. In 1999, he was invited to be a Visiting Research Fellow at the University of Calgary, Calgary, AB, Canada. He was a chair Prof. at King Abdul-Aziz University-KSA for sponsored project \\Demand Side Management and Energy Efficiency\\ from Saudi Electricity Company during period 2008-2010. From 2012, he is the PI for the large scale project \\SMART GRID FREQUENCY MONITORING NETWORK (FNET) ARCHITECTURE AND APPLICATIONS-220kV/500kV\\ NTRA-Egypt (www.helwan-ntra.com)-2012, END-USER Egyptian Electricity Company. From 2013, he is the PI for \\NOVEL OPTIMAL WIDE AREA COORDINATING PROTECTION AND CONTROL SYSTEM BASED ON WIDE-AREA SYNCHRONIZED MEASUREMENTS IN SYSTEMS WITH RENEWABLE ENERGY RESOURCES AND MULTIPLE FACTS EFFECT\\.\n\nDr. Eissa initiated the first application in 2010 at the Middle East by applying the smart grid and the wide area monitoring and application on the Egyptian 220kV/500kV Cairo Zone Grid.\n\nDr. Eissa is the author of more than 120 publications (40/120 IEEE, IET and Elsevier journal papers), including books, book chapters, and papers in the area of digital protection, demand side management and smart grid.\n\nHe is invited as speaker in several Universities and international events, and involved in many Technical Program Committees for international conferences. \n\n150 citations are listed in Web of Science (as of 4th of April 2012)\n\nDr. Eissa received \\State country prize in the advanced technology science from Academy of Scientific Research and Technology (Egypt), 2002, (http://www.asrt.sci.eg)\\, \\Distinguished Researcher Award, October 2005, University of Helwan, and \\Incentive Researcher Award, 2011, University of Helwan (www.helwn.edu.eg). Incentive Researcher Award, 2012- Awarded from \\Program for Continuous Improvement and Qualifying for Accreditation\\ - Ministry of Higher Education-Egypt. (high Citation according to ISI and Scopus)- http://www.qaap.edu.eg/\n\nHe has 7 major scientific reports and more than 150 collected materials in different topics related to industry. \n\nHe has many novel techniques in the digital protections. He has many consultations with the industrial sectors. He has many international and local projects. He has numerous honors for his research, leadership, supervision and teaching. His research interests include topics related to Digital Protection, Smart Grids, Wireless application on power system, Wide area Protection, Demand Side Management, Energy Efficiency, Control Schemes for Renewable Energy Resources using Harmony Search Algorithms, Power Quality and Automation system, Smart Grid based on GIS.",institutionString:null,position:null,outsideEditionCount:0,totalCites:0,totalAuthoredChapters:"4",totalChapterViews:"0",totalEditedBooks:"3",institution:{name:"Helwan University",institutionURL:null,country:{name:"Egypt"}}}],coeditorOne:null,coeditorTwo:null,coeditorThree:null,coeditorFour:null,coeditorFive:null,topics:[{id:"770",title:"Renewable Energy",slug:"engineering-energy-engineering-renewable-energy"}],chapters:[{id:"40210",title:"Load Management System Using Intelligent Monitoring and Control System for Commercial and Industrial Sectors",slug:"load-management-system-using-intelligent-monitoring-and-control-system-for-commercial-and-industrial",totalDownloads:13542,totalCrossrefCites:3,authors:[{id:"35245",title:"Prof.",name:"Moustafa",surname:"Eissa",slug:"moustafa-eissa",fullName:"Moustafa Eissa"}]},{id:"40214",title:"Environmental Design in Contemporary Brazilian Architecture: The Research Centre of the National Petroleum Company, CENPES, in Rio de Janeiro",slug:"environmental-design-in-contemporary-brazilian-architecture-the-research-centre-of-the-national-petr",totalDownloads:2067,totalCrossrefCites:0,authors:[{id:"143770",title:"Prof.",name:"Joana",surname:"Goncalves",slug:"joana-goncalves",fullName:"Joana Goncalves"}]},{id:"40209",title:"Energy Efficient Mobility Management for the Macrocell – Femtocell LTE Network",slug:"energy-efficient-mobility-management-for-the-macrocell-femtocell-lte-network",totalDownloads:2633,totalCrossrefCites:3,authors:[{id:"19443",title:"Dr.",name:"Christos",surname:"Verikoukis",slug:"christos-verikoukis",fullName:"Christos Verikoukis"},{id:"141076",title:"MSc.",name:"Dionysis",surname:"Xenakis",slug:"dionysis-xenakis",fullName:"Dionysis Xenakis"},{id:"145705",title:"Dr.",name:"Nikos",surname:"Passas",slug:"nikos-passas",fullName:"Nikos Passas"},{id:"145707",title:"Dr.",name:"Ayman",surname:"Radwan",slug:"ayman-radwan",fullName:"Ayman Radwan"},{id:"150701",title:"Dr.",name:"Jonathan",surname:"Rodriguez",slug:"jonathan-rodriguez",fullName:"Jonathan Rodriguez"}]},{id:"40204",title:"Tools and Solution for Energy Management",slug:"tools-and-solution-for-energy-management",totalDownloads:2234,totalCrossrefCites:1,authors:[{id:"71933",title:"Prof.",name:"Soib",surname:"Taib",slug:"soib-taib",fullName:"Soib Taib"}]},{id:"40205",title:"High Efficiency Mix Energy System Design with Low Carbon Footprint for Wide-Open Workshops",slug:"high-efficiency-mix-energy-system-design-with-low-carbon-footprint-for-wide-open-workshops",totalDownloads:1576,totalCrossrefCites:0,authors:[{id:"142253",title:"Dr.",name:"Tomas",surname:"Gil-Lopez",slug:"tomas-gil-lopez",fullName:"Tomas Gil-Lopez"},{id:"144313",title:"Dr.",name:"Miguel A.",surname:"Galvez-Huerta",slug:"miguel-a.-galvez-huerta",fullName:"Miguel A. Galvez-Huerta"},{id:"144337",title:"Dr.",name:"Juan",surname:"Castejon-Navas",slug:"juan-castejon-navas",fullName:"Juan Castejon-Navas"},{id:"155420",title:"Mr.",name:"Paul G.",surname:"O'Donohoe",slug:"paul-g.-o'donohoe",fullName:"Paul G. O'Donohoe"}]},{id:"40213",title:"Energy Efficient Control of Fans in Ventilation Systems",slug:"energy-efficient-control-of-fans-in-ventilation-systems",totalDownloads:2474,totalCrossrefCites:0,authors:[{id:"146401",title:"Dr.",name:"Bjorn R",surname:"Sorensen",slug:"bjorn-r-sorensen",fullName:"Bjorn R Sorensen"}]},{id:"40201",title:"Increasing the Energy Efficiency in Compressed Air Systems",slug:"increasing-the-energy-efficiency-in-compressed-air-systems",totalDownloads:3545,totalCrossrefCites:2,authors:[{id:"142441",title:"Dr.",name:"Dragan",surname:"Seslija",slug:"dragan-seslija",fullName:"Dragan Seslija"},{id:"145589",title:"Ph.D. Student",name:"Ivana",surname:"Ignjatović",slug:"ivana-ignjatovic",fullName:"Ivana Ignjatović"},{id:"145591",title:"MSc.",name:"Slobodan",surname:"Dudić",slug:"slobodan-dudic",fullName:"Slobodan Dudić"}]},{id:"40212",title:"Pumped-Storage and Hybrid Energy Solutions Towards the Improvement of Energy Efficiency in Water 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Countries",slug:"comparing-the-dynamic-analysis-of-energy-efficiency-in-china-with-other-countries",totalDownloads:1214,totalCrossrefCites:0,authors:[{id:"146333",title:"Prof.",name:"Liang",surname:"Liang",slug:"liang-liang",fullName:"Liang Liang"},{id:"149913",title:"Dr.",name:"Chenchen",surname:"Yang",slug:"chenchen-yang",fullName:"Chenchen Yang"},{id:"149914",title:"Prof.",name:"Feng",surname:"Yang",slug:"feng-yang",fullName:"Feng Yang"},{id:"149915",title:"MSc.",name:"Xiping",surname:"Xu",slug:"xiping-xu",fullName:"Xiping Xu"}]},{id:"40203",title:"The Reliability Design and Its Direct Effect on the Energy Efficiency",slug:"the-reliability-design-and-its-direct-effect-on-the-energy-efficiency",totalDownloads:1808,totalCrossrefCites:3,authors:[{id:"147403",title:"Dr.",name:"Seongwoo",surname:"Woo",slug:"seongwoo-woo",fullName:"Seongwoo Woo"},{id:"150964",title:"Dr.",name:"Jungwan",surname:"Park",slug:"jungwan-park",fullName:"Jungwan Park"},{id:"150965",title:"Dr.",name:"HongGyu",surname:"Jeon",slug:"honggyu-jeon",fullName:"HongGyu Jeon"},{id:"151661",title:"Dr.",name:"Jongyun",surname:"Yoon",slug:"jongyun-yoon",fullName:"Jongyun Yoon"}]},{id:"40217",title:"Data Processing Approaches for the Measurements of Steam Pipe Networks in Iron and Steel Enterprises",slug:"data-processing-approaches-for-the-measurements-of-steam-pipe-networks-in-iron-and-steel-enterprises",totalDownloads:1451,totalCrossrefCites:0,authors:[{id:"141056",title:"Associate Prof.",name:"Xian-Xi",surname:"Luo",slug:"xian-xi-luo",fullName:"Xian-Xi Luo"},{id:"144411",title:"Prof.",name:"Mingzhe",surname:"Yuan",slug:"mingzhe-yuan",fullName:"Mingzhe Yuan"},{id:"144412",title:"Prof.",name:"Hong",surname:"Wang",slug:"hong-wang",fullName:"Hong Wang"},{id:"157210",title:"Dr.",name:"Li",surname:"Yuezhong",slug:"li-yuezhong",fullName:"Li Yuezhong"}]},{id:"40211",title:"Transport Intensity and Energy Efficiency: Analysis of Policy Implications of Coupling and Decoupling",slug:"transport-intensity-and-energy-efficiency-analysis-of-policy-implications-of-coupling-and-decoupling",totalDownloads:1614,totalCrossrefCites:4,authors:[{id:"140686",title:"Dr",name:"Rafaa",surname:"Mraihi",slug:"rafaa-mraihi",fullName:"Rafaa Mraihi"}]},{id:"40208",title:"Tools for Categorizing Industrial Energy Use and GHG Emissions",slug:"tools-for-categorizing-industrial-energy-use-and-ghg-emissions",totalDownloads:1091,totalCrossrefCites:0,authors:[{id:"149510",title:"MSc.",name:"Teuvo",surname:"Aro",slug:"teuvo-aro",fullName:"Teuvo Aro"}]},{id:"40206",title:"Hierarchical Adaptive Balanced Routing Protocol for Energy Efficiency in Heterogeneous Wireless Sensor Networks",slug:"hierarchical-adaptive-balanced-routing-protocol-for-energy-efficiency-in-heterogeneous-wireless-sens",totalDownloads:3275,totalCrossrefCites:1,authors:[{id:"142233",title:"PhD.",name:"Said",surname:"Ben Alla",slug:"said-ben-alla",fullName:"Said Ben Alla"}]},{id:"40202",title:"Street Lighting 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Vetrò"},{id:"145828",title:"Prof.",name:"Maurizio",surname:"Morisio",slug:"maurizio-morisio",fullName:"Maurizio Morisio"}]},{id:"40220",title:"Energy Efficiency in Cooperative Wireless Sensor Networks",slug:"energy-efficiency-in-cooperative-wireless-sensor-networks",totalDownloads:2087,totalCrossrefCites:0,authors:[{id:"13847",title:"Dr.",name:"Richard Demo",surname:"Souza",slug:"richard-demo-souza",fullName:"Richard Demo Souza"},{id:"141158",title:"Dr.",name:"Glauber",surname:"Brante",slug:"glauber-brante",fullName:"Glauber Brante"},{id:"142430",title:"MSc.",name:"Marcos",surname:"Tomio Kakitani",slug:"marcos-tomio-kakitani",fullName:"Marcos Tomio Kakitani"}]}],productType:{id:"1",title:"Edited Volume",chapterContentType:"chapter",authoredCaption:"Edited 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Kosyachenko",coverURL:"https://cdn.intechopen.com/books/images_new/4479.jpg",editedByType:"Edited by",editors:[{id:"6262",title:"Prof.",name:"Leonid A.",surname:"Kosyachenko",slug:"leonid-a.-kosyachenko",fullName:"Leonid A. Kosyachenko"}],productType:{id:"1",chapterContentType:"chapter",authoredCaption:"Edited by"}},{type:"book",id:"1290",title:"Solar Cells",subtitle:"New Aspects and Solutions",isOpenForSubmission:!1,hash:"52415367e48e5b68d47325bdfc81cdce",slug:"solar-cells-new-aspects-and-solutions",bookSignature:"Leonid A. Kosyachenko",coverURL:"https://cdn.intechopen.com/books/images_new/1290.jpg",editedByType:"Edited by",editors:[{id:"6262",title:"Prof.",name:"Leonid A.",surname:"Kosyachenko",slug:"leonid-a.-kosyachenko",fullName:"Leonid A. Kosyachenko"}],productType:{id:"1",chapterContentType:"chapter",authoredCaption:"Edited by"}},{type:"book",id:"3676",title:"Solar Collectors and Panels",subtitle:"Theory and Applications",isOpenForSubmission:!1,hash:null,slug:"solar-collectors-and-panels--theory-and-applications",bookSignature:"Reccab Manyala",coverURL:"https://cdn.intechopen.com/books/images_new/3676.jpg",editedByType:"Edited by",editors:[{id:"12002",title:"Associate Prof.",name:"Reccab",surname:"Manyala",slug:"reccab-manyala",fullName:"Reccab Manyala"}],productType:{id:"1",chapterContentType:"chapter",authoredCaption:"Edited by"}},{type:"book",id:"1289",title:"Solar Cells",subtitle:"Silicon Wafer-Based Technologies",isOpenForSubmission:!1,hash:"76fb5123cd9acbf3c37678c5e9bd056a",slug:"solar-cells-silicon-wafer-based-technologies",bookSignature:"Leonid A. Kosyachenko",coverURL:"https://cdn.intechopen.com/books/images_new/1289.jpg",editedByType:"Edited by",editors:[{id:"6262",title:"Prof.",name:"Leonid A.",surname:"Kosyachenko",slug:"leonid-a.-kosyachenko",fullName:"Leonid A. Kosyachenko"}],productType:{id:"1",chapterContentType:"chapter",authoredCaption:"Edited by"}}]},chapter:{item:{type:"chapter",id:"38102",title:"Methodology for the Regional Landfill Site Selection",doi:"10.5772/45926",slug:"methodology-for-the-regional-landfill-site-selection",body:'One of the most important causes of environmental pollution is certainly an inadequate waste management. The three factors that have primarily influenced this problem area are: ever increasing amount of municipal solid waste (which causes increasingly pronounced space occupation), increasing amount and types of hazardous waste, as well as lack of awareness on the importance of acting promptly in this field. Particular problems in waste management occur in developing countries, where the awareness of the importance of environmental protection has not yet achieved a satisfactory level and where, out of economic or political reasons, professional guidelines associated with waste management are not observed. Problems emerge either due to a lack of legislation, or obsolete legislation, lack of trained personnel, inadequate waste management infrastructure, financial constraints in the establishment of a modern waste management system, population lacking the awareness about solid waste management, impossibility of selecting appropriate space for landfill development, lack of standards, etc.
Great problems in waste management in Serbia are caused by increasing amount of waste, lack of sanitary landfills built under international standards (which is inefficient and ecologically acceptable), as well as by the fact that the principle of hierarchy in waste management is not observed at all. Problems emerging in the field of environmental pollution and the manner of responding to pollution through the planning documentation, only increase the importance of this problem area.
Waste management is a complex process which implies a control of the entire waste management system (from waste generation, through collection and transportation of waste, to waste treatment and disposal), along with the support of legislation and appropriate institutional organization. The accent in the present paper is placed on spatial planning as an inevitable instrument for strategic waste management. The paper also points out the importance of spatial aspect in the waste management planning process.
The final functional element in the waste management system is waste disposal. Waste disposal is a final fate of all types of waste, either municipal solid waste, collected and transported directly to landfills, or industrial waste or other materials from waste treatment facilities which are of no use-value any longer [1].
Landfill forms the basis of every waste management plan, because there will always be waste to be disposed of.
Sanitary landfills are sites selected for waste disposal, such as natural or artificial (excavated) depressions, engineered facilities, where the waste is, through appropriate technological processes, compacted as densely as practicable to minimize its volume and covered with a layer of soil or some other material in a systematic and sanitary manner. Before proceeding with such work, a terrain to be used must be selected, surveyed and prepared [2].
Sanitary landfills are necessary in any combination, even for some other form of solid waste treatment, because there will always be waste to be disposed of. Uncontrolled dumps must be closed along with necessary sanitation. This requires knowledge of a series of notions, processes and activities which should enable proper landfill planning, design, construction, exploitation and funding, as well as control of landfill environmental impacts [3].
Considering that waste management system is realized in space, it is quite clear that characteristics of space greatly determine the choice of an adequate management system, i.e. its spatial organization. This primarily refers to the selection of sites having physical elements of the system, such as, primarily, sanitary landfills, transfer stations, recycling centers, etc. In this context, physical-geographical and anthropogenetic characteristics of space are of great importance. Relative to these characteristics, conceptual solutions to the waste management system are defined, and landfill site selection process is carried out for elements of the waste management system.
In the waste disposal process, a controlled disposal procedure is unavoidable, either for the disposal of genuine waste or materials that remain after the treatment process, or, as necessary, if the main process cannot be carried out in certain period because of interruption, defect, overhaul, or out of other reasons. Sanitary landfills are necessary in any chosen waste management option, because there will always be waste to be disposed of on landfills. In this sense, locating potential landfill sites, as the most commonly used process through which a huge amount of collected waste is treated, should be given great attention in the waste management process, i.e. in spatial planning process. This is a very delicate and very important process from the viewpoint of the protection of key environmental factors (land, water and air), landscape values, as well as the protection of population health [4]. Out of this reason, it is also necessary to dedicate great attention to the investigation of a character, as well as potential and real landfill impact on the environment. This enables the elaboration and implementation of measures to eliminate or minimize negative effects.
Sanitary landfill planning and construction is only a part of a complex solid waste management process which encompasses the treatment of waste from its generation, through minimization of its amount, selection, recycling, collection, transport and disposal, to landfill recultivation and bringing of land to new use. However, although sanitary landfills are only a part of a wider waste management process, this activity is characterized by a very complex and long-term process which must take into account natural and anthropogenetic characteristics of space.
Sanitary landfill is available land for solid waste disposal at which engineering methods of waste disposal are used in a manner in which threats to the environment are minimized. The landfill site selection and technology of devices and equipment for sanitary waste treatment and disposal should be in the function of the protection and rational use of space.
Sanitary landfill development implies activities in several phases where certain sequence must be obeyed. The process is usually carried out in four phases:
landfill site selection (site investigation process),
identification of a landfill site (through the planning documentation) and elaboration of conditions for bringing it to the intended use,
elaboration of construction (technical) documentation,
landfill construction.
It is necessary to consider the following requirements and requirements for sanitary landfill construction:
Spatial and urban planning requirements
Spatial and regional requirements
Landfill site selection
Required land area
Transportation distances
Local site conditions
Topography
Climate conditions
Hydrogeological conditions
Geological conditions
Geo-mechanical conditions
Environmental protection
Complete sanitary security for people living in the surrounding residential areas, as well as personnel working at landfills
Protection of land, air, ground and surface water from pollution
Rational use of land, as well as save land (increased levels of waste compaction using special machines, as well as a deposition height)
Maximum number of machines and equipment for all types of works
Information system is an arranged set of information on things and facts in surroundings, with the aim to get acquainted with a system. Right decision making in planning and space organization depends to a great extent on knowledge, i.e. the quality and importance of information available to decision makers.
The GIS is a powerful set of computer tools for collecting, storing, searching as necessary, transformation and display of real-world data for various purposes [6].
As one of the most complex information systems that cover all spatial problems, the GIS has many advantages out of which the most significant are:
It covers all elements of geo-space and ecological elements
It includes natural and social elements of space
The use of GIS is appropriate for:
Spatial planning
Mapping for various purposes
Traffic planning
Waste management planning
Natural resource inventory and management
Computer mapping of population and entering of census data
Creating hazard maps and programs of procedures in such cases, etc.
Essentially, GIS contains data on:
Earth’s surface
Water areas
Lithosphere
Biocenosis
Anthropogenetic spatial elements, etc.
The GIS, as already mentioned, consists of spatial data and descriptive data.
Spatial data refer to locations, i.e. spatial relationships between phenomena and objects. They are obtained based on literature, maps, aerial photos taken from aircrafts, etc., and they are useful only if they can be converted into maps. Descriptive data are linked to localities, polygon line or body and are the system accompanying content.The GIS key features are:
Possibility of spatial search of phenomena
Possibility of overlapping contents and combining individual contents into a new quality
Logical operations with spatial and descriptive data
Geographic information systems are most frequently compatible with most of related systems (geodetic, agricultural, geologic, mining, water resources management, forestry, urban planning systems, etc.), but also with census databases, statistical information systems, technological databases, databases associated with health, education, science, etc. Using GIS mapped data, we carry out precisely what an information system should enable: solve a problem, make queries, reach answers, or examine possible solutions. Here, data are manipulated digitally, and not manually, because we manipulate the data on events and activities using digital cartographic objects. In other words, the points, lines and areas in this cartographic database are used for data management.
Therefore, the GIS is a general tool for problem solving. It is created for making a certain project. A successful GIS is built, not bought, and indented for analysts to draw out relevant data for forecasting and planning, as well as various pieces of information associated with a specific space, as well as the problem area which is a subject of analysis.
The role of GIS tools in waste management planning is dominant in landfill site selection process. In addition, GIS tools are also used for distribution and identification of locations for other elements of waste management system such as transfer station network, waste selection and processing centers, for defining transportation corridors, etc.
The method of multicriteria analyses and evaluation is used for identifying locations of elements of a waste management system in the GIS. This approach is inevitable in locating complex objects, such as, for example, regional municipal solid waste landfills. Its complexity is reflected both in the size and function of objects, as well as in relation to various possible spatial impacts, also in negative context.
The use of GIS in defining strategies, analyses and visualization of solutions and alternatives helps us consider and clearly represent various scenarios, as well as select the most suitable solutions through a prism of different relevant criteria (spatial, ecological, hydro-geological criteria, etc.) [7].
Therefore, in using the GIS in the selection of the most suitable landfill sites, two things of key importance are [8].:
Analysis of space, i.e. all of its physical-geographical and anthropogenetic characteristics. It is necessary to comprehensively consider the space on which the problem is to be solved or which can be useful for problem solving. In this process, because of social sensitivity associated with this issue, it is necessary to be impartial in considering a possible landfill site. This can only be achieved if the entire space is considered to the same level of detail and in the same manner;
Visualization of space and its characteristics and impacts. This is necessary so that all participants in the project could have equal chance to perceive and understand the subject problem area. This enables active participation in searching for solutions to an acceptable compromise [9]. All participants must consider the space, as well as its advantages and disadvantages for landfill site selection. This is precisely one of the most important advantages of using GIS tools in landfill site selection, as well as of choosing other elements of a waste management system.
Defining landfill site selection criteria is the main step in landfill site selection process. In the first phase, based on exclusiveness, the sites which do not satisfy these criteria are eliminated. Positive areas within which it is possible to search for the most suitable solutions are the result of this process. This phase represents an activity of microzoning. Using GIS tools, through overlapping cartographic presentations of a certain space carried out based on exclusion criteria, it is rather simple to eliminate unsuitable landfill sites.
After eliminating the unsuitable landfill sites, the attention is dedicated to the nomination of landfill sites within the remaining \'\'conditionally suitable\'\' zones. In this process, local governments and professional institutions can and must be of great importance, but soil investigations and collecting relevant data on physical-geographical and anthropogenetic characteristic of space are indeed of utmost importance.
Through nominating potential landfill sites, preconditions for the selection of the most suitable landfill site are created, which is followed by multicriteria analysis and evaluation of candidate sites. Site selection criteria are entered into tables and weighted for each candidate site based on the entered value scale. In this way, the evaluation process using GIS tools is carried out in an efficient manner and in a short period of time.
The role of GIS tools in the landfill site selection process is in that it enables faster singling out and clearer presentation of suitable and unsuitable sites based on previously given criteria.
In this context, it is evident that selection criteria and value scale for evaluation of candidate landfill sites are of key importance in this process, while GIS tools represent a powerful means which to a great extent facilitate and speed up the process. This refers not only to the landfill site selection process, but also to defining the spatial organization of the entire waste management system, as well as defining the transfer station network.
The most important step in this process is to define landfill site selection criteria.
There are two groups of criteria. The first group includes the so-called exclusion criteria that are used in the first phase of the landfill site selection process. Exclusion criteria are defined relative to the specific situation and they represent restriction criteria.
Some of exclusion criteria can be classified into a group of the following indicators:
Distance from natural elements of space (watercourses, water sources, protected natural resources, etc.)
Distance from anthropogenetic elements of space (infrastructure facilities, settlements, protected cultural structures, etc.)
Terrain morphology
Hydrological and geological characteristics of space
Degradation of space
Recommendations of local authorities in a form of intermunicipal corporation agreements, etc.
According to exclusion criteria, areas which should not be further analyzed are discarded, i.e. areas that will be analyzed and evaluated in consecutive phases singled out. In the elimination phase, a single-criterion method is mainly used.
After that, in cooperation with local institutions and experts, certain number of sites are nominated for which a multicriteria evaluation is carried out. In this context, criteria based on which each candidate site will be evaluated in the same way are defined. This is a second group of criteria.
Site evaluation criteria are mainly classified into several basic groups. Commonly, there are three basic groups of criteria whose definition varies from author to author:
Ecological or environmental criteria,
Socio-economic or social or spatial criteria,
Technical and operational criteria (which usually also involve certain economic, spatial and ecological criteria).
Any variation of groups of basic indicators is possible. Regardless of the formulation of basic groups of criteria, they include approximately either the same or almost the same number of indicators and criteria that are analyzed and compared in the process of selection of the most suitable site for a landfill.
Number of landfill site selection criteria ranges from 20 to over 40. They are classified (or not classified) into groups of criteria to which they belong, which are also similar, but can be differently formulated.
A particularly sensitive and important step in landfill site selection that follows the choice of relevant criteria is to define value scales based on which each individual criteria is evaluated (valued, ranked). Each criteria is assigned its corresponding weight (value) which is determined based on expert’s evaluation and evaluation of participants in the process of sanitary landfill site selection. Here, quantitative evaluation is commonly used (e.g. scores from 1 to 10, or from 1 to 5).
Qualitative/expert assessment can also be used, where criteria can be assessed as suitable, conditionally suitable or unsuitable. Qualitative assessment is today increasingly less used, because the use of new technologies enable more accurate and more sophisticated assessment under the principle of quantitative assessment. In this case, accurate and objective data are obtained that can be compared and used for making right decisions.
When a potential site is assessed according to all given criteria, it is possible to carry out the following two steps:
Adding up all obtained scores
Multiplying the obtained scores by importance values (weights).
The first step in evaluating candidate sites is the simplest one and will low requirements. The best score is obtained through adding up all obtained scores for each criterion. Evaluation of candidate site in this case does not have different scenarios that can be of great help to decision makers.
The second step is more complex as different scenarios can be used. For example, if criteria for locating candidate landfill site are classified into several basic groups, then the number of scenarios to be considered is consistent with the number of criteria groups. Criteria from one group are favored in the first scenario, the most important criteria in the second scenario are those from the second group, and so on. The final option is a situation when groups of criteria are multiplied by the same importance value, without favoring any of criteria group. By presenting the scenarios in synthesis Table, it is easy to identify which candidate sites are the most suitable in which scenarios. The PROMETHEE method [10] is an example of this approach.
The basic advantage of this procedure is in that decision makers have a clear idea of which is candidate site is the most suitable if criteria from a certain group of criteria (ecological or economic or spatial, etc. ) are assessed as the most worthwhile criteria, and if basic criteria groups are dealt with equally. This greatly facilitates decision making. Regardless of which of the many methods for evaluation of potential landfill sites are used, the question of objectivity of the procedure arises taking into account that the selection of evaluation elements (criteria, weights), but also the very decision-making process, is a matter of objectivity of experts and decision makers. This can be considered as a common disadvantage of all methods for potential landfill site selection. Therefore, the subjectivity in this process must be minimized to the utmost limit, while objectivity must be maximized.
We have chosen the area of the Kolubara Region comprising 11 municipalities with 382,000 inhabitant as an example of theoretical knowledge presented in the first part of the present paper.
The Study on the Selection of Micro-location for the Regional Landfill with Recycling Centre and Regional Center for Municipal Solid Waste Management, Regional Plan for Solid Waste Management, as well as Strategic Environmental Assessment (SEA) for the same Plan have been elaborated for the Kolubara Region.
Municipal waste from the territory of 11 municipalities in the Region is disposed of to 10 unarranged sanitary city landfills and a certain number of illegal dumps. All existing landfills should be closed or remediated and recultivated in the shortest possible time. It is recommended to prolong the life-time of the existing landfills through the mentioned remediation projects. Recognizing the need for the final, contemporary waste disposal and management, 11 municipalities of the Region have united together in forming the regions for the development of a waste management. The initiatives that have been launched in this context have resulted in the elaboration of the \'\'Study on the Selection of Micro-Location for the Regional Municipal Waste Landfill with Recycling Center for the Kolubara Region\'\', based on which the location for regional landfill has been selected.
The sanitary landfill construction implies carrying out activities in several phases, whereby it is necessary to observe a specific sequence. The process is mainly carried out in four phases as follows:
Identifying (selecting) the location
Determining the location (through the planning and design documentation) and creating conditions for bringing land to intended use
Elaborating the construction documents (technical documentation)
Landfill construction
The most sensitive and the most important step in making a concept of regional municipal solid waste management is a regional landfill site selection. Relative to the selected regional landfill site, other elements of a waste management system are also located and their spatial distribution carried out.
Once the selection of the most suitable landfill site is made, it is necessary to incorporate it in the planning solutions in order to create conditions for the elaboration of technical documentation, as well as for landfill construction.
The elaboration of the Study on Landfill Site Selection represents the first step in making a concept of municipal solid waste management in the Kolubara Region.
The first step in landfill site selection is to define exclusion criteria.
Taking into account current legislation, Intermunicipal Agreement on Joint Waste Management, basic exclusion criteria used in practice, available data on the space, as well as relevant characteristics of a specific space, the following exclusion criteria have been defined, see [6]:
Seismic activity over 9 MCS
Distance of less than 500 meters from watercourses
Distance of less than 500 meters, or 1.5 km from settlements, if not sheltered
Distances of less than 500 meters from water supply sources
Collision with the existing planning documents
Distance of less than 500 meters from roads of the first category if the site is not sheltered
Terrains with an inclination of over 30%
Terrains of more than 300 meters above sea level
Alluvial plains and karst terrains
Their corresponding areas have been identified using the GIS tools. Through overlapping the corresponding areas, the following is obtained:
Potentially suitable areas for landfill
Unsuitable areas within which it is not possible to locate the landfill.
Once the potentially suitable areas within which its is possible to search for the regional landfill site are singled out, the regional plans for waste management for the Kolubara District and Belgrade administrative area have been considered in which the area of the Kolubara lignite basin has been determined for a macro-location for the regional municipal waste landfill.
Besides, in the Intermunicipal Agreement on the Joint Waste Management it has been agreed that the landfill site will be located in the territory of the Ub municipality since Ub has agreed to accept the waste generated in the newly formed region for municipal solid waste management in its territory.
The location of Carić (within the territory of the Valjevo municipality) has been also considered taking into account that this location has been previously analyzed several times and assessed as a suitable site for a landfill.
In nominating the location, the following has been taken into account:
Preliminary analyses of the entire area and possible central position of potential sites in the region
Data collected during field visits
Consultations and recommendations of relevant local institution and experts
Guidelines set by the EU and the Waste Management Strategy of the Republic of Serbia
Data and information from the existing planning documentation.
Based on the above mentioned, the following three potential landfill site locations have been proposed (Figure 1).
1. Location KALENIĆ, in the area of open pits in the Ub territory
2. Location BOGDANOVICA, city landfill (dump) in Ub
3. Location CARIĆ, for which certain investigations have already been carried out which have indicated certain advantages for landfilling. The location is within the territory of Valjevo municipality.
Position of potential landfill sites in the Kolubara Region
After the nomination of locations, the criteria for the evaluation and selection of the most suitable landfill site have been defined.
New criteria have been defined based on investigation and analysis of previous experiences of other countries and the EU guidelines, as well as on available relevant data for their evaluation. In this context, the following criteria for the selection of micro-location for regional landfill in the Kolubara Region for the municipal solid waste management have been defined:
1. Hydrogeological characteristics
Rock masses with fissure–cavernous porosity and a high water permeability (karstified rocks, limestones and dolostones)
Rocks with intergranular porosity, coarser grained rocks (coarse-grained gravel)
Rocks with low porosity (alluvial and glacial sediments)
Materials with a low water permeability, mainly impermeable complexes of 10-6 k 10-9m/s, or with a low water impermeability, but with small layer thickness of less than 1.0 m;
Water impermeable materials (clay, flysch) of k10-9m/s, the layer thickness 1.0 m.
2. Ground water
Aquifer is, over a brief period and at high water levels of greater frequency, above the bottom of the landfill in one part of its bottom area, while at other water levels, it is beneath the bottom; occasional flooding also occurs at the landfill site
Aquifer, at high water levels of small frequency, rarely rises above the landfill bottom; wetting of the landfill bottom is possible
Aquifer at water levels of 1 to 3 m is beneath the landfill bottom
Aquifer at high water levels 3 m is beneath the landfill bottom
Aquifer does not exist
3. Distance from the boundaries of zones of sanitary protection of water supply sources
Distance from the boundary of
(i) narrower protection zone:(ii) wider protection zone:
0 to 0.2 kmbelt along the protection zone contours
0.2 to 0.5 kmup to 0.5 km
0.5 to 1.0 km0.5 to 1.0 km
1.0 to 1.5 km1 to 2 km
more than 1.5 km 2 km
4. Geological-tectonic characteristics
Pronounced fault zone
Fault carbonate rock masses with numerous surface and underground karst shapes or flat terrain
Flysch sediments, shales, marlsones, sandstones, etc.
Glacial sediments
Magmatic rocks
5. Distance from the closest settlements with concentrated development or residential zones of urban settlements
Distance 1.5 - 2 km, or 0.75 - 1 km if shelter
2 -3 km, or 1 – 1.5 km with shelter
up to 4 km, or 1.5 - 2.0 km with shelter
up to 5 km, or 2.0 – 2.5 km with shelter
more than 5 km, or more than 2.5 km with shelter
6. Relief characteristics of the terrain
Broken relief, very uneven terrain, particularly pronounced in karst landscapes, incompact (scattered) spatial entity encompassing several valleys
Broken relief, uneven terrain, compact spatial entity
Incompact (scattered) spatial entity encompassing several valleys, naturally shaped terrain suitable for formation of valleys
compact waste entity, naturally shaped for locating a landfill site in a steep terrain or in natural depression
Mildly inclined or flat terrain, naturally shaped for locating a landfill site or possibly a landfill in excavated depressions or on earth fills
7. Available space for waste disposal and ancillary facilities
up to 5 yrs
up to 10 yrs
up to 15 yrs
up to 20 yrs
20 yrs
8. Site acceptability
General landfill site disagreement
General agreement, but disagreement from local community
General agreement, but disagreement from certain individuals form local community
General agreement and somewhat moderate disagreement from local community
General acceptance of a landfill site
9. Engineering-geological characteristics
Incoherent rock masses, unstable slopes, slides and falls, active landslides
Complex of incoherent and semi—coherent rock masses (deluvial sediments), possible occurrence of landslides due to undercutting the foot of an existing slope
Semi-coherent rocks, possible occurrence of landslides due heavy falls
Coherent rocks, slightly stoned rock, stable slopes
Solid rocks, stable slopes even those of greater inclinations
10. Current land use
Cultivated agricultural land (ploughland, orchards), individual houses and other residential buildings within holdings, sportsgrounds, etc.
Quality tall forests;
Meadows
Pastures, shrub woods
Uncultivated land, thickets, barren land, excavations, quarries
11. Distance from individual water supply (wells)
100 - 200 m, downstream of the landfill or approximately on landfill level
up to 500 m, downstream of the landfill or on the same level as the landfill
500 to 1000 m, downstream or on the same level as the landfill
downstream of the landfill at the distance up to 200 m, downstream of the landfill at the distance of 1-1.5km;
downstream of the landfill at the distance of more than 200 m, downstream of the landfill at the distance of more than 1.5 km.
12. Landscape characteristics
Highly disturbed and completely changed natural ambience during landfill exploitation and after its closure
Highly disturbed natural ambience during landfill exploitation, and partly after the landfill closure
Natural ambience disturbed during landfill exploitation, and to a less extent after its closure
Natural ambience slightly disturbed during landfill exploitation, and undisturbed after its closure
Ambience not disturbed either during landfill exploitation or after its closure.
13. Linear distance from roads and railroads
more important roads |other roads
without shield| with shield |without shield |with shield
500 m|300 m|300 m|200 m
600 m|400 m|400 m|250 m
800 m|500 m|500 m|300 m
1000 m|600 m|600 m|400 m
1000 m|600 m|600 m|400 m
14. Distance to sacral structures, monuments of culture or protected natural resources
Distance 1.0 – 1.25 km, or 0.5 – 0.75 km where there is a shield
1.25 -1.50 km, or 0.75 - 1,0 km with shield;
1.5 – 2.0 km, or 1.0 - 1.25 km with shield;
2 – 2.5 km, or 1.25 – 1.5 km with shield;
more than 2.5 km, or more than 1.5 km with shield
15. Seismic Activity
9-8 MCS
7 MCS
6 MCS
5 MCS
5 MCS
16. Existing site infrastructure
Absence of any infrastructure
Poor infrastructure
Only one infrastructure segment (access road, water supply line, electricity);
Several infrastructure segments
All or most of the infrastructure segments
17. Distance from surface watercourses
Permanent rivers or standing waters at the distance of 500 to 1000 m, there is a risk of flooding during high waters, defense measures against high waters required
Small watercourses, permanent or periodic ones (brooks, torrents), there is a flood risk, it is necessary to displace or channel these waters
Heavy inflow of rain waters from immediate catchments, defense against these waters requires more complex facilities; there is no flooding
Permanent watercourses at the distance greater than 1 km, no risk from flooding; defense standard solutions applicable
Great distance from watercourses, no risk from flooding, very low inflow of rain waters, simple protection against these waters possible
18. Terrain preparation
Very complex terrain leveling works, including intensive blasting on the greatest part of the site
Complex terrain leveling works, blasting required only in some parts of the landfill site
Terrain leveling works on the greatest part of the landfill site using machines
Terrain leveling on the smaller part of landfill site using machines
Simple terrain leveling works on the smaller part of the landfill site
19. Earth for covering the disposed waste – distance from the borrow site
greater than 5 km,
2-5 km,
1-2 km,
up to 1 km,
on site.
20. Position of the site in the Region
Completely dislocated relative to the central position in the Region; at the edge of the Region
Within the radius of 20 km relative to the central point in the Region,
Within the radius of 10 km relative to the central point in the Region,
Centrally positioned relative to the Region,
Within the radius of 10 km relative to the central point in the Region, but closer to the municipalities with the largest amounts of municipal solid waste.
21. Ownership of land
100 % of land under private ownership, greater number of smaller plots
100 % of land under private ownership, greater plots
About 75 % of land under private ownership, about 25 % of land under state ownership
About 50 % of land under private ownership and about the same amount of land under private ownership
100 % of land under state ownership
22. Precipitations
1500 mm
1000 to 1500 mm
600 to 1000 mm
300 to 600 mm
< 300 mm
23. Air temperature
6 C
6-9 C
9-12 C
2-15 C
15 C
24. Air flow
Very frequent high intensity winds, with prevailing wind direction towards settlements and other localities where people stay and work
Less frequent lower intensity winds with prevailing wind direction towards relevant facilities
Prevailing winds of changeable direction towards relevant facilities
Dominant winds blowing in the opposite direction, from settlements and other places where people stay and work, as well as low intensity winds blowing in direction towards the settlements
Most of the winds blowing in opposite direction, from settlements and other places where people stay and work
25. Distance to individual houses outside settlements
250 m
500 m
1000 m
1500 m
500 m
26. Site shelterness
Visible from all distances and all angles
Locality sheltered to a smaller extent
Locality sheltered to a greater extent
The glimpse of the locality can be caught in the great distance
Not at all visible, except when you come in the locality itself
27. Access road – reconstruction, or construction of a new road
New roadRoad reconstruction
1000 m,>1500 m
500-1000 m800 – 1500 m
200-500 m300 – 800 m
<200 m< 300 m
There is an access road of satisfactory characteristics
28. Providing electricity supply via the distribution network at the distance of:
> 2 km
1 - 2 km
0. 5 - 1 km
300 - 500 m
< 300 m
29. Water supply in the locality
From the public water supply system via connection longer than 4 km, or from a local water supply via a connection longer than 3km
From the public water supply system via connection 2 to 4 km long, or from a local water supply via a connection up to 3 km long
From the public water supply system via connection from 1 to 2 km long, or from a local water supply via connection up to 1 km long
From the public water supply system via connection from 0.5 to 1 km long, or from a local water supply via connection up to 500 m long
From the public water supply system via connection up to 500 m long
30. Distance to agricultural land
100 m
100 - 300 m
300 - 500 m
500 - 1000 m
1000 m
31. Distance from the main transmission line, gas pipeline, crude oil pipeline, drinking water pipeline
up to 100 m
100 - 200 m
200 - 300 m
300 - 500 m
500 m
32. Possibility of construction in phases and extension
No possibility of construction in phases or of extension
Limited possibility of construction in phases, but not of extension
Possibility of construction in phases, but not ofextension
Possibility of construction in phases and of limited extension
Possibility of construction in phases and of unlimited extension
Criteria are presented under the principle of exclusion criteria. More precisely, no detailed guidelines for evaluation have been given for criteria save for exclusion criteria which define requirements which a potential site MUST meet in locating the municipal solid waste landfill site.
Potential micro-location for regional landfill in the Kolubara Region has been determined through multicriteria analysis and evaluation. Chosen criteria have been evaluated by assigning scores from 1 to 5 for each candidate site.
At the same time, depending on their importance in evaluating the locality quality, criteria have been classified into 3 pondering categories (PC). Each weight category has its specific value – weight, which is multiplied by the score of corresponding criteria. In this way, a final score is obtained for each criterion. Values by pondering categories are:
PC1 = 1
PC2 = 1.5
PC3 = 3
The relation between pondering categories (PC) is: Ki+1 = Ki/1.5
PC 3 | PC 2 | PC 1 |
Landfill site selection criteria | ||
1 - 8 | 9 - 20 | 21 - 32 |
Grouping the criteria by pondering categories (PC)
Table 2 indicates that after assigning a score to each criterion, the Kalenić location has been singled out as the most suitable one. The other two locations (Bogdanovica and Carić) have been assigned much poorer scores compared to the Kalenić location. However, in cases when the difference in ranks between candidate locations is extremely small at the end of evaluation process, it is difficult to make a final decision on which site is the most suitable. In this case, it necessary to carry out an additional evaluation which implies the evaluation of candidate sites by different scenarios. The chosen site selection criteria are then grouped into basic groups, while in the \'\'additional\'\' valuation process, the criteria from one of the basic groups are favored in each scenario, see [6].
There are so many scenarios as groups, plus one for the scenario according to which each basic criteria group is evaluated equally (for the last scenario, the data taken from basic evaluation or criteria are multiplied by weight value). In this way, decision makers are given opportunity to choose the option based on their policy, and thus select the most suitable site.
In regional landfill site selection for Kolubara Region, no \'\'additional\'\' evaluation has been required due to evident advantages of location Kalenić.
Criteria | PC | Kalenić | Bogdanovica | Carić |
1. Hydrogeological characteristics | PC 3 | 12 | 9 | 9 |
2. Groundwater | PC 3 | 15 | 6 | 12 |
3. Distance from the boundaries of zones of sanitary protection of water supply sources | PC 3 | 12 | 15 | 15 |
4. Geological-tectonic characteristics | PC 3 | 12 | 9 | 9 |
5. Distance from the nearest settlements with concentrated development or residential zones of urban settlements | PC 3 | 12 | 3 | 12 |
6. Relief characteristics of the terrain | PC 3 | 15 | 15 | 12 |
7. Available space for waste disposal and ancillary facilities | PC 3 | 15 | 3 | 6 |
8. Site acceptability | PC 3 | 15 | 6 | 6 |
9. Engineering-geological characteristics | PC 2 | 3 | 3 | 3 |
10. Current land use | PC 2 | 7.5 | 7.5 | 1.5 |
11. Distance from individual water supply (wells) | PC 2 | 7.5 | 7.5 | 7.5 |
12. Landscape characteristics | PC 2 | 7.5 | 4.5 | 1.5 |
13. Linear distance from roads and railroads | PC 2 | 7.5 | 1.5 | 7.5 |
14. Distance to sacral structures, monuments of culture or protected natural resources | PC 2 | 7.5 | 7.5 | 7.5 |
15. Seismic Activity MCS | PC 2 | 3 | 3 | 3 |
16. Existing site infrastructure | PC 2 | 7.5 | 3 | 1.5 |
17. Distance from surface watercourses | PC 2 | 6 | 1.5 | 7.5 |
18. Terrain preparation | PC 2 | 4.5 | 4.5 | 4.5 |
19. Earth for covering the disposed waste – distance from the borrow site | PC 2 | 7.5 | 3 | 1.5 |
20. Position of location in the Region | PC 2 | 7.5 | 6 | 3 |
21. Ownership of land | PC 1 | 5 | 4 | 1 |
22. Precipitation | PC 1 | 3 | 3 | 3 |
23. Air temperature | PC 1 | 2 | 2 | 2 |
24. Air flow | PC 1 | 4 | 4 | 3 |
25. Distance to individual houses outside the settlement | PC 1 | 3 | 2 | 1 |
26. Location shelterness | PC 1 | 5 | 3 | 4 |
27. Access road - reconstruction or construction of new road | PC 1 | 3 | 3 | 1 |
28. Providing electricity supply via the distribution network at the distance of | PC 1 | 3 | 3 | 2 |
29. Water supply in the locality | PC 1 | 4 | 3 | 1 |
30. Distance to agricultural land | PC 1 | 5 | 4 | 1 |
31. Distance from main transmission line, gas pipeline, crude oil pipeline, drinking water pipeline | PC 1 | 5 | 2 | 5 |
32. Possibility of construction in phases and extension | PC 1 | 5 | 3 | 2 |
Total sum of criteria scores | 231.5 | 154.5 | 154 |
Evaluation of potential site by chosen criteria, see [2].
Had the final results of evaluation for all candidate locations been equal, the \'\'additional\'\' evaluation process would have been carried out in a manner as described in the text that follows. Namely, chosen criteria for additional evaluation would be classified into three basic groups (Table 3).
ECOLOGICAL | SPATIAL | SOCIO-ECONOMIC |
Landfill site selection criteria | ||
1, 2, 3, 4, 6, 9, 10, 12, 15, 22, 23, 24, 26 | 5, 7, 11, 13, 14, 17, 19, 20, 25, 30, 31 | 8, 16, 18, 21, 27, 28, 29, 32 |
Classification of chosen criteria into basic criteria groups
The scores of each criteria obtained in the basic evaluation process would then be multiplied by weight values for criteria groups according to different scenarios (Table 3). Weight values would actually be the percentage values whose sum is 100%.
Scores of each criteria from the basic evaluation process would be then multiplied by weight values for criteria groups according to different scenarios (Table 4).
Weight values would actually be the percentage values whose sum is 100%.
Scenario Basic criteria group | SC 1 | SC 2 | SC 3 | SC 4 |
EKOLOGICAL | 0.50 | 0.25 | 0.25 | 0.33 |
SPATIAL | 0.25 | 0.50 | 0.25 | 0.33 |
SOCIO-ECONOMIC | 0.25 | 0.25 | 0.50 | 0.33 |
Criteria weight values according to different scenarios
After multiplying the criteria values from basic evaluation by weight criteria according to different scenarios and their sum for each candidate site, the ranking of candidate sites according to different scenarios would be obtained (Table 5).
Scenario | SC 1 | SC 2 | SC 3 | SC 4 |
Site ranks | ||||
Candidate site | Kalenić (83.12) | Kalenić (77.50) | Kalenić (73.32) | Kalenić (76.23) |
Bogdanovica (63.12) | Carić (53.25) | Bogdanovica (47.40) | Bogdanovica (50.98) | |
Carić (58.62) | Bogdanovica (48.87) | Carić (45.07) | Carić (50.82) |
Ranking of candidate sites according to different scenarios
Through multicriteria evaluation according to different scenarios, several options and different arguments for the selection of the most suitable site are made available to decision makers. Implementation of different scenarios is based of the PROMETHEE method.
In this case, it has been shown that the location Kalenić has the best values in all four scenarios, while it is evident that the remaining two locations differ depending on scenario. The location Carić is better valued for the scenario 2, while location Bogdanovica is better valued in other three scenarios.
In selecting the landfill site in the Kolubara Region for municipal solid waste management, the GIS tools have been implemented in singling out areas to be eliminated. The areas to be eliminated have been singled out based on defined exclusion criteria. Each of exclusion criteria has been presented graphically (cartographic presentation), and corresponding areas have been identified using GIS technology. Through overlapping maps of each exclusion criteria, negative areas have been singled out that should not be further analyzed in the landfill site selection process for the municipal solid waste management. Negative areas are shown in the synthesis map (Figure 2).
Analsys of land use structure based on CORINE information system [11].
Figure 2. depicts the structure of land use in Kolubara Region based on the CORINE (Coordination of Information on the Environment). The CORINE program is the European information base as support to the sustainable development policy of the European Union. The database contains data on: urban areas, crop yield, meadows, forests and natural vegetation, waters,. as well as other dynamic processes in the environment. All mentioned data are cartographically presented, which enables a more simple analysis of the subject area. The CORINE program was initiated in 1985. At the beginning, the program was developed and tested on 10 regions of the European Union by demonstrating the feasibility of the approach. Satellite photographs on which the CORINE database is based have been geometrically and radiometrically supplemented and with abundance of data which are in the CORINE Land Cover organized hierarchically in three levels classified in 44 classes (correspondingly presented spatial features and data). After showing positive results, in 1994 the European Environment Agency based in Copenhagen undertook the maintenance and use of the CORINE Land Cover database. Since then, the CORINE Land Cover (CLC) has been affirmed which is reflected in the fact that an increasing number of European countries are involved in the CLC project which has provided them with an opportunity to more efficiently pursue their environmental protection and sustainable development policies, as well as to carry out analyses for various needs and development strategies. Today, 64 European countries are involved in the CORINE Land Cover 2000 Project, with clearly defined and synchronized methodology for collection, processing, as well as presentation of data, in the function of the elaboration of environmental management plans [12].
In the elaboration of the \'\'Study on the Selection of Micro-Location for the Regional Municipal Waste Landfill with Recycling Center for the Kolubara Region\'\', the CORINE information base has not been available for Serbia, thereby for the Kolubara Region either. However, once the information on the environment from the CORINE program have become available for users in Serbia, all results from the elimination phase of landfill site selection contained in the Study have been checked and, what is even more important, confirmed. By using the CORINE program in accordance with the defined eliminating criteria for Kolubara Region, the selection of “negative” areas has been much easier and faster. The CORINE Information base to a great extent meets the needs of elimination phase in landfill site selection, thus this phase should be used as much as possible.
On the synthesis map (Figure 3), which is a final phase in the process of elimination of “negative” areas, the areas which do not satisfy basic conditions relative to the established exclusion criteria are denoted by red color. These are mainly corridors along watercourses, first category roads, distances to settlements, areas at over 300 meters above sea level, water supply sources, etc. Thus, it is the matter of exclusion criteria represented by minimum required distance of the future landfill site relative to them [13].
In the elimination phase, it is also possible to use some other criteria such as, for example, central position of a landfill relative to the Region. This means that, because of the cost-effectiveness of the waste management system, i.e. transportation costs, it is necessary to position a landfill within the radius of 20 or 30 km relative to the central point of the Region. However, in such case, a great number of areas that merit further analysis by their characteristics can be excluded, while the problem of central positioning of a landfill can be overcome through a good organization of transfer station network in the Region. In this context, it is important to emphasize that it is not necessary to introduce a great number of exclusion criteria, but to limit the choice of exclusion criteria to the most relevant ones, as shown on the example of the Kolubara Region.
Suitability/elimination map
Once the consultations with relevant entities have been carried out, as well as preliminary analysis of areas that have not been eliminated in the first phase of the landfill site selection process, three sites have been singled which have been included in the process of detailed analysis and multicriteria evaluation.
The use of GIS information base in this phase of landfill site selection has considerably accelerated the process of evaluation according to 32 given criteria. Once the location Kalenić has been assessed as the most suitable one and singled out as the most acceptable one, the landfill site selection process has been completed. However, this is not where the use of GIS tools ends. Their role is also in implementation of a uniform information system for waste management which consolidates data on landfills, transfer stations, waste generation, waste flows, as well as other data important for an efficient waste management. In this sense, GIS tools represent an information support in the functioning of the waste management system.
Landfill site selection is the most sensitive task placed before the participants in the process of planning spatial organization of a waste management system, particularly in countries in which there is insufficient awareness and lack of information in the population, and, consequently, there is a resistance to plans to locate a landfill in their area, known as NIMBY (not in my backyard) syndrome. Out of these reasons, this problem is overcome through defining the elimination and basic criteria for landfill site selection based on which an multicriteria evaluation is carried out, along with mandatory inclusion of all relevant stakeholders in the process of selecting the most suitable landfill site. In the present paper, such exclusion criteria have been chosen that are appropriate to the specific space which has been the subject of our investigation, as well as according to available spatial data. In this context, the paper emphases the fact that the choice of exclusion criteria is conditioned by a specific physical properties of space. After the phase of elimination of \'\'negative\'\' areas, a multicriteria analysis of sites that have been nominated based on a set of basic criteria has been carried out. Altogether 32 criteria have been defined that are based on efficient functioning of a landfill, as well as on efficient environmental protection at specific landfill site and its surroundings. A multicriteria evaluation model has been offered and value scale for evaluation of each criteria defined. The multicriteria evaluation model has been also used for different scenarios. In this context, basic criteria for landfill site selection have been grouped into several basic groups, while in the evaluation process for each criteria only one of the basic groups has been evaluated. Such approach enables decision makers to choose the most suitable option and to make best decision according to their policy.
Comprehensive consideration of the problem associated with landfill site selection for physical elements of waste management system implies the use of GIS tools, thus providing a more sophisticated process of spatial analysis and searching for better options, as well as accelerating and visually enriching the process. Advantage of using GIS tools is in that it enables faster singling out and clearer presentation of suitable and unsuitable landfill sites based of previously given criteria. The paper shows the example of advantages and disadvantages, as well as possibilities of implementing GIG in regional landfill site selection for municipal solid waste management in the Kolubara Region. The GIS applications are particularly suitable for elimination phase where, based on the given exclusion criteria and spatial data, the \'\'negative\'\' areas within which potential landfill sites are not be searched are very quickly and easily eliminated. The entire process is presented cartographically. The possibility of implementing the CORINE Program – a uniform European information base on the environment and space usage, which is particularly suitable for elimination phase in landfill site selection as it provides abundance of geospatial data, has been highlighted. Furthermore, the possibility of efficient waste management using database in the GIS is highlighted. The system supported by such data enables quality and fast waste management, monitoring, waste data updating, as well as the best basis for planning waste management strategy at regional level.
This work has resulted from research within the scientific project: “Sustainable spatial development of Danube area in Serbia ” (TR 036036), which was financed within the program Technological development by the Ministry of Education and Science of the Republic of Serbia from 2011 to 2014.
Voltammetry is an electrochemical technique for current-voltage curves, from which electrode reactions at electrode-solution interfaces can be interpreted. Since current-voltage curves, called voltammograms, include sensitive properties of solution compositions and electrode materials, their analysis provides not only chemical structures and reaction mechanisms on a scientific basis but also electrochemical manufacture on an industrial basis. The voltammograms vary largely with measurement time except for steady-state measurements, and so it is important to pay attention to time variables. Voltage is a controlling variable in conventional voltammetry, and the current is a measured one detected as a function of applied voltage at a given time.
\nThe equipment for voltammetry is composed of electrodes, solution, and electric instruments for voltage control. Electrodes and electric instruments are keys of voltammetry. Three kinds of electrodes are desired to be prepared: a working electrode, a counter one, and a reference one. The three will be addressed below.
\nLet us consider a simple experiment in which two electrodes are inserted into a salt-included aqueous solution. When a constant current is applied to the two electrodes, reaction 2H+ + 2e− → H2 may occur at one electrode, and reaction 2OH− → H2O2 + 2e− occurs at the other. The current is the time variation of the electric charge, and hence it is a kind of reaction rate at the electrode. Since the applied current is a sum of the two reaction rates, one being in the positive direction and the other being in the negative, it cannot be attributed to either reaction rate. A technique of attributing the reactions is to use an electrode with such large area that an uninteresting reaction rate may not become a rate-determining step. This electrode is called a counter electrode. The current density at the counter electrode does not specifically represent any reaction rate. In contrast, the current density at the electrode with a small area stands for the interesting reaction rate. This electrode is called a working electrode. It is the potential difference, i.e., voltage, at the working electrode and in the solution that brings about the electrode reaction. However, the potential in the solution cannot be controlled with the working electrode or the counter one. The control can be made by mounting another electrode, called a reference electrode, which keeps the voltage between an electrode and a solution to be constant. However, the constant value cannot be measured because of the difference in phases. A conventionally employed reference electrode is silver-silver chloride (Ag-AgCl) in high concentrated KCl aqueous solution.
\nAn electric instrument of operating the three electrodes is a potentiostat. It has three electric terminals: one being a voltage follower for the reference electrode without current, the second being a current feeder at the counter electrode, and the third being at the working electrode through which the current is converted to a voltage for monitoring. A controlled voltage is applied between the working electrode and the reference one. These functionalities can readily be attained with combinations of operational amplifiers. A drawback of usage of operational amplifiers is a delay of responses, which restricts current responses to the order of milliseconds or 10 kHz frequency.
\nVoltammetry includes various types—linear sweep, cyclic, square wave, stripping, alternating current (AC), pulse, steady-state microelectrode, and hydrodynamic voltammetry—depending on a mode of the potential control. The most frequently used technique is cyclic voltammetry (CV) on a time scale of seconds. In contrast, currently used voltammetry at time as short as milliseconds is AC voltammetry. We describe here the theory and tips for practical use of mainly the two types of voltammetry.
\nThe theory of voltammetry is to obtain expressions for voltammograms on a given time scale or for those at a given voltage. First of all, it is necessary to specify rate-determining steps of voltammograms. There are three types of rate-determining steps under the conventional conditions: diffusion of redox species in solution near an electrode, adsorption on an electrode, and charging processes at the double layer (DL). Electric field-driven mass transport, called electric migration, belongs to rare experimental conditions, and hence it is excluded in this review. When a redox species in solution is consumed or generated at an electrode, it is supplied to or departed from the electrode by diffusion unless solution is stirred. When it is accumulated on the electrode, the change in the accumulated charge by the redox reaction provides the current. Whenever electrode voltage is varied with the time, the charging or discharging of the DL capacitor causes current. Therefore, the three steps are frequently involved in electrochemical measurements.
\nA mass transport problem on voltammetry is briefly described here. The redox species is assumed to be transported by one-directional (x) diffusion owing to heterogeneous electrode reactions. Then, the flux is given by f = −D(∂c/∂x), where c and D are the concentration and the diffusion coefficient of the redox species, respectively. Redox species in solution causes some kinds of chemical reaction through chemical reaction rates, h(c, t). Then the reaction rate is the sum of the diffusional flux and the chemical reaction rate, ∂c/∂t = −∂f/∂x − h(c, t). Here the equation for h = 0 is called an equation of continuum. Eliminating f with the above equation on the assumption of a constant value of D yields ∂c/∂t = D(∂2c/∂x2) − h(c, t). This is an equation for diffusion-chemical kinetics. The expression at h = 0 is the diffusion equation. A boundary condition with electrochemical significance is the control of c at the electrode surface with a given electrode potential. If the redox reaction occurs in equilibrium with the one-electron transfer at the electrode, the Nernst equation for the concentrations of the oxidized species, co, and the reduced one, cr, holds.
\nwhere Eo is the formal potential. If there is no adsorption, the zero-flux condition in the absence of accumulation is valid:
\nThe other conditions are concentrations in the bulk (x → ∝) and the initial conditions.
\nIf the mass transport is controlled only by x-directional diffusion, cr and co are given by the diffusion equations, ∂c/∂t = D(∂2c/∂t2) for c = cr or co. An electrochemically significant quantity is not concentration in any x and t, but a relation between the surface concentrations and the current (the flux at x = 0). On the assumption of Do = Dr = D, of the initial and boundary conditions, (cr)t = 0 = c*, (co)t = 0 = 0, and (cr)x = ∞ = c*, (co)x = ∞ = 0, a solution of the initial-boundary problem is given by [1].
\nwhere j is the current density. The common value of the diffusion coefficients yields co + cr = c* for any x and t. Inserting this relation and Eq. (3) into the Nernst equation, (co)x = 0 = c*/[1 + exp[−F(E − Eo)/RT]], we obtain the integral equation for j as a function of t or E.
\nWhen the voltage is linearly swept with the time at a given voltage scan rate, v, from the initial potential Ein, Eq. (3) through the combination with the Nernst equation becomes
\nThe above Abel’s integral equation can be solved by Laplace transformation. When the time variation is altered to the voltage variation through E = Ein + vt, the current density is expressed as
\nwhere ζ = (E − Eo)F/RT and ζi = (Ein − Eo)F/RT. Evaluation of the integral has to resort to numerical computation. Current at any voltage should be proportional to v1/2, as can be seen in Eq. (5). The voltammogram for v > 0 rises up from Eo, takes a peak, and then deceases gradually with the voltage. The decrease in the current is obviously ascribed to relaxation by diffusion. The peak current density is expressed by
\nat Ep = Eo + 0.029 V at 25°C, where 0.446 comes from the numerical calculation of the integral of Eq. (5).
\nPractical voltage-scan voltammetry is not simply linear sweep but cyclic voltammetry (CV), at which applied voltage is reversed at a given voltage in the opposite direction. The theoretical evaluation of the voltammogram should be at first represented in the integral form with the time variation and then express the time as the voltage. One of the features of the diffusion-controlled cyclic voltammograms is the difference between the anodic peak potential and the cathodic one, ΔEp (in Figure 1), of which value is 59 mV at 25°C.
\nVoltammograms calculated from Eq. (5) for v = (a) 180, (b) 80 and (c) 20 mV s−1.
AC voltammetry can be performed when the time variation of voltage is given by E = Edc + V0eiωt, where ω is the frequency of applied AC voltage, i is the imaginary unit, V0 is its voltage amplitude, and Edc is the DC voltage. A conventional value of V0 is 10 mV. When this voltage form is inserted into Eq. (3) together with the Nernst equation, the AC component of the current density is represented by [2].
\nA voltammogram (j vs. Edc) at a given frequency takes a bell shape, which is expressed by sech2{(Edc − Eo)/RT}. The functional form of sech2 is shown in Figure 2. The peak current appears at Edc = Eo.
\nVoltammogram calculated from Eq. (10).
The AC-impedance technique often deals with the real impedance, Z1, = 1/2Y1 and the imaginary one, Z2 = −1/2Y1, where Y1 is the real admittance given by
\nHere Y2 is the imaginary admittance, equal to Y1. Since Z1 = −Z2, the Nyquist plot, i.e., −Z2 vs. Z1, is a line with the slope of unity. The term 1 + i in Eq. (7) has come from (Dω)1/2, originating from (Diω)1/2. Therefore, it can be attributed to diffusion. In other words, diffusion produces the capacitive component as a delay.
\nWhen the redox species with reaction R = O + e− is adsorbed on the electrode and has no influence from the redox species in the solution, the sum of the surface concentrations of R and O is a constant, Γ*. Then the surface concentration of the oxidized species, Γo, is given by the Nernst equation:
\nThe time derivative of the redox charge corresponds to the current density, j = d(FΓo)/dt. Application of the condition of voltage sweep, E = Ein + vt, to Eq. (9) yields.
\nThe voltammogram takes a bell shape (Figure 2), of which peak is at E = Eo, similar to the AC voltammogram. The current at any voltage is proportional to v. Since the negative-going scan of the voltage provides negative current values, the cyclic voltammogram should be symmetric with respect to the I = 0 axis. The peak current is expressed as jp = F2Γ*v/4RT. The width of the wave at jp/2 is 90 mV at 25°C.
\nSince a phase has its own free energy, contact of two phases provides a step-like gap of the free energy, of which gradient brings about infinite magnitude of force. In order to relax the infinity, local free energy varies from one phase to the other as smoothly as possible at the interface. The large variation of the energy is compensated with spontaneously generated space variations of voltage, i.e., the electric field, which works as an electric capacitor. The capacitance at solution-electrode interface causes orientation of dipoles and nonuniform distribution of ionic concentration, of which layer is called an electric double layer (DL).
\nWhen the time variation of the voltage is applied to the DL capacitance, Cd, the definitions of the capacitance (q = CdV) and the current lead
\nwhere Cd generally depends on the time. This dependence is significant for understanding experimentally observed capacitive currents.
\nThe DL capacitance has exhibited the frequency dispersion expressed by Cd = (Cd) 1Hz f −λ, called the constant phase element [3, 4, 5] or power law [6, 7], where λ is close to 0.1. Inserting this expression and V = V0eiωt into Eq. (11) yields
\nThis is a simple sum of the real part of the current and the imaginary one, indicating that the equivalent circuit should be a parallel combination of a capacitive component and a resistive one, both depending on frequency. Since the ratio, −Z2/Z1, for Eq. (12) is 1/λ, the Nyquist plots have slopes less than 10 rather than infinity.
\nIf the capacitive charge is independent of the time, the capacitive current should be I = d(CV)/dt = C(E − Eo)/v. Therefore, it takes a horizontal positive (v > 0) and a negative line (v < 0), as shown in Figure 3 (dashed lines). When the time dependence of C, i.e., Cd = (Cd)0t−λ, is applied to Eq. (11), for the forward and the backward scans, respectively, we have
\nCapacitive voltammograms by CV at v= 0.5 V s−1 for (dashed lines) the ideal capacitance and for Eq. (13) (solid curves) at λ = 0.2.
The variation of CV computed from Eq. (13) (Figure 3, solid curves) is similar to our conventionally observed capacitive waves.
\nVoltammograms can identify an objective species by comparing a peak potential with a table of redox potentials and furthermore determine its concentration from the peak current. Their results are, however, sometimes inconsistent with data by methods other than electrochemical techniques if one falls in some pitfalls of analytical methods of electrochemistry. For example, a peak potential is influenced by a reference electrode and solution resistance relevant to methods. Peak currents are varied complicatedly with mass transport modes as well as associated chemical reactions. Since the theory on voltammetry covers only some restricted experimental conditions, it can rarely interpret the experimental data successfully. This review is devoted to some voltammetric tips which can lead experimenters to reasonable interpretation.
\nIt is rare to observe a reversible voltammogram in which both oxidation and reduction waves appear in a symmetric form with respect to the potential axis at a similar peak potential, as in Figure 1. Frequently observed voltammograms are irreversible, i.e., either a cathodic or an anodic wave appears; a value of a cathodic peak current is quite different from the anodic one in magnitude; a cathodic peak potential is far from the anodic one. These complications are ascribed to chemical reactions and/or phase transformation after the charge-transfer reaction. A typical example is deposition of metal ions on an electrode. The complications can be interpreted by altering scan rates and reverse potentials.
\nA wave at a backward scan is mostly attributed to electrode reactions generated by experimenters rather than to species latently present in the solution. That is, it is artificial. It is caused either by the reaction of the wave at the forward scan or the reaction of the rising-up current just before the reverse potential. A source of the backward wave can be found by changing the reverse potentials.
\nSome voltammograms have more than two peaks at one-directional scan. The appearance of the two can be interpreted as a two-step sequential charge-transfer reaction. However, multiple waves appear also by combinations of chemical reactions and adsorption. The peak current and the charge for this case are quite different from the predicted ones, as will be described in Section 3.2. Change in scan rates may be helpful for interpreting the multiple waves.
\nIt is possible to predict theoretically a controlling step of voltammograms from their shape (a bell type corresponding to an adsorption wave or a draw-out type corresponding to a diffusion wave). However, the shape strongly depends on chemical complications, adsorption, and surface treatment of the electrodes. When redox species in solution is partially adsorbed on an electrode, the electrode process is far from a prediction because of very high concentration in the adsorbed state. A draw-out-shaped wave can be observed even for the adsorbed control. It is important to estimate which state the reacting species takes on the electrode. Potentials representing of voltammetric features do not express a controlling step in reality although the theory does. One should pay attention to the current. The peak current controlled by diffusion with one-electron transfer is given by Ip = 0.27 cAv1/2 μA (c, bulk concentration mM; A, electrode area mm2; v, potential sweep rate mV s−1). The microelectrode behavior sometimes comes in view at v < 10 mV s−1, A < 0.1 mm2, so the measured current is larger than the estimated value. On the other hand, the peak current controlled by adsorption is given by Ip = 1.6 Av nA when one redox molecule is adsorbed at 1 nm2 on the electrode. The voltammogram by adsorption often differs from the ideal bell shape due to adsorbed molecular interaction and DL capacity. Division of the area of the peak by the scan rate yields the amount of adsorbed electricity. Comparison of this with the anticipated amount of adsorption may be helpful for understanding the electrode process.
\nThe peak potential difference ΔEp between the oxidation wave and the reduction wave (Figure 1) has been used for a prediction of the reaction mechanism. For example, ΔEp = 60 mM suggests the diffusion-controlled current accompanied by one-electron exchange, whereas ΔEp = 30 mM infers a simultaneous reaction with two electrons. Then what would happen for 120 mV which is sometimes found? A half-electron reaction might not be accepted. Potential shift over 60 mV occurs by chemical complications. In contrast, the voltammogram by adsorbed species shows theoretically a bell shape with the width, E1/2 = 90 mV, at the half height of the peak (Figure 2). This value is based on the assumption of the absence of interaction among adsorbed species. However, adsorption necessarily yields such high concentrations as strong interaction.
\nIt is necessary to pay attention to the validity of analyzing ΔEp and E1/2. The peak potential is the first derivative of a voltammogram. Since ΔEp is a difference between the two peaks, it is actually the second-order derivative of the curves in the view of accuracy. In other words, the accuracy of ΔEp is lower than that of peak current. Furthermore, peak potentials as well as E1/2 readily vary with scan rates owing to chemical reactions and solution resistance. One should use the peak current for data analysis instead of the potentials.
\nVoltammograms of a number of redox species have been reported to be diffusion controlled from a relationship between Ip and v1/2. The redox species exhibiting diffusion-controlled current is, however, limited to ferrocenyl derivatives under conventional conditions. Voltammograms even for [Fe(CN)6]3−/4− and [Ru(NH3)6]3+ are deviated from the diffusion control for a long-time measurement. Why have many researchers assigned voltammograms to be the diffusion-controlled step? The proportionality of Ip to v1/2 in Eq. (6) has been confused with the linearity, Ip = av1/2 + b (b ≠ 0). The plot for the adsorption control (Ip = kv) also shows approximately a linear relation for Ip vs. v1/2 plot in a narrow domain of v, as shown in Figure 4B. The opposite is true (Figure 4A). Therefore, it is the intercept that determines a controlling step of either the diffusion or adsorption. Some may say that the intercept can be ascribed to a capacitive current. If so, the peak current should be represented by Ip = av1/2 + bv, which exhibits neither linear relation with v1/2 nor v.
\nPlots of Ip of (A) K3Fe(CN)6 and (B) polyaniline-coated electrode against v1/2 and v. Both plots show approximately linear relations.
There is a simple method of determining a controlling step either by diffusion or adsorption. Current responding to diffusion-controlled potential at a disk electrode in diameter less than 0.1 mm would become under the steady state after a few seconds [8]. Adsorption-limited current should become zero soon after the potential application. Many redox species, however, show gradual decrease in the current because reaction products generate an adsorbed layer which blocks further electrode reactions.
\nIt is well known that currents vary not only with applied voltage but also with the time. It is not popular, however, to discuss quantitatively time dependence of CV voltammograms. Enhancing v generally increases the current and causes the peak potential to shift in the direction of the scan. A reason for the former can be interpreted as generation of large current at a shorter time (see Eqs. (6) and (10)), whereas the latter is ascribed to a delay of reaction responses as well as a voltage loss of the reaction by solution resistance. Then the voltage effective to the reaction is lower than the intended voltage, and so the observed current may be smaller than the predicted one. Although Ip is related strongly with Ep, the relationship has rarely been examined quantitatively.
\nA technique of analyzing the potential shift is to plot Ip against Ep, [9] as shown in Figure 5. If the plots on the oxidation side (Ip > 0) and the reduction side (Ip < 0) fall each on a straight line, the slope may represent conductivity. If values of both slopes are equal, the slope possibly stands for the conductivity of the solution or membrane regardless of the electrode reaction. The potential extrapolated to the zero current on each straight line should be close to the formal potential. Since this plot is simple technically, the analytical result is more reliable than at least discussion of time dependence of Ep.
\nPlots of Ip vs. Ep by CV of the first (circles) and the second (triangles) peak of tetracyanoquinodimethane (TCNQ), and ferrocene (squares) in 0.2 M (CH3)4NPF6 included acetonitrile solution when scan rates were varied, where triangles were displayed by 0.4 V shift.
Most researchers have quoted the Randles-Sevcik equation, jp = 0.446 (nF)3/2c*(Dv/RT)1/2, for the diffusion-controlled peak current without hesitation, where n is the electron transfer number of the reaction. According to Faraday’s law, the electrolytic quantity is proportional to nc*. Why is the peak current proportional to n3/2 instead of n? Let us consider voltammetry of metal nanoparticles (about 25 nm in diameter) composed of 106 metal atoms dispersed in solution. Faraday’s law predicts that the current is 106 times as high as the current by the one metal atom. However, Randles-Sevcik equation predicts the current further (106)1/2 = 1000 times as large, just by the effect of the potential scan. The order 3/2 is specific to CV. The order of n for AC current and pulse voltammetry is 2 [10]. On the other hand, the diffusion-controlled steady-state currents at a microelectrode and a rotating disk electrode are proportional to n. Comparing the differences in the order by methods, we can predict that the time variation of the voltage increases the power of n.
\nLet a potential width from a current-rising potential to Ep be denoted by ΔE. When an n-electron transfer reaction occurs through the Nernst equation at which F in Eq. (1) is replaced by nF, the concentration-potential curve takes the slope n times larger than that at n = 1 (see co/cr ≅ nF(E − Eo)/RT near E = Eo in Eq. (1)). Then we have (ΔE)n = (ΔE)n = 1/n. The period of elapsing for (ΔE)n becomes shorter by 1/n, as if v might be larger by n times. Then v in Eq. (6) should be replaced by (nv)1/2. Combining this result with the flux j/nF, the current becomes n3/2 times larger than that at n = 1. Therefore, the factor n3/2 results from the Nernst equation. This can be understood quantitatively by replacing F in Eq. (3) by nF. There are quite a few reactions for n ≥ 2 both for Nernst equation and in the bulk as stable species. The term n3/2 is valid only for a concomitant charge-transfer reaction, i.e., simultaneous occurrence n-electron transfer rather than a step-by-step transfer. Apparent two-electron transfer reactions in the bulk, for example, Cu, Fe, Zn, and Pb, cause other reactions immediately after the one-electron transfer.
\nAn electrochemical response is observed as a sum of the half reactions at the two electrodes. In order to extract the reaction at the working electrode, a conventional technique is to increase the area of the counter electrode so that the reaction at the counter electrode can be ignored. If the counter electrode area is increased by 20 times the area of the working electrode, the observed current represents the reaction of the working electrode with an error of 5%. Let us consider the experiment in which nanoparticles of metal are coated on a working electrode for obtaining capacitive currents or catalyst currents. Then, the actual area of the working electrode can be regarded as the area of the metal particles measured by the molecular level. Then, the area will be several thousand times the geometric area so that the observed current may represent the reaction at the counter electrode. This kind of research has frequently been found in work on supercapacitors. On the other hand, if the electrode reaction is diffusion controlled, the current is determined by the projected area of the diffusion layer. Then the current is not affected by the huge surface area of nanoparticles.
\nIt is important to examine whether or not a reaction is controlled by at a counter electrode. A simple method is to coat nanoparticles also on the counter electrode. Then the current in the solution may become so high that the potential of the working electrode cannot be controlled. It is better to use a two-electrode system. Products at the counter electrode are possible sources of contaminants through redox cycling.
\nThe Ag-AgCl electrode is most frequently used as a reference electrode in aqueous solution because of the stable voltage at interfaces of Ag-AgCl and AgCl-KCl through fast charge-transfer steps, regardless of the magnitude of current density. The “fast step” means the absence of delay of the reaction or being in a quasi-equilibrium. The stability without delay is supported with high concentration of KCl.
\nWhen an Ag-AgCl electrode is inserted to a voltammetric solution, KCl necessarily diffuses into the solution, associated with oxygen from the reference electrode. Thus, the reference electrode is a source of contamination by salt, dichlorosilver and oxygen. It is interesting to examine how much amount a solution is contaminated by a reference electrode [9]. Time variation of ionic conductivity in the pure water was monitored immediately after a commercially available Ag-AgCl electrode was inserted into the solution. Figure 6 shows rapid increase in the conductivity as if a solid of KCl was added to the solution. Oxygen included in the concentrated KCl may contaminate a test solution. Even the Ag-AgxO electrode, which was formed by oxidizing silver wire, increased also the conductivity, probably because the surface is in the form of silver hydroxide. As a result, no reference electrode can be used for studying salt-free electrode reactions. If neutral redox species such as ferrocene is included in a solution, the potential reference can be taken from redox potential of ferrocene.
\nTime-variation of conductivity of water into which (circles) Ag|AgCl, (triangles) Ag|AgxO, and (squares) AgCl-coated Ag wire were inserted. Conductivity measurement was under N2 environment.
When a constant voltage is applied to the ideal capacitance C, the responding current decays in the form of exp(−t/RC), where R is a resistance in series connected with C. It has been believed that a double-layer capacitance in electrochemical system behaves as an ideal capacitor, where R is regarded as solution resistance. However, any exponential variation cannot reproduce transient currents obtained at the platinum wire electrode in KCl aqueous solution, as shown in Figure 7. The current decays more slowly than by exp(−t/RC), because it is approximately proportional to 1/t. The property of non-ideal capacitance is the result of the constant phase element of the DL capacitance, as described in Section 2.3. The dependence of 1/t can be obtained approximately by the time derivative of q = V0C0t−λ for the voltage step V0.
\nChronoamperometric curves when 0.2 V vs. Ag|AgCl was applied to a Pt wire in 0.5 M KCl aqueous solution. Solid curves are fitted ones by exp(-t/RC) for three values of RC.
The slow decay is related with a loss of the performance of pulse voltammetry, in which diffusion-controlled currents can readily be excluded from capacitive currents. The advantage of pulse voltammetry is based on the assumption of the exponential decay of the capacitive current. Since the diffusion current with 1/t1/2 dependence is close to the 1/t dependence, it cannot readily be separated from the capacitive current in reality. A key of using pulse voltammetry is to take a pulse time to be so long as a textbook recommends.
\nHigh-performance potentiostats are equipped with a circuit for compensation of resistance by a positive feedback. Unfortunately, the circuit is merely useful because voltammograms depend on intensity of compensation resistances of the DL capacitance. It should work well if the DL capacitance is ideal.
\nAC techniques have an advantage of examining time dependence at a given potential, whereas CV has a feature of finding current-voltage curves at a given time. The former shows the dynamic range from 1 Hz to 10 kHz, while the latter does conventionally from 0.01 to 1 Hz. This wide dynamic range of the AC technique is powerful for examining dynamics of electrode reactions. Analytical results by the former are often inconsistent with those by the latter, because of the difference in the time domain. The other scientific advantage of the AC technique is to get two types of independent data set, frequency variations of real components and imaginary ones by the use of a lock-in amplification. The independence allows us to operate mathematically the two data, leading to the data analysis at a level one step higher than CV. An industrial advantage is the rapid measurement, which can be applied to quality control for a number of samples. The analysis of AC impedance necessarily needs equivalent circuits of which components do not have any direction relation with electrochemical variables.
\nData of the electrochemical AC impedance are represented by Nyquist (Cole-Cole) plots, that is, plots of the imaginary component (Z2) of the impedance against the real one (Z1), as shown in Figure 8. The simplest equivalent circuit for electrochemical systems is the DL capacitance Cd in series with the solution resistance RS. The Nyquist plot for this series circuit is theoretically parallel to the vertical axis (Figure 8A-a), but experiments show a slope of 5 or more (Figure 8A-b). This behavior, called constant phase element (CPE) and the power law, has been verified for combinations of various materials and solvents [6, 7, 11, 12]. The equivalent circuit for Eq. (12) is a parallel combination of capacitance and resistance (Figure 8B). Even without an electrode reaction, current always includes a real component.
\n(A) Nyquist plots for a RC-series circuit with ideal capacitor (a) and DL capacitor (b). (B) Equivalent circuit with the power-law of Cd. (C) Randles circuit.
The equivalent circuit with the Randles type is a parallel combination of the ideal DL capacitor Cd with the ideal resistance Rct representing the Butler-Volmer-type charge-transfer resistance. Practically, the Warburg impedance (the inverse of Eq. (8)) due to diffusion of redox species is incorporated in a series into Rct (Figure 8C). Rct cannot be separated from the DL resistance because of the frequency dispersion. Since even the existence of Rct is in question (Section 3.12), it is difficult to determine and interpret Rct. The usage of a software that can analyze any Nyquist plots will provide values of R and C. Even if analyzed values are in high accuracy, researches should give them electrochemical significance.
\nResidual current varies with treatments of electrodes such as polishing of electrode surfaces and voltage applications to an extremely high domain. It can often be suppressed to yield reproducible data when the electrode is replaced by simple platinum wire or carbon rod having the same geometric area. Simple wire electrodes are quite useful especially for measurements of DL capacitance and adsorption. One of the reasons for setting off large residual current is that the insulator of confining the active area is not in close contact with the electrode, so that the solution penetrated into the gap will give rise to capacitive current and floating electrode reactions. Since the coefficient of thermal expansion of the electrode is different from that of the insulator, the residual current tends to get large with the elapse from the fabrication of the electrode. This prediction is based on experience, and there are few quantitative studies on residual currents.
\nUnexpected gap has been a technical problem at dropping mercury electrodes. If solution penetrates the inner wall of the glass capillary containing mercury, observed currents become irreproducible. Water repellency of the capillary tip has been known to improve the irreproducibility in order to reduce the penetration. A similar technique has been used for voltammetry at oil-water interfaces and ionic liquid-water interfaces at present.
\nVoltammograms are said to vary with electrode reaction rates, and the rate constants have been determined from time dependence of voltammograms. The fast reaction of which rate is not rate determining has historically been called “reversible.” In contrast, such a slow reaction that a peak potential varies linearly with log v is called “irreversible.” A reaction between them is called “quasi-reversible.” The distinction among the three has been well known since the theoretical report on the quasi-reversible reaction by Matsuda [1]. This theory is devoted to solving the diffusion equations with boundary conditions of the Butler-Volmer (BV) equation under the potential sweep. As the standard rate constant ks in the BV equation becomes small, the peak shifts in the direction of the potential sweep from the diffusion-controlled peak. Steady-state current-potential curves in a microelectrode [13] and a rotating disk electrode also shift the potential in a similar way. According to the calculated CV voltammograms in Figure 9, we can present some characteristics: (i) if the oxidation wave shifts to the positive potential, the negative potential shift should also be found in the reduction wave. (ii) Both the amounts of the shift should have a linear relationship to log v. (iii) The shift should be found in iterative measurements. (iv) The peak current should be proportional to v1/2.
\nCV voltammograms (solid curves) at a normally sized electrode and steady-state voltammograms (dashed curves) at a microelectrodes in 12 μm in diameter, calculated theoretically for v = 0.5 V s−1, D = 0.73 × 10−5 cm2 s−1, ks = (a) 0.1, (b) 0.01, (c) 0.001, (d) 0.0001 cm s−1. The potential shift of CV is equivalent to the wave-shift at a microelectrode through the relation, v = 0.4RTD/αFa2 (a: radius).
The authors attempted to find a redox species with the above four behaviors. Some redox species can satisfy one of the four requirements, but do not meet the others. Most reaction rate constants have been determined from the potential shift in a narrow time domain. They are probably caused by follow-up chemical reactions, adsorption, or DL capacitance. For example, CV peak potentials of TCNQ and benzoquinone were shifted at high scan rates, whereas their steady-state voltammograms were independent of diameters of microdisk electrodes even on the nanometer scale [14]. The shift at high scan rates should be due to the frequency dispersion of the DL capacitance, especially the parallel resistance in the DL (Figure 8B). Values of the heterogeneous rate constants and transfer coefficients reported so far have depended not only on the electrochemical techniques but also research groups. Furthermore, they have not been applied or extended to next developing work. These facts inspire us to examine the assumptions and validity of the BV formula.
\nLet us revisit the assumptions of the BV equation when an overvoltage, i.e., the difference of the applied potential from the standard electrode potential, causes the electrode reaction. The rate of the oxidation in the BV equation is assumed to have the activation energy of α times the overvoltage, while that of the reduction does that of (1 − α) times. This assumption seems reasonable for the balance of both the oxidation and the reduction. However, the following two points should be considered. (i) Once a charge or an electron is transferred within the redox species, the molecular structure changes more slowly than the charge transfer itself occurs. The structure change causes solvation as well as motion of external ions to keep electric neutrality. These processes should be slower than the structure change. If the overvoltage can control the reaction rate, it should act on to the slowest step, which is not the genuine charge-transfer process. (ii) Since a reaction rate belongs to the probability theory, the reaction rate (dc/dt) at t is determined with the state at t rather than a state in the future. In other words, the rate of the reduction should have no relation with the oxidation state which belongs to the future state. The BV theory assumes that the α times activation energy for the oxidation is related closely with 1-α times one for the reduction. This assumption is equivalent to predicting a state at t + Δt from state at t + 2Δt, like riding on a time machine. This question should be solved from a viewpoint of statistical physics.
\nDevelopment of scanning microscopes such as STM and AFM has allowed us to obtain the molecularly and atomically regulated surface images, which have been used for interpreting electrochemical data. Then the electrochemical data are expected to be discussed on a molecular scale. However, there is an essential problem of applying photographs of regularly arranged atoms on an electrode to electrochemical data, because the former and the latter include, respectively, microscopically local information and macroscopically averaged one. A STM image showing molecular patterns is information of only a part of electrode, at next parts of which no atomic images are often observed but noisy images are found. Electrochemical data should be composed of information both at a part of the electrode showing the molecular patters and at other parts showing noisy, vague images. Noisy photographs are always discarded for interpreting electrochemical data although the surfaces with noisy images also contribute electrochemical data.
\nAn ideal experiment would be made by taking STM images over all the electrodes that provide electrochemical data and by obtaining an averaged image. However, it is not only impossible to take huge amounts of images, but the averaged image might be also noisy. It may be helpful to describe only a possibility of reflecting the STM-imaged atomic structure on the electrochemical data.
\nVoltammograms by adsorbed redox species, called surface waves, are frequently different from a bell shape (Figure 2). Really observed features are the following: (i) the voltammogram does not suddenly decay after the peak, exhibiting a tail-like diffusional wave; (ii) the peak current and the amount of the electricity are proportional to the power less than the unity of v; (iii) the oxidation peak potential is different from the reduction one; (iv) the background current cannot be determined unequivocally; and (v) voltammograms depend on the starting potential. Why are experimental surface waves different from a symmetric, bell shape in Figure 2?
\nA loss of the symmetry with respect to the vertical line passing through a peak can be ascribed to the difference in interactions at the oxidized potential domain and at the reduced one. Since redox species takes extremely high concentration in the adsorbed layer, interaction is highly influenced on voltammetric form. When the left-right asymmetry is ascribed to thermodynamic interaction, it has been interpreted not only with Frumkin’s interaction [15] but also Bragg-Williams-like model for the nearest neighboring interactive redox species [16]. On the other hand, most surface waves are asymmetric with respect to the voltage axis even at extremely slow scan rates. This asymmetry cannot be explained in terms of thermodynamics of intermolecular interaction, but should resort to kinetics or a delay of electrode reactions. There seems to be no delay in the electrode reaction of the monomolecular adsorption layer, different from diffusion species. The delay resembles the phenomenon of constant phase element (CPE) or frequency power law of DL capacitance, in that the redox interaction may occur two-dimensionally so that the most stable state can be attained. This behavior belongs to a cooperative phenomenon [17]. A technique of overcoming these complications is to discuss the amount of charge by evaluating the area of the voltammogram. It also includes ambiguity of eliminating background current and assuming the independence of the redox charge from the DL charge.
\nThe simplest theories for voltammetry are limited to the rate-determining steps of diffusion of redox species and reactions of adsorbed species without interaction. Variation of scan rates as well as a reverse potential is helpful for predicting redox species and reaction mechanisms. Furthermore, the following viewpoints are useful for interpreting mechanisms:
comparison of values of experimental peak currents with theoretical ones, instead of discussing ΔEp and E1/2;
examining the proportionality of Ip vs. v or vs. v1/2, i.e., zero or non-zero values of the intercept of the linearity;
a reference electrode and a counter electrode being a source of contamination in solution;
attention to very slow relaxation of DL capacitive currents;
inclusion of ambiguity in the equivalent circuit with the Randles type.
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\\n\\nAs a gold Open Access publisher, an Open Access Publishing Fee is payable on acceptance following peer review of the manuscript. In return, we provide high quality publishing services and exclusive benefits for all contributors. IntechOpen is the trusted publishing partner of over 118,000 international scientists and researchers.
\n\nThe Open Access Publishing Fee (OAPF) is payable only after your full chapter, monograph or Compacts monograph is accepted for publication.
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\n\n*These prices do not include Value-Added Tax (VAT). Residents of European Union countries need to add VAT based on the specific rate in their country of residence. Institutions and companies registered as VAT taxable entities in their own EU member state will not pay VAT as long as provision of the VAT registration number is made during the application process. This is made possible by the EU reverse charge method.
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