docrisc şi securitate inustrială - Universitatea "Vasile Alecsandri"
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risc şi securitate inustrială - Universitatea "Vasile Alecsandri"
ROMÂNIA MINISTERUL EDUCAŢIEI NAŢIONALE ŞI CERCETĂRII ŞTIINŢIFICE UNIVERSITATEA “VASILE ALECSANDRI” din BACĂU FACULTATEA de INGINERIE Calea Mărăşeşti, Nr. 157, Bacău, 600115, Tel./Fax +40 234 580170 http://inginerie.ub.ro, [email protected] PHD THESIS SUMMARY RISK MANAGEMENT AND INDUSTRIAL SAFETY FOR PREVENTION, PROTECTION AND INTERVENTION IN THE EVENT OF MAJOR ACCIDENTS TO AN OBJECTIVE TYPE SEVESO COORDINATOR, Univ. dr. eng. Dr. h. c. Valentin NEDEFF Doctorand, eng. FELEGEANU DANIEL-CĂTĂLIN BACĂU - 2016 Thanks With the completion of this stage of my life, I want to express words of gratitude to the most important personalities who guided me and gave me the necessary support for development and completion of this doctoral thesis. First of all, I want to thank and to express my gratitude to my scientific coordinator, Univ. Prof. Dr. eng. Dr.h.c Valentin Nedeff, for his outstanding support for ongoing guidance, encouragement and remarkable ideas given over the period of preparation and elaborating of this doctoral thesis. Through the professionalism of his high academic support, patience and understanding manifested, and through the shared knowledge, permanent encouraging and guidance during the successive stages, especially in difficult times, he had a very important contribution in ellaborating and completion of this work. Equally, I would like to thank to assoc. Prof. doctor engineer Mirela Panainte Lehadus who guided and supported me constantly throughout the correction and doctoral studies for both the thesis and for achieving the realization of the published articles. Also, I am grateful to Mrs. prof. Dr. dr. eng. Luminiţa Bibire for the way in which she directed and supported me during this period, for all the scientific support provided, but also for the permanent welcome, criticism, which helped me to get out of the jams taken at certain steps. Special thanks to Mr. assist. univ. dr. Mircea Horubeţ, from the Department of Foreign Languages and Literatures, for the support during the thesis ellaboration. I also want to thank to my colleague from the Inspectorate for Emergency Situations Bacau County, Mrs. Professor Lidia Axinte and to Mrs. Professor Enache Veronica for their support during this thesis ellaboration. I want to thank in particular to Mr assoc. Prof. dr. eng. Emilian Mosnegutu for his support to achieve the schemes of the thesis. I want to thank to the Company's management of Amurco LLC Bacau and particularly to the civil protection inspector Mrs Anca Mihai for her technical support and the offered documentation, her trust in the use of data and implementation of accident scenarios that constituted the subject of study of this thesis. Sincere thanks I want to bring to the doctoral fellows from the University "Vasile Alecsandri" of Bacau, which over five years have contributed in a certain to achieve, develop and complete in good conditions and successfully this thesis. Particularly thanks to my former colleagues at the Regional Centre for Training of Civil Protection Bacau for their support in 2015 to ensure the necessary time to achieve the documentation and structure of this thesis. Special thanks to my wife, Liliana, who has supported me unconditionally throughout the doctoral studies, and who had the power to motivate my absences from the domestic activities, especially during the last period. I also want to thank especially to my children Larisa -Elena and Eduard-Constantin, to my mother, my brother and my sisters and to all our friends who have supported me permanently, for the understanding they have shown, their moral and spiritual encouragement, so necessary, especially during the difficult moments we went through sometimes. 2 SUMMARY GENERAL CONSIDERATIONS.............................................................................................. DEFINITION OF MAIN TERMS............................................................................................. CHAPTER 1. RISK AND INDUSTRIAL SECURITY............................................................ 1.1. RISK MANAGEMENT.............................................................................................. 1.1.1. RISK................................................................................................................... 1.1.2. CLASSIFICATION OF RISKS....................................................................... 1.1.3. RISK MANAGEMENT – STEPS IN THE PROCESS OF MANAGEMENT. 1.1.3.1. Risk identification.................................................................................. 1.1.3.2. Risk analyses.......................................................................................... 1.1.3.3. Planning.................................................................................................. 1.1.3.4. Monitoring.............................................................................................. 1.1.3.5. Control.................................................................................................... 1.1.3.6. Communication....................................................................................... 1.2. INDUSTRIAL RISK FACTORS IN DIFFERENT AREAS OF ACTIVITY........ 1.2.1. INDUSTRIAL RISK FACTORS IN MACHINERY BUILDING.................. 1.2.2. INDUSTRIAL RISK FACTORS IN THE FIELD OF CHEMISTRY AND PETROCHEMISTRY..................................................................................................... 1.2.2.1. Accidents, damages, explosions and fires.............................................. 1.2.2.2. Risks arising from substances that can be used by operators................. 1.2.3. FIRE RISK FACTORS IN INDUSTRIAL AND CIVIL AREA.......................... 1.2.4. INDUSTRIAL RISK FACTORS IN NUCLEAR FIELD.................................... 1.2.5.INDUSTRIAL RISK FACTORS IN THE TRANSPORT OF DANGEROUS SUBSTANCES................................................................................................................ 1.3. INDUSTRIAL SECURITY........................................................................................ 1.3.1. INFLUENCING FACTORS OF SECURITY IN DIFFERENT INDUSTRIAL AREAS.................................................................................................. 1.3.1.1. Influencing factors of industrial security in machinery building.............. 1.3.1.2. Influencing factors of industrial security in the field of chemistry and petrochemistry................................................................................................ 1.3.1.2.1. The safety report (in the context of Seveso)................................... 1.3.1.2.2. Major accidents prevention policy.................................................. 1.3.1.2.3. Internal and external emergency plan............................................. 1.3.1.2.4. Plans to prevent accidental pollution............................................... 1.3.1.2.5. Risk maps........................................................................................ 1.3.1.2.6. Measurements of emissions and imissions, monitoring of technological processes in order to prevent pollution................................... 1.3.1.2.7. Report analyses and evaluation of environmental pollution........... 1.3.2. INFLUENCING FACTORS OF SECURITY AT FIRE...................................... 1.3.2.1. Management structure that will ensure fire safety..................................... 1.3.2.2. The activities to be carried in case of fire.................................................. 1.3.3. INFLUENCING FACTORS OF SECURITY IN TRANSPORT OF DANGEROUS SUBSTANCES..................................................................................... CHAPTER 2. MANAGEMENT OF MAJOR ACCIDENTS INVOLVING DANGEROUS SUBSTANCES............................................................................................................................... 2.1. MAJOR ACCIDENTS THAT INVOLVED DANGEROUS SUBSTANCES....... 2.1.1. BRIEF HISTORY OF THE ACCIDENT AT SEVESO ITALY......................... 2.1.2. OTHER MAJOR INDUSTRIAL ACCIDENTS THAT TOOK PLACE IN THE WORLD ALONG THE TIME.............................................................................. 8/8 10 14/11 14/11 15/12 15/12 20 20 20 21 21 21 22 22/14 22 25 25 26 26 30 31/14 32/15 33/15 33 35/16 35/16 36/17 38 38 39 39 40 40 41 41 44 49/19 49/19 50/19 51/21 3 2.2. LEGAL ISSUES.......................................................................................................... 2.2.1. CHARACTERISTICS OF SEVESO DIRECTIVE............................................ 2.2.2. IMPLEMENTATION OF SEVESO DIRECTIVE II......................................... 2.2.3. SEVESO DIRECTIVE IMPLEMENTATION IN ROMANIA......................... CHAPTER 3. THEORETICAL SOLUTIONS REGARDING THE CONTROL OF MAJOR ACCIDENTS RISK....................................................................................................... 3.1. INDUSTRIAL RISK EVALUATION METHODS IN WHICH ARE INVOLVED DANGEROUS SUBSTANCES.................................................................. 3.1.1. HAZOP METHOD............................................................................................. 3.1.1.1. Generalitie................................................................................................. 3.1.1.2. Details of the HAZOP methodology......................................................... 3.1.2. METHOD OF PROTECTION BARRIERS LOPA (LAYER OF PROTECTION ANALYSIS)......................................................................................... 3.1.2.1. Generalities................................................................................................. 3.1.3. TECHNICAL/ TECHNOLOGICAL RISK ANALYSIS METHOD – MOSAR........................................................................................................................ 3.1.4. ARAMIS METHOD............................................................................................ 3.1.4.1. Presentation ARAMIS project targets....................................................... 3.1.4.2. The main results of ARAMIS project....................................................... 3.1.4.2.1. Basic concepts.............................................................................. 3.1.4.3. Evolution, takeover and application of the project................................... 3.1.4.4. The method application............................................................................ 3.1.5. METHOD QRA..................................................................................................... 3.1.5.1. Selecting installations for QRA................................................................ 3.1.5.2. Defining the produced events and their frequency.................................... 3.1.5.3. Modelling the dangerous phenomena intensity......................................... 3.1.5.4. The calculation and presentation of results............................................... 3.1.6. OCTAVE METHOD............................................................................................. 3.1.7. MEHARI METHOD............................................................................................. 3.1.8. CHECKLIST METHOD FOR RISK ANALYSIS............................................... 3.1.8.1. Describing analysis stages of risk............................................................... 3.1.8.1.1. Identification of relevant security installation............................... 3.1.8.1.2. Dangers identification................................................................... 3.1.9. METHODS BASED ON CONSEQUENCES....................................................... 3.1.10. METHODS BASED ON RISK............................................................................ 3.1.11. THE ”DETERMINISTIC” APPROACH............................................................. 3.1.12. COMBINED METHODS.................................................................................... 3.2. ANALYSIS AND SELECTION OF STRONG POINTS IDENTIFIED AT THE STUDIED RISK EVALUATION METHODS......................................................... 3.3. ANALYSIS OF WEAK POINTS IDENTIFIED AT THE STUDIED RISK EVALUATION METHODS.............................................................................................. 3.4. ADVANTAGES OF THE EXISTING METHODS FOR ELLABORATING A NEW METHOD............................................................................................................... 3.5. THE PRINCIPLE OF CARMIS METHOD............................................................... 3.6. STAGES AND METHODOLOGY FOR THE IMPLEMENTATION OF THE CARMIS/DS METHOD............................................................................................. 3.6.1. DESCRIPTION OF STAGES................................................................................. 3.6.2. SWOT ANALYSIS OF CARMIS METHOD........................................................ CHAPTER 4. BASE DESIGN AND IMPLEMENTATION OF TECHNICAL RESEARCH ON INDUSTRIAL AND SECURITY MANAGEMENT................................... 4.1. GENERAL STAGES OF RISK ANALYSIS......................................................... 55/22 56 57 58/23 60/25 61/26 62 62 62 64 64 67 70 70 70 70 72 72 73 73 74 74 74 75 76 77 78 78 78 81 81 82 82 90 91 2/34 93/35 93/35 95 101/37 102 103 4 4.2. SIMULATION PROGRAMS USED IN RISK EVALUATION AND ITS ENVIRONMENTAL AND POPULATION IMPACT................................................. 4.2.1. SIMULATION PROGRAM EFFECTS 7.......................................................... 4.2.2. SIMULATION PROGRAM SLAB View.......................................................... 4.2.3. SIMULATION PROGRAM SEVEX View....................................................... 4.2.4. SIMULATION PROGRAM PHA Pro 7............................................................ 4.2.5. SIMULATION PROGRAM ISC- AERMOD.................................................... 4.2.6. SIMULATION PROGRAM ALOHA............................................................... 4.3. DATABASE OF OBJECTIVES TO BE ANALYSED REQUIRED FOR THE IMPLEMENTATION OF CARMIS METHOD............................................................. 4.4. PLANS AND SCENARIOS FOR THE EXERCISES AND APPLICATIONS................................................................................................................ CHAPTER 5. SETTING RESEARCH METHODOLOGY FOR RESEARCH , CORRELATIONS AND MATHEMATICAL MODELS......................................................... 5.1. INFLUENCE OF ENVIRONMENTAL FACTORS ON MAJOR ACCIDENTS INVOLVING DANGEROUS SUBSTANCES........................................ 5.2. METHODOLOGY FOR THE IMPLEMENTATION OF CARMIS METHOD BASED ON A CASE STUDY AT S.C. AMURCO S.R.L.......................... 5.2.1. ESTABLISHMENT OF EVALUATION TEAM................................................. 5.2.2. DEFINING THE SYSTEM ANALYSIS (INSTALLATION/ TECHNOLOGY)............................................................................................................. 5.2.2.1. Location of installation (location).............................................................. 5.2.2.2. General technical plan of the economic operator....................................... 5.2.2.3. Describing the system (process, chemical installation).............................. 5.2.2.4. Process or control installations................................................................... 5.2.2.5. Normative manufacturing , tehnological schemes , operating Procedures.............................................................................................................. 5.2.2.6. Quantities of dangerous substances and their characteristics..................... 5.2.2.7. Metheorological conditions of the area to place the objective................... 5.2.2.8. Seismic characteristics of the area............................................................. 5.2.3. ANALYSIS OF THE LAND AND IDENTIFICATION OF RISK FACTORS IN THE SYSTEM......................................................................................... 5.2.3.1. Presentation of the installation, identifying of sources of danger............... 5.2.3.2. Inventory of dangerous substances............................................................. 5.2.3.3. Identifying danger, risk assessment and control......................................... 5.2.3.4. Identification the area with the highest risk............................................... 5.2.3.5. Setting targets for prevention...................................................................... 5.2.4. ESTABLISHING CHECKLISTS........................................................................... 5.2.5. DRAFTING THE TREES OF FAILURE............................................................... 5.2.6. ELABORATING THE ACCIDENT SCENARIO.................................................. 5.2.6.1. SIMULATION OF DISTRUCTION OF CHEMICAL TANK OF AMMONIA REALIZED WITH THE SIMULATION PROGRAM LOHA............. 5.2.6.1.1. THE EVENT SCENARIO, INTRODUCTION OF DATA INTO THE PROGRAM.............................................................................................. 5.2.6.1.2. DESCRIPTION OF THE SITE........................................................ 5.2.6.1.3. THE METHEOROLOGICAL SITUATION................................... 5.2.6.1.4. ESTABLISHING THE SOURCES FOR THE SCENARIO........... 5.2.6.1.5. THE CHEMICAL DANGEROUS SUBSTANCE.......................... 5.2.6.1.6. ONE CHOOSES THE SITUATION WHEN THE SUBSTANCE DOES NOT BURN........................................................................................... 5.2.6.1.7. MATHEMATIC MODELING AND PRINCIPLES REGARDING THE NUMBER SIMULATION.............................................. 105 105 106 107 108 108 109 111 111 112/38 112 114 114/38 115/39 115/39 116/40 117/41 118/42 119/44 121/45 122/46 123/47 123/47 124/48 124/48 125/49 126/50 130/54 131/55 133/57 134/58 138/62 140/64 141/65 142/66 143/67 143/67 144/67 145/69 5 5.2.6.1.8. QUANTITY AND AMMONIA LEAK TIME.................................. 5.2.6.1.9. AMMONIA LEAK FREE ZONE WITHOUT FIRE....................... 5.2.6.1.10. INFLAMABIL AREA..................................................................... 5.2.6.1.11. AREA OF EXPLOSION.................................................................. 5.2.6.1.12. ESTABLISHING THE EVACUATION ZONES............................ 5.2.7. ASSESSING RISK FACTORS IDENTIFIED IN TERMS OF SERIOUSNESS............................................................................................................. 5.2.8. EVALUATION OF INITIATING FREQUENCY EVENTS AND CONFIDENCE LEVELS OF BARRIERS................................................................... 5.2.9. ESESTIMATING THE DIRECT IMPACT OVER THE ASSETS, THE DATES AND INFORMATION, INFRASTRUCTURE AND THE STAFF............... 5.2.10. EVALUATION OF THE EXISTING PROTECTION FACTORS, COMPENSATION AND REHABILITATION............................................................ 5.2.11. PERFORMANCE EVALUATION OF SAFETY BARRIER.......................... 5.3. METHODOLOGY FOR THE IMPLEMENTATION OF THE METHOD CARMIS/DS FOR A CASE STUDY AT S.C. CHIMCOMPLEX S.A.......................... 5.3.1. ESTABLISHMENT OF EVALUATION TEAM............................................... 5.3.2. DEFINING THE SYSTEM ANALYSIS (INSTALLATION/ TECHNOLOGY).......................................................................................................... 5.3.2.1. Location of the installation (location)..................................................... 5.3.2.2. Activity profile........................................................................................ 5.3.2.3. Process or control installations............................................................... 5.3.2.3.1. Chlor installation...................................................................... 5.3.2.4. Quantity of dangerous substances and their characteristics..................... 5.3.2.4.1. Chlor – Cl2............................................................................... 5.3.2.4.2. Ammonia - NH3...................................................................... 5.3.2.4.3. Monomethylamine................................................................... 5.3.2.5. The metheorologic situation of the area for the location of the objective............................................................................................................... 5.3.3. ANALYSIS OF THE LAND AND IDENTIFICATION OF RISK FACTORS IN THE SYSTEM......................................................................................................... 5.3.3.1. Identification of the dangers, risk evaluating and control....................... 5.3.3.1.1. Identification of the danger of substances.................................. 5.3.3.1.2. Risk evaluation........................................................................... 5.3.3.2. Identification of the the area with the highest risk.................................... 5.3.3.2.1. Chlor installation........................................................................ 5.3.3.2.2. Identification of highest risk areas............................................. 5.3.4. ESTABLISHMENT OF CHECKLISTS.............................................................. 5.3.5. DRAFTING THE TREES OF FAILURE............................................................ 5.3.6. ELABORATION OF THE ACCIDENT SCENARIO......................................... 5.3.6.1. SIMULATION OF THE CHEMICAL ACCIDENT WITH THE CHLORINE TANK CRACKING, SIMULATION PROGRAM COMPLETED WITH THE ALOHA..................................................................... 5.3.6.1.1. THE EVENT SCENARIO, ENTERING DATA IN THE PROGRAM................................................................................................. 5.3.6.1.2. DESCRIPTION OF THE SITE........................................................ 5.3.6.1.3. THE METHEOROLOGICAL SITUATION................................... 5.3.6.1.4. SCENARIOS FOR DETERMINING THE SOURCE.................... 5.3.6.1.5. MATHEMATIC MODELING AND PRINCIPLES REGARDING THE NUMBER SIMULATION............................................. 5.3.6.1.6. THE QUANTITY AND THE TIME FLOW CHLORINE.............. 5.3.7. EVALUATION OF RISK FACTORS IDENTIFIED FROM THE GRAVITY 146/69 149/72 150/73 151/73 152/74 152/74 153/75 158/80 158/80 161/83 163 163 163 163 164 164 164 165 165 165 166 167 168 168 168 168 169 169 170 170 171 171 173 173 174 174 175 178 180 6 POINT OF VIEW........................................................................................................... 5.3.8.EVALUATION OF INITI ATING EVENTS AND THE CONFIDENCE LEVELS OF BARRIERS................................................................................................ 5.3.9. ESTIMATION OF DIRECT IMPACT ON THE GOODS, DATES, INFORMATION, INFRASTRUCTURE, STAFF.......................................................... 5.3.10. EVALUATION FACTORS FROM PROTECTION, COMPENSATION AND REHABILITATION OF EXISTING............................................................................... 5.3.11. PERFORMANCE EVALUATION OF SAFETY BARRIERS............................ CHAPTER 6. OBTAINED EXPERIMENTAL REZULTS..................................................... 6.1. OBTAINED EXPERIMENTAL REZULTS AND THEIR INTERPRETATION......................................................................................................... 6.2. DRAFTING SECURITY REPORT, THE MAIN DOCUMENT OF THE MANAGEMENT OF SECURITY SYSTEM................................................................. GENERAL CONCLUSIONS...................................................................................................... BIBLIOGRAPHY.......................................................................................................................... 181 181 182 183 184 186/85 186/85 188/87 190/89 197/96 APPENDIX NO. 1 – Economic operators from Bacau county ranked in terms of SEVESO III. Directive APPENDIX NO. 2 – Situation of objectives at risk -chemical accident from Bacau County. APPENDIX NO.3 – Fire situation on settlement and causes in 2014 . APPENDIX NO. 4 – Security report at S.C. AMURCO S.R.L. BACĂU. APPENDIX NO. 5 – Security report at S.C. CHIMCOMPLEX S.A. ONEŞTI. 7 GENERAL CONSIDERATIONS The existence of the sources of risk and the production of natural and technological disasters are increasingly more in the attention of scientists and specialists from institutions with responsabilities in this area. The phenomena and disaster risk sources , the causes and the consequences of events are analysed more thoroughly by the specialists within the studies at work , research in the field, symposia, scientific communications and other forms. The first necessary condition for economic growth and for the protection of the employees is the security of the economic operators that use dangerous substances in the manufacturing process and its implementation can be done by developing a new concept of security in the chemical industry. This concept must follow the approach of technological and ecological problems of the economic operator , the security aspects of the environment and protect the site in terms of physical security from fire and natural disasters as well as the limitation of the consequences of producing the events which still occur and the complete restoring of the production capacity [63]. Risks are present in all the economic and industrial activities that are marked both by economic loss from damage occuring at the installations or machinery, as well as by producing minor or major accidents with particularly serious consequences resulting in deaths and injuries or the pollution of the environment. [64]. The evaluation of risk levels stimulates the economic operators to improve their working conditions and the environment respectively to take measures for passing from higher levels of risks to lower, acceptable levels. The application and the generalization of such methods allows the establishment of social security allowances which can vary according to the level of risk/security of the economic operators including the criteria of safety in their wages and the criteria of productivity and complexity of work. [12]. The activity of risk management developed both from a conceptual and practical point of view , became an industry in the countries with functioning financial markets, but in Romania few organizations have developed their own mechanisms for measurement and covering the risks, but others do not even know the benefits they would get by applying the procedures already established [13]. The active participants in the process of harmonizing risk evaluation methods recommend a quantitative estimation method for major accident risk. According to the possible consequences of the accident, major security systems installation and protection of the employees and the people of the incidence are established. An accurate estimation of the risk of a major accident offers the possibility of providing better protection for potential receptors. The factors necessary for changing 8 legislation regarding the prevention of major accidents in Europe were not enough deepen and modelled up to present and the relationship between a major accident and changing legislation is still unclear [111]. Globally, the chemical industry has held a series of major accidents. In Europe, the accident in Seveso-Italy in 1976 led to the adoption of legislation to prevent and control such accidents. In 1982 the European Council adopted Directive no. 501/EC of 24 June 1982 on the major accident hazards of certain industrial activities - Seveso I Directive replaced by the Seveso II Directive Council Directive 96/82/EC from 9 December 1996 regarding the control of major accident hazards involving dangerous substances, subsequently amended and repealed by the Seveso III Directive 2012/18/EU of the EUROPEAN PARLIAMENT and of the COUNCIL from 4 July 2012 on the control of major accident hazards involving dangerous substances [12, 63]. Industrial accidents involving dangerous substances, often have very serious consequences. Some serious accidents, well known as those from Seveso, Bhopal, Schweizerhalle, Enschede, Toulouse and Buncefield have caused significant loss of life and/or environmental destruction as also costs of billions of euros. After these accidents, the political awareness level regarding risk recognition and initiation of appropriate precautions to protect citizens and communities has increased significantly [104]. Seveso II Directive, which covers approximately 10,000 entities in the European Union, had an essential role in reducing the probability of producing chemical accidents and their consequences .However, it is necessary at all times to ensure the maintenance of high levels of existing protection and, if possible, such protection to be further improved. Major accidents produced in Toulouse France Enschede - Netherlands, Bhopal - India, Baia Mare - Romania have been studied in depth by specialists of the European Union, resulting in the need to change legislation in this area with immediate effects on the activities of economic operators who use dangerous substances in the production process or transport of dangerous substances [6, 34]. Seveso II Directive was transposed into Romanian legislation by H. G. no. 95 of 2003 on "control of the activities of major-accident hazards involving dangerous substances", replaced in 2007 by H.G. no. 804. Accidents produced in recent years and the development of science and technology have demonstrated the limits and difficulties of the existing methods of risk evaluation [7]. Seveso II Directive requirements need to achieve the required development of new methods of risk evaluation, demonstrating authorities with responsabilities in the area and citizens that: • the economic operator concerned has taken all the necessary measures to analyze the risks covering ; • allows communicating the results of the risk assessment to all the persons likely to be 9 affected by a major accident. Risk identification is the most difficult because of the multitude and diversity of events. Possibilities of occurrence of events can be estimated by statistical studies. Chances of getting reliable results through the strict application of theoretical relationships are very limited. Risk analysis is a matter of great complexity and difficulty [64]. Establishing limits of acceptability of the consequences and the use of methods, means and procedures of prevention of major accidents, limiting and removing their consequences are determined by the environmental assessor’s average experience [125]. 10 CHAPTER 1 . RISK AND INDUSTRIAL SECURITY 1.1. RISKS MANAGEMENT Risk management is a systematic and rigorous process of identification, analysis, planning, control and risk communication. Each identified risk passes sequentially through the other functions, continuously and concurrently. Risks are usually pursued in parallel with the identification and analysis of new ones and the plans of attenuation for risk can produce other risks [13]. Risk management is conducted in any decision-making process and, in order to be effective, it is necessary to reconsider the current rocesses of analysis and decision taking. An effective risk management process also represents a set of specific, continue and systematic activities of exchange of relevant information in an open environment. Risk management provides a rigorous and active environmental decision-making for [10]: • continuously assessing what could have unwanted consequences; • determination of significant risks, to be studied; • implementation of strategies for managing these risks; • ensuring the effectiveness of the implemented strategies. Implementing the processes for identification, analysis, planning, control and risk communication of any kind shall, at any level, ensure a number of advantages, including [13]: • avoiding surprise: continuous evaluation of what can end badly anticipate events and their consequences; • increasing the likelihood that events occur as expected: the results of the decisions may be influenced by weighing the potential impacts andthe associated probabilities; the understanding of risk enables better decision making; • changing the emphasis from treatment of a crisis on its prevention: management of risks can identify and then prevent the potential problems when it is easier and cheaper to do, before conversion to real problems and then the crisis (the prevention factor is more pronounced); • focusing on the main objectives and detecting the events that may affect the achievement of these objectives; Identifying in time the potential problems (the practical approach ) as a possible support in decisions making in resource allocation. 11 1.1.1. RISK In broad, RISK can be defined as a potential event that, if produced, causes loss, damages, distructions, sufferings etc. According to the domain they can occur or depending to their nature, one can talk about a great diversity of risks [17, 64]. One can give as a characteristic of risk the existence exposure to negative consequences of population, material goodss, heritage or environment. Another criterion one can operate with in identifying and arranging specific risks represents the vulnerability of the elements exposed to risk [30, 47]. This fact highlights how much a person and his goods are exposed to various hazards, indicating the likely level of damages that can be produced by a certain phenomenon. The negative effect taken into consideration when defining specific risks is usually the level of losing human lives, of the injujured number, of damages produced on properties and economic activities by a certain phenomenon or a group of phenomena in a certain place and at a certain period of time. As a consequence, risk is the probability to human and goods exposure to a particular hazard of a certain size and can be expressed mathematically as the product of hazard, risk and vulnerability of the elements exposed [133]: R = f(H x E x V/C) (1.1) unde: R represents - risk ; H – hazard; E – elements exposed to risk (persons, goods); V – vulnerability; C – capability (capacity to adapt / the answer of the comunity). It follows that the risk exists depending on the size of danger, of all groups of people and material goods endangered and their vulnerability and can be defined as a predictive mathematical loss of life, injuries, property damage and damage to economic activity over a period of reference in a given region, for a specific hazard [7]. 1.1.2. CLASSIFICATION OF RISKS Depending on the area of production risks can be divided into : cross-national, regional, county and local risks [148]. Cross-national risks are risks that according to their manifestation, affect a part of the area of a country or many countries. [19, 28]. National risks are risks that, according to their way of manifestation, affect more than half of a country. Regional risks are the ones that, according to their way of manifestation, affect a part of a 12 county or more surrounding counties. County risks are risks that, according to their manifestation, affect only localities from the same county. Depending on the way of production and the consequences generating events, risks can be: natural risks; technological risks; biological risks; fire risk. Fire risk is a risk that occurs with greater frequency and with consequences more or less increased in comparison with other risks for which will be treated separately. In figure 1.1 one can see the events generating situations of emergency produced by technological risks: FALLING OF COSMIC OBJECTS FROM THE ATMOSPHERE MAJOR ACCIDENTS IN THE CHEMICAL INDUSTRY ACCIDENTS PRODUCED DURING TRANSPORT EVENTS GENERATING EMERGENCY SITUATIONS NUCLEAR ACCIDENTS DISCOVERED AMMUNITION REMAINED UNEXPLODED DURING MILITARY CONFLICTS DETECTION OF PUBLIC UTILITIES AND PRODUCTION OF MAJOR DAMAGES THE COLLAPSE OF SOME BUILDINGS OR INSTALLATIONS Figure 1.1 Events generating situations of emergency 1.2. INDUSTRIAL RISK FACTORS IN DIFFERENT AREAS OF ACTIVITY 1.2.5. INDUSTRIAL RISK FACTORS IN THE TRANSPORT OF DANGEROUS SUBSTANCES Dangerous substances are present in all areas of industry and industries where the risk associated with the specific sites known but for which no action is taken to minimize or eliminate them [9, 86]. 13 Accidents during transport represent a particular risk, particularly for urban or rural areas that do not have industrial activity which could cause accidents involving dangerous substances, the local population is not ready for self-protection in case of such an event [121]. In figure 1.2. one can see the transport ways where can be produced accidents involving dangerous substances. ROADS 50% MARITIME AND WATER WAYS 20% RAILROADS 30% Figura 1.2. The transport ways where can be produced accidents involving dangerous substances. Dangerous substances are transported in tank wagons, tankers, containers or special packaging, able to [121]: gas at normal pressure; compressed gas; liquefied gas; liquid; solid (compact, cristals, dust). About 15% from all the transported staff along a year period is represented by the staff containing dangerous substances. Given the fact that the circumstances in which accidents may occur namely: the quantities of dangerous substances released into the atmosphere and on the ground after the accident, can not feasibly be provided and can not be taken any preventive measures. Because of this aspect, the population in areas of communication lines can not be forewarned and protected from any consequences of such an accident. After an accident involving dangerous substances there can be caused an explosion followed by fire, direct in the means of transport or due to the release of dangerous substance on the ground, thus there exists the risk of the 14 threat of human and animal health, risk of environmental contamination, risk of partial or total damage to buildings, damage to material goods that produce major effects of short or long on holding community activities [103]. 1.3. INDUSTRIAL SECURITY For the productivity growth for operators using dangerous substances in the production process, it is necessary to identify a security concept to be linked to aspects of quality, environmental and technological and security issues in the business environment. Mitigation of unwanted accidents consequences and short while restoring production capacity is a prerequisite of the security concept [67]. 1.3.1. INFLUENCING FACTORS OF SECURITY IN DIFFERENT INDUSTRIAL AREAS 1.3.1.2. Influencing factors of industrial security in he field of chemistry and petrochemistry Natural and technological risks affect the economic and social development of the regions exposed. They have destructive effects on both the environment and on the economy and life safety. It is generally impossible to prevent, and in recent years the frequency of their manifestation has significantly increased [48]. Even if now most resources are focused on response actions and recovery following a disaster to most communities, prevention and mitigation of the consequences is much more important [58]. The complexity of industrial sites, the variety of materials used and technological processes determine the need for using more methods and techniques for identifying and assessing hazards and risks [84]. Such risk evaluation is a complex study, which is based on a series of qualitative and quantitative analysis methods, which estimates the probability and severity of technological accidents and sets measures to limit or eliminate the consequences of accidents [85]. Evaluation studies of natural and technological risks affecting the population becomes a necessity and serve to identify those critical points for achieving effective solutions to reduce the risks where necessary and promote the growth of industrial safety by applying field factors influence of industrial safety [56, 110]. In the chemical and petrochemical domain, the determinant factors of industrial safety are [111]: the security reports; the policy of preventing major accidents; 15 internal and external emergency plans ; plans for preventing accidental pollution; maps of technological risk; emission and immission measurements and monitoring of processes in terms of pollution prevention; reports of analyzing and evaluation of medium pollution. 1.3.1.2.1. The security report (in the context of SEVESO DIRECTIVES) The security report is made according to article 10 of SEVESO Directive III which specifies obligation operator with high risk to develop a safety report which is documentation drawn up by natural or legal persons certified under the legal provisions necessary for targets where dangerous substances are present [103, 106]. By means of the safety report one demonstrates that [107]: • "There are efforts to implement the policy to prevent major industrial accidents and the system of technological safety management; • All major hazards have been identified and have measures in place to prevent accidents and also to limit the possible effects; • ensure a high level of safety and security during design, operation, construction, etc .; • emergency internal and external plans are prepared, which represents all measures to be taken within the objective to limit and remove the consequences of any situation which lead to uncontrolled developments during the operation of industrial facilities that can endanger the health of staff and/or more dangerous substances in relation to the target; • There is basic information on territorial planning decisions ". 1.3.1.2.2. Major accidents prevention policy The general policy for preventing, preparing and responsibility in case of industrial accidents is based on the following principles [125]: prevention, which assumes operation in such a way as to prevent uncontrolled development of the abnormal operations, the consequences of any accidents to be minimum and in accordance with the best available security techniques; identification and evaluation of major risks through systematic studies of hazard and operability and detailed security analysis for each identified individual cases; evaluation of security necessities prioritized according to the "nature and extent of danger expected" based on the quantities of dangerous substances and industrial activities and relevant susceptible to accidents. 16 The policy of preventing major accidents in case of economic operators constitute an assurance and continuous engagement to safety in the operation of facilities and equipment in all places of employment, to reduce risk of incidents and accidents arising from the storage and handling of dangerous products on their location [ 87, 133]. In the case of the economic operator will be applied specific measures for maintaining safety in operation, that will help to achieve the following objectives [125]: reducing to minimum the potential medium risks through an accurate evaluation of security necessities ranked according to the "nature and extent of danger expected"; ensuring compliance with legal rules and regulations; training the whole staff in order to know the risks and medium problems that their work involves; evaluation of risks associated to the activities whenever changes occur in processes, practices or resources; providing staff schooling required in operating practices and use of equipment and devices safety; carrying out of emergency planning, performance monitoring and review; continuous improving of health and safe conditions at work by drawing up plans to prevent potential risks and to minimize the consequences of possible accidents; constant communication with all the stakeholders to ensure transparency regarding the possiblenegative consequences of their activity in the external environment. The management program will ensure the necessary resources to adopt safety measures and investment in equipment, monitoring by periodic environmental audits performances [88]. Management objective is to obtain economic and financial performance in terms of environmental protection and optimum safety and health for the employees, which set out the measures to prevent and reduce risks of injury and illness of staff. In figure 1.4. lines of action are presented in health and safety at work, in which the management of the objective must undertake [13]: 17 CURRENT LOW COMPLIANCE WITH HEALTH END SAFETY AT WORK IMPROVING THE SECURITY PERFORMANCE THE TRAINING OF THE STAFF FOR TECHNICAL COMPLIANCE MEASURES PERIODIC REVIEW OF THE ACTIVITY OF WORK HEALTH AND SECURITY REDUCING OR REMOVAL OF INJURY RISK Figure 1.4. Lines of action in safety and health at work 18 CHAPTER 2. MANAGEMENT OF MAJOR ACCIDENTS INVOLVING DANGEROUS SUBSTANCES The major accident caused by dangerous substances "is an event (emission of dangerous substances, fire, explosion) occurred in uncontrolled developments during the operation of an objective, which leads to immediate or delayed aparition of some serious dangers to human health and/ or environment, inside or outside the objective and involving one or more dangerous substances "[12, 29, 89]. The general policy for prevention, preparing and responsibility to industrial accidents is based on the following principles [111]: - prevention which involves the operation so as to prevent the uncontrolled development of abnormal operations, the consequences of possible accidents to be minimal and in line with the best security techniques available; - Identify and evaluate the major risks through systematic studies of danger and operability and detailed security analysis for each identified individual cases; - Evaluating the security needs prioritized according to the "nature and extent of danger expected" based on the quantities of dangerous substances and industrial activities and relevant susceptible to accidents. Policy to prevent major accidents to operators constitute a continuous assurance engagement to safety in the operation of installations and equipment in all places of employment, to reduce risks of incidents and accidents arising from the storage and handling of dangerous products on their location [95 ]. 2.1. MAJOR ACCIDENTS THAT INVOLVED DANGEROUS ACCIDENTS Major accidents produced in Toulouse - France Enschede - Netherlands, Bhopal - India, Baia Mare - Romania have been studied in depth by specialists of the European Union, resulting in the need to change legislation in this area with immediate effects on the activities of economic operators who use the dangerous substances in the production or transport of dangerous substances [5, 103, 104]. 2.1.1. SHORT HISTORY OF THE ACCIDENT FROM SEVESO ITALY Seveso is the name of a city in Italy, north of Milan where, on July 10, 1976, there was an accident at the chemical pesticide factory ICMESA. At the production of trichlorophenol, by 19 overheating, there was eliminated in the atmosphere a form of highly poisonous tetrachlorodibenzodioxines and since then, this chemical compound is called Seveso poison and dioxin and polychlorinated represent symbolically highly toxic materials. In Fig. 2.1. A and B are shown the pictures of the accident at Seveso Italy [24]. After the accident there occurred approximately 6 tons of toxic substances into the atmosphere, resulting in the occurrence of a condition of chloracne (a dermatitis caused by exposure to chlorine and its derivatives) among the population living in the impact zone and exposing a large number of over 35,000 people, more than 700 citizens affected resettled in an area of 110 ha (the oak forest today at Seveso); there were sacrificed 80,000 animals in order to prevent contamination through the food chain affected and more than 4% of the animals at farms in the vicinity died. Figure 2.1. A Figure 2.1. B Figure 2.1 Images from the SEVESO accident, Italy [24]. This accident was a warning which prompted the European Community to take steps to prevent similar situations. After the accident at Seveso, the European Community has defined the concept of 'major accident' (high risk) as an event (an emission of substances, fire or explosion) in relation to the uncontrolled development of technological activities that generate a serious danger inside or outside the enterprise by releasing one or more toxic substances. Directive "SEVESO I – European Council Directive no. 82/501/EC on major accident risks of certain industrial activities "was adopted on 24 June 1982 and includes a set of bonds, aimed at employees of industrial factories and national authorities. According to this directive, the European Commission is aimed at identifying and controlling the risk of major accidents from industrial installations [78, 135]. 20 2.1.2. OTHER MAJOR INDUSTRIAL ACCIDENTS THAT TOOK PLACE IN THE WORLD ALONG THE TIME The major industrial accidents that occurred in the world over the past 77 years highlight the potential effects of accidents that originate from dangerous substances. In table 2.1. major industrial accidents that occurred in the world over the last 77 years are presented [46]. Table 2.1. Major industrial accidents that occurred in the world over the last 77 years [46]. Year 1939 1976 1979 1979 1984 Country Romania (Zărneşti) Italy (SEVESO) Canada Romania (Bucharest) Type of accident Substace Deads Number of Number of intoxicated evacuated persons persons Explosion of a tank Chlor - 600 - Accident at a reactor Erbicides - 500 730 - - 250.000 27 175 - 3.598 100.000 200.000 452 4.248 31.000 1 350 100.000 55 3.600 - - 15.400 - Transport accident Propan, ( railroad ) chlor Accident at a tank Ammonia India Accident at a pesticides Methyl (Bhopal) factory isocyanate Explosion of a tank Benzine Mexic 1984 (Ciudad de Mexico) 1985 India 1987 China 1988 China Major toxic leaks Sulfur trioxide Accident due to Methylated a human error alchool Contamination of water Ammonia bicarbonate 21 Continuare Tabel 2.1. Year 1988 1989 1992 1992 1994 2001 2001 Country Type of accident Romania Accident due to (Fălticeni) a human error USA Fire at a chemical factory Haiti Explosion at a chemical factory Senegal Explosion of a tank South Accident at a golden Africa mine Romania Accident due to (Fălticeni) a human error France (Toulouse) Explosion at a deposit Substace Number of Number of intoxicated evacuated persons persons - - 400 - - 16.000 10 154 - 100 400 - 77 450 - - 150 - 25 2.442 - Dea ds Acetone cyanohydrin, sulfuric acid Sulfuric acid Mixtures of toxic substances Ammonia Cyanide and hydrogen cyanide Acetone cyanohydrin, sulfuric acid Ammonium nitrate 2.2. LEGISLATIVE ASPECTS The necessary factors for changing legislation to prevent major accidents in Europe were not enough to understand and shape the present relationship of a major accident and changing legislation is still unclear [67, 71]. In Europe, the accident in Seveso - Italy in 1976 led to the adoption of legislation to prevent and control such accidents. In 1982 the European Council adopted Directive no. 501/EC of 24 June 1982 on the major-accident risks of certain industrial activities - Seveso I was replaced by Seveso II Directive - Council Directive 96/82/EC of 9 December 1996 on the control of major accident risks involving dangerous substances, subsequently amended and repealed by the Seveso III Directive 2012/18/EU oF THE EUROPEAN PARLIAMENT and of the COUNCIL of 4 July 2012 on the control of major accident risks involving dangerous substances. This applies to sites which "mean the whole area under the control of an operator where one or more installations, including infrastructures or common activities or related substances are hazardous establishments are either lower-tier or upper-tier "[9, 13]. 22 The new Seveso III Directive aims "to establish rules to prevent major accidents involving dangerous substances and limit their consequences on human health and the environment, to ensure a high level of protection throughout the Union in a consistent and effective manner "[104]. The SEVESO Directive grants more rights to population regarding both the access to information and to consultation. Both public authorities and operators have clear obligations to inform the public. It's about the passive information, which consists of continuous access to information, but also the active one. The operators and competent authorities should actively participate by distributing leaflets and brochures, for example, informing the public about the behaviour in case of an accident [63, 111]. However, the competent authorities are required to organize an inspection system that ensures systematic evaluation of the operators or at least one inspection a year at each level [111]. 2.2.3. TRANSPOSITION OF THE SEVESO DIRECTIVE IN ROMANIA In Romania, the Seveso II Directive has been transposed by Government Decision no. 804/2007 on the control of major accident risks involving dangerous substances, amended by Government Decision no. 79 from 11 February 2009, which amends art. 10 paragraph (5) a) art. 17 paragraph (1) and (2) and repealed art. 22 paragraph (2)from the Government Decision no. 804/2007. The SEVESO Directive II establishes two classes of risk (major and minor) for the industrial establishments that use or store dangerous substances. The Directive 96/82/1996 was amended and subsequently repealed by Seveso III Directive 2012/18/EU OF THE EUROPEAN PARLIAMENT AND OF THE COUNCIL of 4 July 2012 regarding the control of major accident hazards involving dangerous substances. In Romania there are 333 industrial objectives that fall under this directive (245 in the category of high risk and 88 with minor risk). The highest density of operators is recorded in the North - East (including the counties of Bacau, Iasi, Neamt and Suceava), where there are inventoried 22 objectives and in the Central Region - with 21 operators. In figure 2.4. the industrial units with technological risks from Romania are presented [63]. 23 Figure 2.4. Industrial units with technological risks [63]. Romania joined the international law in the field of technological hazards elaborating an inventory of industrial units falling under the Directive 2012/18 / EU SEVESO III, most of them related to chemical and petrochemical industry (144 units with high risk and 55 with minor risk) [104]. 24 CHAPTER 3. THEORETICAL SOLUTIONS REGARDING THE CONTROL OF MAJOR ACCIDENTS Major accidents that may occur on an industrial site represent the result of a natural disaster or technological event giving rise to the additional effects such as explosions, fire and the release of dangerous toxic substances. The consequences of such accidents are often very serious, even catastrophic, these consequences being materialized in loss of lives and material goods and the environmental damage [1,4]. Limiting and even eliminating the risk of a major accident involving dangerous substances is achieved through a coherent and efficient prevention and protection overall measures aimed at limiting the probability of a major accident production and the severity of the consequences on the site and the environment. SEVESO III Directive states explicitly the obligation that the operators should identify and quantify the risks of a major accident and the necessity to take into account the environment likely to be affected by the consequences of such an accident and oblige the economic operator to draw up a security report in order to provide the competent authorities to carry out work on site [3, 66]. In Romania the authorities responsible for applying the SEVESO III Directive have not identified so far a method to national risk evaluation on the sites of premises under the incidence of this Directive. The methods of analysis and risk evaluation allow a site for the identification and quantification of risks, mandatory steps in the development of the safety report. Depending on the type of industrial installation and the dangerous substances existing in the world there is a great variety of methods of analysis and risk evaluation. The assembly is characterized by a variety of methods, both from the point of view of the general approach, and the field of applicability [9]. Taking into account the above mentioned things and the fact that there is a likelihood of a major accident on a site that uses in the production process the dangerous substances with a destructive effect and besides it is necessary to develop a combined and complex method capable to consider measures/actions protection / intervention in order to limit and remove the consequences of a possible major accident. In order to elaborate this method, it is necessary to conduct a thorough study of the components of methods of analysis and risk evaluation existing at the moment globally, method that can be applicable on the industrial sites type SEVESO, that use the production process for dangerous substances, establishing the weak points of the methods studied to be removed from the new method, the strength points to be taken in the new combined method, and supplementing it with new elements that will support the competent authorities and the economic operators. 25 Worldwide there are several methods of risk evaluation that can be used by the specialists for the analysis and evaluation such as: the Hazop Method, the Hazan Method, the Lopa Method, the Mosar Method , the Aramis Method, the Checklist Method, the QRA Method, the Octave Method, the Mehari Method etc. 3.1. INDUSTRIAL RISK EVALUATION METHODS IN WHICH ARE INVOLVED DANGEROUS SUBSTANCES There are two kinds of analysis, of identification and of characterization of risk [75]: Qualitative analysis (Hazard Operability Study); Quantitative analysis (CPQRA - Chemical Process Quantitative Risk Analysis). The decision on the choice of the analysis and the degree of depth of the work are linked to the probabilistic risk tolerance scale. The risk identification techniques used to discover them presented in the process and the techniques for their evaluation - to decide how to act on them in order to eliminate or reduce them to protect the population and the environment are often confused. Summing these two categories of techniques are distinguished following general components [2, 8]: To identify risk: their intrinsic presence, the observation of what happens, the checklist - HAZOP (Hazard & Operability Analysis) is a method for identifying operational problems associated with the design, maintenance or operation of a system safety. It is an objective process to evaluate the various parts of a given system, which provides a systematic and well documented evaluation of potential dangers; Risk Evaluation: their intrinsic presence, previous experience, codes of practice HAZAN (Hazard Analysis) an estimation method used to evaluate hazards in order to decide how to act to eliminate or reduce the risk. 26 Tabelul 3.5. Analiza SWOT a metodelor de evaluare a riscurilor industriale studiate. NO. TYPE OF GOAL/OBJECTIVES METHOD STRONG POINTS OF THE METHOD WEAK POINTS OPPORTUNITIES THREATE NINGS - imposes the - the use of non-classical deviations is - for each deviation, recommended only if these were not the relevant cauded are covered inside the analysis based on deviations and - it analyses the safety of an analysed, theoretical a checklist. - general components for risk the dangerous identified scenaries installation/place and it consequences and the identification: are are further analyzed by -their intrinsic presence; discoveres the vulnerable existent protections; points(technically, - all the claaaical quantitative risk analysis; - observation of everything the checklist; - it is a qualitative method; THE 1. HAZOP METHOD covering of organizing, operationally), deviations are covered - it ellaborates a plan in order to in the analysis; rectify/ improve them. does not measures/actions dangers through establish of the that happens; protection/ -checklist. - it is dependent on LOPA methodology; - the probability of producing a - it is realised by a intervention necessary to limit and major accident team. remove the consequences of a with loss of lives possible major accident. and material goods. -it is realised by one or two experts; THE 2. HAZAN METHOD - it is a quqntitative method; -it - it measures/actions realizes probabilistic evaluation. a risk does not establish of - general components for risk the identification: protection/ -their intrinsic presence; - the probability of producing a major accident intervention necessary to limit and - earlier experience; with loss of lives remove the consequences of a - practical codes; and material possible major accident. - analyse and risk evaluation. goods. 27 Continuation Table 3.5. NO. TYPE OF GOAL/OBJECTIVES METHOD OF THE METHOD STRONG POINTS WEAK POINTS OPPORTUNITIES THREATE NINGS - it requires the use of a previous analysis results of risks of process, identified through - the probability for an event to produce and develop to a scenary - a quantitative method that evaluates 3. the necessary THE LOPA barriers to prevent major METHOD accidents and to reduce risks in installations up to acceptable level. credible with the worst consequences is closely linked to individual scenario risks; - it is applied to any identified dangerous scenario, generated by the risks associated to the process, respectively the scenarios dedicated to process deviations provided. that can be checklistor - It is dependent on the the previous HAZOP Method, so it is not a results of other methodology of independent evaluation - the analysis of the risk evaluation; -according to the severity of protection barriers; the credible - prevention of dangerous worst consequences, a certain events; methods and it requires bigger costs; - the probability number and/ or a certain - reducing risks; of producing a quality of the barriers, it is - it will be written in the major accident necessary in order to have a security report or as a with loss of lives tolerable/acceptable risk in the support document of the and material end goods. for every individual system of security analysed scenario; management. -it does not establish the measures/ protection/ the actions of intervention necessary to limit and remove the consequences of a possible major risk. 28 Continuation Table 3.5. NO. TYPE OF METHOD GOAL/OBJECTIV ES OF THE STRONG POINTS WEAK POINTS THREATE OPPORTUNITIES NINGS METHOD - it places special emphasis on the link between risk processes and systems components of an installation being specially adapted for studying the effects of accidents or "domino" chain. - it represents a symbiosis between analytical and systemic approaches of -it is an integrated technological risks, being based on 4. THE method which allows identifying the interactions between the MOSAR a stepwise analysis of investigated system components - seen METHOD an industrial objective as specific risks. sub-components with structures, functions and own ends - on the one hand and between the system and the It does not establish the measures/ the actions of protection/ intervention necessary to limit and remove the consequences of a possible major risk. Identifying risks of malfunction; - The risk assessment through trees failures; - Negotiation of a precise objective of prevention; - Improvement of prevention; - Risk management. - the probability of producing a major accident with loss of lives and material goods. environment on the other hand; -it is a method of structured analysis in modules and stages; -it is a participatory approach of the technological risk problem and it creates the premises of team work. 29 Continuation Table 3.5. NO. TYPE OF METHOD GOAL/OBJECT IVES OF THE STRONG POINTS WEAK POINTS THREATE OPPORTUNITIES NINGS METHOD -it is not possible to - identification of determine the most equipments - it adopts with difficulty public functions and security barriers; lifelike scenarios and identification setting of according - and the decisions based on risk assessment - to an alternative solution 5. to the THE strictly ARAMIS deterministic or METHOD probabilistic approaches risk to assessment strictly. they use; - by addressing - Elaboration of accident probabilistic estimation with the undesirable events; difficult because it is based butterfly difficulty scenario to the of the public decisions security are taken very hard; - the risk can not be based on accident precision and it confidence levels of assessment and to the public; safety - the possibility that to the the efforts to control the risk done management of influence of the people chemical industry; can transmitted barriers, incorrectly on a -the social risk based on statistical barrier characteristic approach; equipment used in the by the operator; with be frequency initiating events and be knot data does not reflect local reality or - corresponding of assessment result, - estimating the probability of the evaluated - realization of accident understood by the population; scenarios omplete purely barriers; a scenarios by identifying communicating the easy performance quantities of substances using worst case scenarios; - this method is the might not system on the level of trust understand the result - the absence of decision criteria barriers; of the estimation; - this method allows the that allow the use of graphic - the establishment of reference - the probability of definition of a list of representation hazardous events. vulnerability. of gravity and scenarios to be modeled determine the severity index. to producing a major accident with loss of lives and material goods. 30 Continuation Table 3.5. NO. TYPE OF GOAL/OBJECTIVES OF METHOD THE METHOD STRONG POINTS WEAK POINTS OPPORTUNITIES THREATE NINGS - it considers nothing but - It is less adapted for iaking onto consideration the specific security lethal effects on site- people; barriers - It does not studied; - Only the security barriers - selecting installations; that allow the limitation or - Definition of unwanted 6. THE QRA METHOD - method of evaluation the likelihood of damage from a potential accident. - it presents similiarities ARAMIS methods. a with and ot of the LOPA reduction of loss of central associated events and containment can be explicitly frequencies; taken into calculating account the in - Modeling the intensity of final the dangerous phenomenon; probability of damage; - Exposure modeling and -it does not establish the consequences. measures/ protection/ the actions of intervention necessary to limit and remove the consequences of a possible major risk. provide for consideration of barriers of specific prevention designed to reduce the likelihood of loss of containment; - the probability of producing a major accident with loss of lives and material goods. 31 Continuation Table 3.5. NO. TYPE OF GOAL/OBJECTIVES METHOD OF THE METHOD STRONG POINTS WEAK POINTS THREATE OPPORTUNITIES NINGS - the safety report or the document - It examines the safety - All the individual issues on the checklist of an installation / site are covered in the analysis; THE 7. CHECK LIST METHOD and discovers the of management - Hazard identification process related to the measures/ the - The (technical, using the checklist. One danger arises from intervention necessary (regulations, organizational, an event which incidentally can be to limit a to to their importance. rectify / improvements. actions instructions, and remove safety systems, procedures, and approached in an installation or sccording the consequences of a test plan will documents or the corresponding installations are performed actions of protection/ necessary develops system -it does not establish include the checklists in full; vulnerabilities operational), security possible major risk. reports, minutes of control, shift report etc.) are - the probability of producing a major accident with loss of lives and material goods. used for protective measures presented in the analysis. 32 N TYPE OF GOAL/OBJECTIVES OF O. METHOD THE METHOD STRONG POINTS WEAK POINTS OPPORTUNITIES Continuation Table 3.5. THREATE NINGS - identification and anakyss of risks; - modernization of plans of reducing -It THE 8. OCTAVE METHOD defines the evaluation and -it does not establish risk risks and the measures of security of the the the objective; actions of protection/ technical planning with the - a team of 3-5 experts is working for measures/ intervention purpose of achieving the achieving the objectives, who collects necessary objective and of security data and analyzes the information protection. the to limit remove the obtained, elaborates security measures consequences of and plans to reduce and eliminate the possible major risk. - Hazard profiling based on existing values in goal; -Identifying the infrastructure vulnerabilities. - the probability of producing a major accident with loss of lives and material a goods. risks identified; - natural exposure assessment; 9. -addresses to both analysis and risk THE management MEHARI evaluates the quantitative METHOD and factors. qualitative and risk - it enables calculations, simulations -it does not establish and optimizations; the - it uses a complete set of measures/ the actions of protection/ questionnaires serving on audit and intervention detailed list of scenarios; necessary to limit - It makes an evaluation as safe and impact of consequences of a over objective. the values the remove the possible major risk. - Evaluation of deterrence and prevention (building components, equipment, procedures, specialized personnel); - Evaluation of the impact of direct property data and information, infrastructure, personnel; - Evaluating the protective factors, - the probability of producing a major accident with loss of lives and material goods. compensation and recovery. 33 3.4. ADVANTAGES OF THE EXISTING METHODS FOR ELLABORATING A NEW METHOD This work aims to develop a method for risk evaluation involving dangerous substances, the implementation of which will be taken into consideration and will use the advantages offered by the methods for the existing risks evaluation and set out in subchapter 3.1. In table 3.6. one can see the advantages of the methods studied and selected in order to be used by the new resulting method. Table 3.6. Advantages offered by the existing methods for the elaboration of a new mehod. NR. TIPUL CRT. METODEI THE 1. MOSAR METHOD AVANTAJE - It allows identifying the risks of malfunction; - It performs risk assessment through trees failures; - It requires improved means of prevention. - It allows evaluating the results of safety barriers; - It realizes the likelihood of an accident scenario depending on the frequency of THE 2. ARAMIS METHOD the initiating events and confidence levels of barriers; - It allows assessment of the safety management system and its influence on the level of trust barriers; - It allows the selection of reference scenarios, that is the scenarios to be modeled to determine the severity index. - It prepares the checklists present in the safety report or in the document support THE 3. CHECK LIST METHOD THE 4. OCTAVE to management system of security; -It uses the existence of some documents of the economic operator (regulations, instructions, operator action, safety systems, procedures, cause-effect diagram, test reports, inspection reports, report lap etc.). - it allows a threat profile building based on the existing values in the objective. METHOD - it realizes the evaluation of the safety factors and prevention; 5. THE - It allows the direct impact evaluation over the property, data and information, MEHARI infrastructure, personnel; METHOD - It carries out an evaluation of protection factors, compensation and recovery. 34 By combining the strong points of the five methods studied and selected, a new method of evaluating risks, called THE CARMIS METHOD (Combined Analysis and Assessment Method of Risks and Industrial Safety). 3.5. THE PRINCIPLE OF CARMIS METHOD The elaborated method resulting from the combination of strong points of the five methods selected from the studied methods, called the CARMIS METHOD, has as aim the quantitative and qualitative determination of the risk/security level for the installations/technologies of the economic operators that use dangerous substances in the production process and can produce major accidents with serious implications for people, property and the environment. The new elaborated method implies: identification of all risk factors from the analysed system; the elaboration of the accident scenario according to the frequency of the initiating events and confidence levels of the security barriers (to prevent major accidents and to reduce risks in installations or on site up to the acceptable levels); assessing the direct impact on staff, goods, data and information, infrastructure, assessing protective factors, compensation, rehabilitation and establishment of measures/actions of protection/intervention to limit and remove the consequences of a possible major accident (using checklists); drafting the safety report, the main document of the security management system. 3.6. STAGES AND METHODOLOGY FOR THE IMPLEMENTATION OF THE CARMIS METHOD The method comprises these compulsory steps: a) Establishing the evaluating team; b) Definition of the anlyzed system (installation/ technology); c) The analysis in the field and identifying the risk factors in the system; d) Making and consulting the checklists; e) Preparing the trees failure; f) Evaluating the risk factors identified from gravity point of view; g) Evaluating the frequency of the initiating events and the confidence levels of security barriers; h) Elaborating the accident scenary ( by simulation with the Aloha program); i) Estimating the direct impact over the goods, dates and information, infastructure, staff; j) Evaluating the protection, compensation and existing rehabilitation factors; 35 k) Evaluating the performances of the existing security barriers; l) Drawing up the safety report as supporting document of the security management system. According to the security report drawn up after completing all the compulsory steps, there will be carried out by the economic operator or will be outsourced following activities: Establishing the measures/protection/intervention actions for limiting and removing the consequences of a possible major accident- procedures; Implementing the measures plan for improving the performances of the security barriers; Monitoring the application of the security report and the efficiency of the established measures (Feed-back of the implementation). In figure 3.13. one can see the drawing of the general principle of the method CARMIS Assessment team formation 1. Know in details the assessment method, the instruments and procedures to be used 2. Have information in advance on the workplaces and technological processes they are going to analyse/assess Defyning the system (/installation(s)/technology) 1. Installation location 2. Sytem description (process, chemical installation etc.) 3. Operator’s general layout 4.Process/control diagram 5. Manufacturing instructions, technological schemes, processing procedures 6.Quantities of dangerous substances and their characteristics 7. Regional meteorological characteristics 8. Regional seismic characteristics Examination of the establishment and identification of the risk factors Checklists elaboration CARMIS METHOD 1. Presentation of the installation and identification of the hazard sources 2. Hazard identification and accident scenarios development 3. Risk evaluation 4. Establishing prevention objectives 5. Defyning safety barriers 1. Specific to the establishment/process 2. Based on incidental events 3.External Accident scenario representation using the butterfly node ELABORATION OF THE SAFETY REPORT Assessment of the risk factors seriousness Evaluation of the initial events frequency and safety barriers reliability levels Development of the accident scenario Assessment of the direct impact of the accident on man Through Aloha Programme simulation Evaluation of the protection, compensation and recovery factors Evaluation of the existing safety barriers performance Figure 3.13. Drawing of the general principle of the method CARMIS 36 3.6.2. SWOT ANALYSIS OF THE CARMIS METHOD Advantages and disadvantages of the CARMIS METHOD are presented in table 3.7. Table 3.7. SWOT analysis of the CARMIS METHOD. NO. TYPE OF AIM/ OBJECTIVES METHOD OF THE METHOD STRONG POINTS WEAK OPPORTUNITIES POINTS CARMIS - makes a full risk - identification of METHOD assessment; factors from the -makes quantitative and system; qualitative -evaluation of the factors of for risk reduction; protection, - Develop risk determination of the all risk - realised by 4-5 analyzed experts; -drafting the THREATENINGS current protection strategy; - high costs. assessment to the - The choice of concepts complexity of the site and compensation, existing installations . reducing level of risk / security rehabilitation; plans; for the -setting measures / actions of - protection/ necessary protection strategy. intervention to limit and schiţarea strategiei curente installations /technologies economic who of the operators use dangerous substances in the cause possible major accident. major accidents with serious implications for people, property and Identify de protecţie; remove the consequences of a production process and can - increasing costs for the the environment. 37 changes in CHAPTER 5. SETTING RESEARCH METHODOLOGY FOR RESEARCH, CORRELATIONS AND MATHEMATICAL MODELS To establish the research methodology, the correlations and the mathematical models, I checked the efficiency of the method that I realized by combining the strong points, the covering of the weak points and the thretenings, the so-called CARMIS method, that I applied to an economic operator who deposits and uses dangerous substances in the production process, respectively ammonia, in an accident scenario based on a case study at S.C. AMURCO S.R.L. Bacău, following and completing all the steps of the established method in subchapter 3.6. 5.2. METHODOLOGY FOR THE IMPLEMENTATION OF CARMIS METHOD BASED ON A CASE STUDY AT S.C. AMURCO S.R.L. The economic operator must establish, implement and maintain a procedure (procedures) for the continuous identification of the dangers, the risk evaluation and the establishment of the necessary controls which must consider all the identified dangers, generated both inside the emplacement that can affect staff”s health and security as well as the dangers outside the emplacement created by activities related to the technological process of the operator, infrastructure, equipments and the materials used at work. 5.2.1. ESTABLISHMENT OF EVALUATION TEAM According to the methodology presented in subchapter 3.6.1. point a), the evaluation team will be constituted of: a specialist of activities with dangerous substances, a specialist who develops activities in safety and security of work and environment, a specialist in civil protection, a physician within the medical system and an appropriate internal specialist at Private Service for Emergency Situations. The members of the team must know the technological installations to be analyzed, the characteristics and the behavior of dangerous substances. Before beginning the activities, the members of the team must: know the evaluation method in detail, the instruments used and the concrete work procedures; have a minimum prior documentation on jobs and processes to be analyzed and evaluated; after setting up the team for analysis and evaluation, that is after acquiring the method, one can proceed to completing the steps themselves. 5.2.2. DEFINING THE ANALYSED SYSTEM (INSTALLATION/TECHNOLOGY) From the documents provided by the economic operator regarding the system analyzed, there were collected information on the location of the installation (location), describing the system (process, chemical installation), the general plan of the economic operator, the diagram of process or control, manufacturing normatives, technological schemes, operating procedures, weather conditions of the area to place the objective, characteristics of the seismic area, so [141]: 5.2.2.1. Location of the installation (location) [132] Amurco Bacău is a chemical factory in Bacau owned by the group Interagro since 1997 and it was founded in 2005 by taking over part of the actions of the chemical factory Sofert Bacau, which resulted from the conversion of full Chemical Fertilizer Bacau (CIC Bacau) established in 1974. Through the GD 1200/1990 Bacau Sofert company was set up under Law 15/1990. AMURCO chemical platform is a complex facility located in the industrial area south of Bacau, at a distance of about 3 km from the city of Bacau, which covers an area of approximately 78,000 sqm and it is located in the built-up area. In the period under review the area was affected by the presence of several industrial facilities including: CET Bacau - South S.C. Bistrita S.A., SC CONBAC S.A., household waste dump in Bacau, Bacau LETEA etc. In table 5.1. the places and the economic operators from neighborhood of S.C. Amurco LLC Bacau that may be affected in the event of a major accident. By developing Bacau city, the residential area is continuously expanding all around Bacau and the unincorporated areas considered in the past are now in the immediate vicinity of the industrial objectives. The chemical company's platform is located on the contour line of 150 m to 140 m on the right bank of the river Bistrita. The local topography in the form of a bump of land at the confluence of the river Bistrita with Siret river and a wide terrace step. In the immediate proximity of the chemical platform there are are not habitats or protected species. The ammonia tank is located in the south of the site society. On the outside it is fitted with flooding devices in the event of accidental drains. 39 Table 5.1. Localities and economic operators from the neighbourhood S.C. AMURCO S.R.L. Bacău [132]. Located in the area of external Located in the area of 500 m emergency planning Number The economic operator Distance( Locality of km) (km) (loc.) LUIZI CĂLUGĂRA 8 6.283 employees BACĂU CITY Distance Population 3 35.000 S.C. I.L.S. S.R.L Bacău 0,2 40 MĂGURA 10 3.947 S.C. CONBAC S.A 0,2 60 MĂRGINENI 8 7.985 S.C.SSAB AG S.R.L 0,3 85 LETEA-VECHE 5 4.813 S.C. BAC DELPHI S.R.L 0,2 40 BUHOCI 7 5.039 S.C. CONBAC S.A 0,3 40 TAMAŞI 6 6.059 C.E.T BACĂU 0,5 150 NICOLAE BĂLCESCU 4 10.949 S.C. GLOBALSERV SRL 0,1 10 MUN. BACĂU 3 140.261 SC CARPAT BETON SRL 0,5 4 SAUCEŞTI 15 3.775 S.C. SELENA Pista Kart 0,5 40 BEREŞTI BISTRIŢA 20 3.195 SC INTERSERV SRL 0,2 17 NEGRI 36 3.529 SC INTER BRANDS 0,5 150 TRAIAN 24 5.830 SC REGAL GLASS 0,4 8 SECUIENI 31 4.344 SC MELINDA IMPEX STEEL 0,4 10 RĂCĂCIUNI 20 6.763 SC.WATCH & CATCH 0,1 38 CLEJA 15 6.718 SC AVEGO NEGRESTI 0,1 15 FARAOANI 12 5.884 SC FIBROMAR SRL 0,2 10 SĂNDULENI 30 4.272 SC BETON DENIS SRL 0,2 7 SCORŢENI 34 3.328 5.2.2.2. The general technical plan of the economic operator a) General data: Capacity charging/recharging ammonia: At charging: 40t/h, max.320 t/ day( for 2 changes); At discharging: approx. 50 t/h (capacity of discharging through the ramp storage tank is limited because the ammonia deposit is not equipped with cooling system- it has only temperature maintaining installation) [137]. 40 b) The compnents: the ramp itself, with 4 holes loading, pipework and fittings flexible; ammonia water tank, V= 90 000 L; two pumps for loading/ unloading ammonia and ammonia water. c) Connections external to the ramp: the main route to store ammonia for receiving ammonia for loading in tanks and delivery; connecting pipes with the ammonia manufacture installation; hot ammonia gas pipeline for discharging tanks; pipe nitrogen gas pressurization and inerting tanks of ammonia. In figure 5.1. one can see the technical plan of the economic operator [137]. CISTERN NH3 TANK OF AMMONIA NH3 RAMP AMMONIA EMISSIONS pp VESSEL AMMONIA WATER HEAT EXCHANGER pp. AMMONIA FROM THE TANK AMMONIA FROM THE CISTERN AZOTE GAS Figure 5.1. The general technical plan of the economic operator [137]. 5.2.2.3. Describing the system (process, chemical installation) The ammonia reservoir ( given in use in August 1978) is a cylindrical shaped ground construction, made of carbon steel lined with isolating material provided anti-thermal (provides a temperature of - 40°C), placed in a vat of concrete retention. It has a metal supporting structure, the parts of the structure are represented in elevation of a wall made of steel with a thickness of 25 mm at the bottom, up to 10 mm from the top [132]. The reservoir of ammonia ensures the safe ammonia storage having the following features: volume: V =12.000.000 m3; exterior diameter of the mantal = 27,6 m; height : H thermo-isolated = 20,5 m; 41 refill degree: maximum 80%; capacity to deposit : maximum 15.000 t (minimum 700 t). In figure 5.2. the ammonia reservoir is presented, this image being resulted from its characteristics introduced in the simulation program ALOHA. Figure 5.2. The ammonia reservoir. 5.2.2.4. Instalations of process or control. a) The installation of ammonia KELLOGG. General data [132]: Year of commissioning:1979; Projected capacity: 300.000 t/an. Technology: licence KELLOGG – technology U.S.A., modernized in 1990, degree of automation 98%. Phases of the technological process [132]: Preparation of synthesis gas: - Compress and natural gas desulphurization; - Reforming the primary natural gas, medium pressure; - Catalitic Reforming of natural gas secondary air technology; - Catalitic conversion of carbon monoxyde in two temperature stages. 42 Purification of yhe synthesis gas [132]: Purification for removing CO2, by chemical absorbtion in the soil. K2CO3 activated with cu diethanolamine – system Carsol; Methanisation: catalytic reaction of transforming carbon oxydes to methan. Synthesis and ammonia refrigeration [132]: Synthesis gas compression; Pressure ammonia synthesis with separation of ammonia by refrigeration; Refrigeration and ammonia storage. b) Auxiliary installation, component parts of the ammonia factory [137]: Facility for generation, distribution and recovery of the steam; Degassing facility condensation process; Facility for storage and distribution of liquid ammonia. 105 bar steam generation system is integrated, with use at high energy recovery level, the steam generated being used for a technological purpose and turbines driving compressors and main pumps from the installation. It uses natural gas as fuel. c) Finished products[137]: Liquid ammonia – main product , 99,8% NH3, used as raw material in the manufacture of urea; carbon dioxide– secondary product. d) Evaluation BAT (Best Availablle Techniques – The best technologies available) [137]: BAT is defined as being the current stage of development of processes, facilities or methods of operation which indicates how appropriate is basically a measure for limiting discharges. To determine whether a series of processes, facilities or methods of operation represents the best technology available for general or individual cases, a particular attention should be paid to the following aspects [132]: the process of manufacturing ammonia applied in S.C. Amurco S.R.L. Bacău installation: it falls into the category of conventional reforming, this being considered a production process BAT; 43 the installation of ammonia KELLOGG exploited by S.C. Amurco S.R.L. Bacău: it belongs to the second technological generation, having the proper moral and physical wear; facility operation in recent years was made at a level of 20-70 % of its capacity, the recorded exceeding BAT levels; the installation was modernized in the 1994 – 1996 period. 5.2.2.5. Normative manufacturing, technological schemes, operation procedures The process of manufacturing ammonia applied in SC Amurco SRL Bacau installation falls into the category of conventional steam reforming of natural gas. In figure 5.3. one can see the technological flux scheem at the ammonia installation [137]. 44 COMPRESSION Natural gas Natural Gas RESIDUAL GAS HEATING DESULPHURISATION Technological air PRIMARY REFORMING COMPRESSION Technological air SECONDARY REFORMING CONVERSION CO AT HIGH TEMPERATURE CONVERSION CO AT LOW TEMPERATURE Solution K2CO3 WASHING CO 2 CO2 la consumatori METHANISATION Ammonia water at deposit COMPRESSION synthesis gas RECOVERY HYDROGEN Spent catalists SYNTHESIS AMMONIA STORAGE AMMONIA AMMONIA FINITE PRODUCT Figure 5.3. Yje technological scheme of btaining ammonia [137]. 5.2.2.6. Quantities os dangerous substances and their characteristics SC AMURCO SRL Bacău has as main activity [132]: production of urea, nitrogen fertlizer, used in agriculture and marketed internally and internationally; producing ammonia, this being an intermediate product mainly used in the urea production platform – the liquid ammonia as well as its aqueous solution is commerciallized for different industrial uses; producing and commercializing the alimentary ammonium bicarbonate. 45 In table 5.2. one can see the main finite products obtained in the production process [132]. Table 5.2. No. Product name Installation Capacity of of production production (t/year) Way to store and Destination delivery 1. Run as feedstock in 1. Ammonia Ammonia installation Liquid 300.000 ammonia, the process of NH3 manufacturing urea on 99.8%, delivered in the form the same site; of liquid ammonia 2. delivered to third parties in tanks C.F. or automobiles Ammonia 2. water sollution 25% The Depending ammonia on market installation demand Ammonia water tank with V = 90,000 liter delivered to third parties in tanks C.F. or automobiles Urea pearl humidity 0,35 0,5% urea stored in bulk 3. Urea Urea installation 420.000 storage, capacity 30,000 t; Delivery: bulk or in double bags of polypropylene and Various beneficiaries of chemical fertilizers or technical urea polyethylene nitrogen gas Installation 4. Azote 600 m³ / h for separation of Liquid air (nitrogen) nitrogen 60 L / h Nitrogen gas concentration of 99%. Liquid nitrogen: - Cryogenic storage tank with V = 5000 liters Internal consumers Various beneficiaries Delivery in special containers Bottled oxygen in the Air 5. Oxygen oxygen gas installation of bottling , in separation 80 m³ / h, special containers , installation p = 150 atm Storage bottles - in specially Various beneficiaries designed storage. 46 5.2.2.7. The metheorological situation of the area to place the objective The altitudinal layout step with wide opening to the east has conditioned, in a great measure, the characteristics of Bacău climates. The continental influences are modeled by the air masses from the western and northwestern Europe which arrive in Bacau through saddles of the Carpathian and increase the rainfall [30]. The annual medium average wind speed frequency shows its predominance from north, northwest and from the south and southeast. Weather phenomena that are of special interest are the fog and the frost. The fog occurs frequently during winter time and the transition of hot weather to cold or cold to hot, with a maximum frequency in December and January. In the autumn months fog is a common phenomenon on the river valleys, too, reducing the brightness [133]. The climatic conditions for Bacău city are: • 42.2% of the time in the city of Bacau is represented by weather condition favorable for the spread of toxic fumes; 12,6 % of the time in the city of Bacau is represented by weather conditions very unfavourable for dispersion of toxic fumes; 45,2 % of the time in the city of Bacau is represented by weather conditions unfavourable for dispersion of toxic fumes. 5.2.2.8. The seismic characteristics of the area In order to study the impact of an earthquake occurrence in the reservoir area, there were used studies of Iaşi branch INCERC vibration measurements, which aimed (INCERC, 2002) [136]: for the reservoir, determining its own oscillation frequency domain, identifying the areas on which there might appear significant amplifications of a dynamic disturbing external action (conducted at microseismic agitation and low-intensity shocks applied to the dome); For site, the identification of dominant dscilation frequency ( made only for the microseisms). Modeling of seismic wave action was realised using the program with a finite element type SELL (plate and membrane) SAP 2000. The lowest natural frequency of oscillation determined by the modeling exercise was 33.7 Hz. The results of numerical simulations presented in the report, concluding that the cover insulation and aluminum protection mantala are resistant to severe seismic actions up to 7.4 on 47 the Richter scale. Such the seismic hypothesis of the waves action is not supported by the container especially since the area at the time of the incident were not recorded significant earthquakes ( according to data obtained from the website of the National Institute for Earth Physics - real-time archive) [101]. 5.2.3. ANALYSIS OF THE LAND AND IDENTIFICATION OF RISK FACTORS IN THE SYSTEM Identification of the risk factors is is based on detailed risk analysis of the evaluated site and requires an initial analysis of risks. The identified risk factors are written in an " Evaluation system sheet ” [12, 68]. Identification of RISC factors through ,,Macroscopical analysis”, comprises the following stages [68]: Presenting the installation , identification of the sources of danger; Inventary of dangerous substances; Identification of danger, evaluation and control of risk; Identification of the area with the biggest risk; Setting targets for prevention. 5.2.3.1. Presentation of the installation, identifying of sources of danger Ammonia warehouse and loading ramp - unloading ammonia, for depositing liquid ammonia and delivery to internal and external consumers and are located in the south part of S.C. Amurco LLC BACĂU. The description of the installation was presented in subchapter 5.2.2.3. Identification of the sources of danger is realised according to the checklists presented in subchapter 3.1.8. respectively: Specific dangers of the site/process; Dangers based on the incidental events; External general dangers. 5.2.3.2. Inventary of the dangerous substances. In table 5.3. are presented dangerous substances used in the production process, the degree of danger and the relevant quantities[137]. 48 Table 5.3. Dangerous substances used, degree of danger and the relevant quantitaties [137]. The chemical Danger substance Risk phases Natural gas Inflamable F+; R12 Anhidrous Toxic,corosive ammonia dangerous T; R23 for the environment C; R34 , R10 Maximum Maximum used capacity of quantity/ produced storage anually It is not stored 535000 mc/a year 15000 t 300.000 t/ a year N; R50 Ammonia water At a concentration >25% C; R34 80 t it is toxic, dangerous for N; R50 According to orders the environment Catalytic Formaldehyde solution 25% cracking toxic 3T;R23/24/ 100 t 6300 t 25–34-4043 Hydrogen Inflamable F+; R12 It is not stored Oxygen Oxidant O; R8 - According to orders Sulfuric acid Toxic, corosive R23 R35 3000 t 3000 t Toxic, corosive R23 R35 30 t 550 t Concentration 98% Hydrochloric acid solution 36% The effects of ammonia over tge employees and population health: Ammonia is an extremely irritating gas for mucous and its its aqueous solutions are caustic. A part of the inhalated ammonia is neutralized by the carbon dioxide at the level of alveoli, the rest coming in circulation, then being eliminated through urine and sweat. Acute intoxication with ammonia is manifested by feelings of suffocation strong access of coughing, agitation, delirium, uncertainty in walking, blood flow disorders. Death can occur in heart failure and pulmonary edema. Concentrations of 0,25% - 0,45% ammonia in the air, that is 1897-3415 mg NH3/m3 air can cause the apparition of an acute form of intoxication. An exposure of about 5 minutes in a 49 medium having concentration of 0,5 % – 1 % ammonia in the air, that is 7589 mg NH3/m3 air can cause death. Accidental ingestion of ammonia solutions is accompanied by phenomena of gastric intolerance, erythema, global edema. Ammonia affects the conjunctiva and cornea, causing the appearance of conjunctivitis, palperal spasm and in severe cases, corneal clouding or perforation [137]. In table 5.4. are presented the maximum admitted values for the ammonia concentration at work places and in habitable zones. Table 5.4. The maximum admitted values for the ammonia concentration at work places and in habitable zones. Reglementari in vigoare U.M. Valoare limita termen scurt Valoare limita Law no. 319/2006 regarding security and health at work mg/m3 air 36 (15 min.) 14 (8 hours) mg/m3 air 0,3 (30 min.) 1(24 hours) (at work places) MMPS 2002 STAS 12574/78 (for the habitable zones) Under the legislation presented in Table 5.4., the maximum permissible concentration of ammonia in the working environment is 36 mg / m3 air and in protected areas 0.3 mg / m3 air. 5.2.3.3. Identification of danger, evaluation and risk control. Determination and evaluation of risks of major accidents at Amurco society establishes the process of identifying all dangers, risk evaluation on the chemical platform for compliance with legislative requirements regarding occupational health and safety arising from [132]: activities conducted currently on the platform; new or modified activities; curent operation of installations and procedures a instalaţiilor şi procedurile issued for cases of normal / abnormal operation, occasional pr periodical procedures; controlling of an operation which has potential in initiating risks; using products and services provided by third parties. 50 To achieve the identification process of major dangers resulting from normal and abnormal operation, as well as the evaluation of their likelihood and severity, one has resorted to systematic identification to adopt and implement the most appropriate procedures. For the efficiency of the realised study, there were considered data about toxicity, degree of ignition, poyential of explosion and reactions in chain in the following situations [132]: starting; normal operation; normal stop; crashes; maintenance. For identification, analysis and risk evaluation at the chemical platform Amurco, we took into account the history of the spent events over 30 years of activity in the production of chemical fertilizers. According to data from the Environmental Balance after 1997, after taking over the company by SC INTERAGRO S.A. no major incidents were reported during the finctioning of the installation at Amurco, following hich to have killed at least one employee, or might have led to serious intoxication of a number of people both in and outside its amplansament [137]. 5.2.3.4. Identifying the area with the highest risk. In order to determine the highest risk installations, the company has been divided into individual areas, on each area we conducted a thorough analysis pursuing the following factors: probability of producing an accident; consequences in case of producing this accident; hystory of each installation. After an analysis on the platform of AMURCO, the following installations are highlighted, each of them having a different potential when producing a major accident[132]: ammonia synthesis installation; urea synthesis installation; ammonia storage reservoir; ammonia loading ramp. A relevant accident is linked to the loss of ammonia at one of the four installations presented and for this reason each facility has an associated risk and a degree of danger which 51 characterise it. The probability of appearing an emergency situation is reduced by [137]: equipping with safety elements and systems; automation and control of risk parameters; qualification of the staff in operating and mintenance of the facilities; training and education for staff intervention; alternative ources of power supply; alternative sources of water supply. The potential danger that the chemical platform AMURCO represents for both the location and population (situated in Bacău and the neighboring localities), is determined by the coexistece and the possibility of manifestation of multiple risk factors: Dangerous properties of ammonia; Occurence of troubled in the installations of the society. Risks that can be produced on the emplacement of S.C. AMURCO l.L.C. Bacău : 1. natural risks [132]: Earthquake and landslides (p); Falling of cosmic objects (s); 2. technological risks [132]: terrorist attak with heavy weapons; (s); chemical accidents (p); rail transport accidents (p); explosions (p); fires (p). where : (p) = main risk , (s) = secondary risk. The natural risks, once manifested may trigger, in turn, additional specific effects on the platform AMURCO like the technological risks mentioned above. The emergency situations are treated according to the type of risk that manifests or tha combination of their consequences in direct correlation with the quantities of dangerous substances and their concentration. For the AMURCO platform, the types of potential risks to be considered are [132]: massive releases of dangerous sucstances in the air (chemical accident); fires; 52 explosions; combinations of dangers determined by the damage character. The main factors that lead to the chemical risk outbreak ( generally ) are: technical errors; uncontrolled chemical reactions determined by errors in projection; the improper maintenance of facilities; lack of control or procedural errors; the human factor. The typology of the possible emergencies on Amurco internal chemical platform, based on the history of events leading to accidental crash and knowing the risks associated with the installations as well as the properties of their substances danger is presented in the table 5.5. [137]. Table 5.5. Types of emergency situations possible to be produced in S.C.AMURCO L.L.C. [137] Type of event Massive ammonia emissions Gas flammable substance leak (gas, synthesis gas, hydrogen) Flammable liquid spill Corrosive liquid spills Technological damage at the ammonia installation Technological damage at the urea installation Technological damage at the Ammonia tank installation and loading ramp Technological damage at CET installation Technological damage at section electro SRA Technological damage at nitrogen installation Technological damage at oxygen installation Damage to storage of flammable liquids - fuels Where? air soil water x Pollution Fire Explosion x x Toxic cloud x x x x x x x x x x x x x x x x x x x x x x x x x x x X x x x x x x x x x x x x 53 Continuation Table 5.5. Type of event Where? air Damage to deposits of finished product- urea Failures, derailments during: loading, manipuating and / or transportation of dangerous substances on the factory railways soil water Pollution Fire Explosion Toxic cloud x x x x x x x x The types of emergencies outlined in Table 5.5. will be managed by S.C. Amurco LLC while applying procedures specified in the content of plans of intervention and the operating instructions of the departments. The most toxic substance potential from the platform that presents a potential risk triggering a major accident is ammonia. For leakage of ammonia from the installations that produce, use and manipulate ammonia, the accidents can occur due to dispersion of toxic fumes [137]. In the installations for the production of ammonia and urea it is supposed to be unlikely to produce a major accident which will endanger health and civil community life. The existing safety equipments in these installations, the degree of technology, the existence of clear operating instructions within each section, enable stopping the source of the event through technological intervention [132]. The deposit of ammonia is classified as being a strategic objective for the population due to its vulnerability to external, violent, mechanical action. The existing ammonia depozit in Amurco is a goal achieved by respecting storage technologies for the properties of the stored substances. These technologies ensure minimum accepted risks regard ting the protection and safety in exploitation [132]. In conclusion: major events such as the catastrophic cracking of the tank of ammonia do not occur as a consequence of technological process, human error, attack with light weapons or unfavorable meteorological conditions (lightning, hail, strong wind), but only by violent action of an external agent (meteorite, heavy weapons); as a measure of safety , the storage reservoir is not filled at its designed capacity, (maximum load capacity is 80% of the designed capacity); in the technological process, the human factor is insignificant, as the pressure and temperature regulation in ammonia storage is automatic; the cryogenic cover was fully restored in 2001-2002. 54 The storage tank of ammonia as a whole was designed and built to resist to an earthquake of up 8˚ on the Richter scale according to the code for seismic design P100/1992 [136]. 5.2.3.5. Setting targets for prevention The potential for major danger in producing accidents, representing the Amurco site justifies the need of establishing: the safety report, internal emergency plan and a policy of prevention, for the following reasons [137]: the existence of some technologies and installations which produce, use, manipulate, deposit dangerous substances; the existence, at a certain moment, of large stocks of dangerous substances; the existence of a large number of persons who work on the platform and the possibility of a human error in operation; the possibility of involvement in events with serious consequences in neighborhood in case of massive emissions of dangerous substances; the possibility of surface water pollution. This potential danger is determined by the co-existence and manifestation of several risk factors that can cause and trigger at one time a certain type of risk (eg earthquakes or landslides with complementary effect, terrorist attacks or falls of cosmic objects ). The worsening consequences of an accident involving dangerous substances is influenced by the location and technological specific which may favor simultaneous expression of multiple risk factors with possibility of involvement in the "domino effect" of several installations. 5.2.4. ESTABLISHING CHECKLISTS. General dangers checklists are used to identify relevant dangers specific to the installations/sites. General external dangers are treated at the level of the entire site. In tables 5.6., 5.7. and 5.8. the checklists are presented for ammonia tank. 55 Table 5.6. Checklists for dangers specific to the site/ process. Nr. 1. 2. 3. 4. 5. 6. 7. 8. 9. 10. 11. 12. 13. 14. 15. 16. 17. 18. 19. 20. 21. 22. 23. 24. 25. 26. 27. 28. 29. 30. General dangers Wrong design Incorrect manufacture and assembly Operating pressure over the permissible limit Temperatura de funcţionare necorespunzătoare Malfumctions due to corrosion, aging, normal wear or process Failures due to vibrations / fatigue Failure of components: flanges, joints, valves, gaskets,fittings, pipes, hoses, etc. The bearings jam Moving permanent component failure The occurrence of unexpected chemical reactions Nonfeeding with substances for operation Failure of the control device Nonfeeding with electricity, cooling water, steam, nitrogen, etc.) Failures arising during normal operation Failures occurred during startup and shutdown Failures occurred during carrying out maintenance / repair Failures occurred during transportation of dangerous substances Appearance of flammable / explosive substances due to failure Creating occurrence of explosion due to uncontrolled leakage of substances Creating occurrence of explosion due to human error Creating occurrence of explosion due to malfunction of the control system parameters Creating local occurrence of unexpected explosions Creating occurrence of explosion due to loss of energizing substance The production of mechanical sparks due to friction The emergence of flame and hot gases The occurrence of undesirable chemicals, materials igniting easily (eg FeS) Electrostatic Discharge current production and equalization Electrical sparks Uncontrolled emergence of electromagnetic waves Overheating surfaces due to friction and mechanical sparks appearance YES NO X X X X X X X X X X X X X X X X X X X X X X X X X X X X X 56 Table 5.7. Checklists for dangers based on incidental events. Nr. 1. 2. 3. 4. 5. 6. 7. 8. 9. 10. 11. 12. 13. 14. 15. 16. 17. 18. 19. 20. 21. 22. 23. 24. 25. 26. 27. 28. General dangers Unfulfilment of all necessary prevention and fire protection Failure to ensure the required dimensions of the vessel or the retention tank Insufficient release of the substance in the plant The equipment failure or the insufficient measures to limit and control the spread of the released substances No emergency exits are provided for personnel at the job The minimum distances between installations are not respected The installations are not equipped with defense systems The fire alarm and the fire detection system do not work The installation is not equipped with fire extinguishing agents The etinguishing fire means are not checked and do not work There is not enough room for intervention No organization is made for intervention in emergencies The injury of the intervention personal due to the effects of physical / chemical properties of the event The personnel at the job is not ready for intervention The detection systems do not work Failure to comply timely measures to limit the substances released Failure to comply distances Limiting means of explosions are not made according to the technical rules Failure to comply the detection of Gas devices / dangerous pollutant substances Leaks of dangerous substances are not detected Leakage of the dangerous substances into sewer system/ wastewater without being detected The increasing uncontrolled concentration of dangerous substances The released toxic substances are not separated sufficiently The substances which are dissolved in water from the solids ones in the flue gas can not be separated The toxic clouds expansion due to the application of measures of dispersion (ex: the curtain of water) The dangerous substances are not retained enough The dangerous substances are not neutralized The flare for thermal elimination of the substance does not work YES NO X X X X X X X X X X X X X X X X X X X X X X X X X X X 57 Table 5.8. The checklists for the external general dangers. Nr. General dangers 1. Failure in taking flood protection measures Failure in implementation of measures to protect against 2. earthquakes Failure in making safeguards against dangerous weather 3. phenomena 4. Failure in making fire safety measures outside Failure in making lightning conductors or dangers caused 5. by the presence of high voltage line The pipelines crossing the installation and containing 6. dangerous substances are not protected against producing an unforeseen accident Failure in taking protection measures against the impact of 7. transport or nearby objects Failure in implementation of measures to protect against 8. explosions from the outside (shell effect) Failure in implementation of measures to protect against 9. unauthorized access Failure in making protection measures and intervention 10. systems to unauthorized access Services performed through contract by other companies on 11. site are faulty The intervention vehicles have not accesses to the 12. installation The intervention equipment, protection and means of 13. extinguishing / neutralization are uninsured or out of order There are no plans for cooperation with forces outside the 14. establishment Failure in making training intervention forces during 15. emergency situations 16. Making faults in evaluation and eliminating dangers 17. The entire staff can not be alarmed in case of an accident YES NO X X X X X X X X X X X X X X X X 5.2.5. DRAFTING THE TREES OF FAILURE The identification of deviations from normal system operation and all the possible risks are made on direct observation and logical deduction based on the simulation of the system operation [25]. The identification of accident scenarios is based on the use of butterfly node comprising trees of failure and trees of events [27]. This step allows the defining of a list of critical events for each couple consisting of one device and the substance which it contains. For each critical event there is associated a tree of failure that can be changed to match the features of the studied system. In the same way, starting from a critical event and the dangerous substance involved, this stage allows the construction of a tree of events, which combined with the tree of failure forms the butterfly node characteristic for more accident scenarios [25,27]. 58 In figure 5.4. one can see the scheem of trees of failure, realised for an ammonia tank, but which can be used for other dangerous substances, too. FUNCTIONAL STABILITY TAMPER PROTECTION STOP WITHOUT MISTAKES CONTINUOUS FUNCTIONING CONTINUOUS SUPPLY EARTHQUAKE PROTECTION FIRE PROTECTION MEANS O F ESCAPE MEANS O F PREVENTIO N EVACUATIO N PO MPS WATERPROOF CONSTRUCTION TANK 3 TANK 2 TANK 1 PENALTIES RESPONSAB ILITIES PROFESSIONALISM MAINTENANCE PERMANENT SUPERVISIO N RELIABLE EQ UIPMENT SAFETY INFORMATION ACCESS CO NTRO L Figure 5.4. Scheme of trees of failure. 5.2.6. ELABORATING THE ACCIDENT SCENARIO a) Building an accident scenario For major accident scenario development there were taken into account the following elements [132]: the conditions of AMURCO objective conditions takin into account the position of the urban and rural settlements in the area; the danger presented for the staff of the AMURCO society; the quantity of dangerous substsnces ( ammonia) present installations and stored when the accident occurs; the characteristics of the involved substances that can occur during failures and can increase the accident consequences; modeling regarding emissions propagation according to studies, as well as producing fires after explosions; the way of propagation and dispersion of the dangerous substance in the air , water or soil where there would be an escape followed by explosion and fire; the security management established by the AMURCO society manager, the capacity to answer in situations of emergency to limit and remove the consequences of a major accident on the site and outside; 59 knowing the behaviour in time of the maximum concentrations for evacuation or protection measures. In order to establish the emergency planning zones there will be considered scenarios with the highest range. At the implementation of he scenario, there will not be taken into account scenarios that may be excluded and are "still hypothetical accidents that may occur." The accidents that might occur and that had not an immediately planned response from the operator, are not taken into account because they deviate from the purpose of the scenario (eg "terrorist attack with heavy guns/bombs/high power explosive ", "fall of a sizeable meteorite over the ammonia tank fully loaded "or" collapse of an aircraft over the tank of ammonia. "These accidents require the establishment of special security measures, the operative plans of intervention, involving the intervention of institutions responsible for security (The Gendarmerie, The County Inspectorate for Emergency Situations, The County Police Department/The Municipal Hall Police, air Forces, The ambulance, etc. SRI) [132]. The result of the established scenario must update the evolution of the dangerous effects in time and space that determines the maximum degree of danger and protective and intervention measures needed to be taken to limit and remove the consequences. In order to write a realistic scenario in which the probability of occurrence is high, one should consider [137]: analysing and evaluating the effect of the produced event; the characteristics of the neighboring buildings: vulnerabilities, the domino effect, the produced meteorological conditions; the specific data of the installations that use dangerous substances in the manufacturing process which represent a major danger; the quantity of the existant substance in the installation and the flow released during the event; the quantity of the dangerous substance released by producing a technological malfunction; the level of training of the staff participating at the production process; the special training of the staff who works at the classified installations with major risk for the intervention and conducting simulation interventions for maintaining workplace skills; establishing and displaying the work instructions for each installtion for normal work conditions but also for accidentally appeared defects; special equipments for protection and intervention; 60 protection systems and safety installations; optical and acoustic notification-allarm systems; organizing, equipment and preparing the Private Service for Emergency Situations of S.C. AMURCO L.L.C. Bacău in relation to the existing risks of the site and the competence approved by the I.S.U.J. and with the performance criteria established by the elaborated by the General Inspectorate for Emergency Situations. For the evaluation efficiency one must take into account data about the toxicity, degree of ignition, exploison potential and reactions in chain in the following situations: starting, normal operation, normal stop, temporary emergency stop, maintainance, starting from the question “ what happens if …..”, taking into account potential ways of failure for every component, the cause of failure and the potential consequences[132]. For the events where fire and explosions are the causes of producing major accidents, leading to the release of a mixture of more dangerous substances, defining the scenario of an accident is done for the more dangerous substance, also considered the guiding substance, namely the ammonia. In figure 5.5. one can see the scheme of the accident effects for the ones that may however be produced [102]. The notices represent: STV = efficiency domain of accident prevention measures; STB = efficiency domain of measures of limiting the effects of accidents; Indices: I = Inventary; CMI = the biggest quantity implied; K = critical; SA = security analysis. INSTALLATION MASS FLOW RATE SURROUNDINGS PROPAGATION EMISSIONS PERCENTAGE DOMAIN Mi MCMI QRCMI MK QRK ACCIDENTS THAT STILL CAN BE PRODUCED QTCMI QTK QRSA MSA VALUE Acid evaluation De ex.AEGL-2 QTSA STV STB Critical points of reference ( Residential area Distance Figure 5.5. Scheme of the effects of accidents for the accidents that may however be produced [102]. From figure 5.5. there follow two deliitation criteria for the accidents that may however be produced, so[102]: Criterion 1 ( inferior limit): The possible courses of incidents from an installation 61 with leaking of dangerous substances, fire or explosion, the failure of measures to prevent accidents, these being classified as accidents that still can be produced, if the CMI of a dangerous toxic substance, inflamable or explosive from the installation exceeds a critical quantity MK, (that quantity whose leak, fire or explosion reaches the relevant value of evaluation of accident just at the critical point of reference); Criterion 2 ( superior limit): There will be taken into consideration the bigget possible accidents that may still occur in an installation, those running incidents with dangerous substance leak, fire or explosion. The installations with major risk in causing accidents involving dangerous substances are [132]: ammonia synthesis installation ; urea synthesis installation; ammonia storage tank; ammonia loading ramp. According to the established scenario, the probability of producing a major accident at S.C. AMURCO L.L.C.Bacău was reduced as frequency but can cause very serious consequences, that is the event was not expected to be produced in the lifetime of the operator, but it can be produced once in the lifetime of the operators of the type. b) Producing the event The event was produced on the tenth of July 2015 around two o’clock p.m. Due to vibrations caused by an earthquake with a magnitude of 8,2º Richter Scale, there occured a major rift to four meters of tank base, which led to the release of a large quantity of ammonia in the atmosphere. The tank was loaded at 80%of its maximum capacity. c) Descrbig the event When the event was produced there was heard a very loud noise that initiated the destruction of the sheath of alluminium sheet, the mineral wool insulation and FOAMGLAS isolation. The objective resonated and the vibrations led to the failure of thermoisolation, this process continuing until the distruction of cryogenic cover up to 90 %, the building becoming unusable for the purpose for which it was created, namely the maintenance of the ammonia in 62 liquid estate in conditions of security (temperature of -40˚C). The produced event affected the backbone of the tank causing a rift with a diameter of 3 m, which led to the release of large ammounts of ammonia in the atmosphere and, due to the high concentration, 25 employees died and over 40 citizens from the population were in lethal zone of the dangerous substance and it also affected the environment[138]. 5.2.6.1. SIMULATION OF DISTRUCTION OF CHEMICAL TANK OF AMMONIA REALIZED WITH THE SIMULATION PROGRAM ALOHA ALOHA software program is a free program developed and used by the USEPA (United States Environmental Protection Agency). With this program one can forecast air concentrations of gas discharges from damaged tanks [130]. The mathematical model as a base of the program works well with certain limitations (low wind speeds - which has no interaction phenomena, very stable atmospheric conditions, slow changes of the wind direction, slow variations of concentrations) [130]. The program objective is to support the decision-makers responsible for the chemical releases into the atmosphere to deal with emergency situations and training activities to establish protective measures and intervention in such situations. The main stages of the ALOHA program are: input, running and retrieving the results, their representation and interpretation. It is used a GIS program for taking an aerial zone picture ongoing process and a program of photographic processing, able to overlap on scale the graphic result of the program over the aerial image captured with the software GIS transparency necessary to the recognition of the main reference objects of the graphic image [130]. The results of the program are presented under different forms: numeric listing; graphically, the plan distribution of the concentration of polluant at the desired hight; graphically, the concentration variation in time in a point from the chosen space; variation in time of the flow source. The interpretation of the obtained results: the plan distribution of the ammonia concentration at different heights, allow the demarcation of areas according to their dangerous toxicity levels at various time intervals, less than 60 minutes, because there are certain rules that, due to the atmospheric instability prohibit forecast programs on longer timeframes[130]. Knowing the most exposed areas to the effects of the pollutant, allow taking preventive measures (equipment of population, isolation, discharge, etc.). Determination pollutant 63 substances and the level of danger in a certain point at a certain distance from the source, it can be done using graphics of temporary variation of concentration [130]. With the help of ALOHA program 5.4 there will be calculated the consequences of an accident at the ammonia tank from SC Amurco LLC Bacau, taking into account the following inputs: the description of the location, the weather conditions (the air temperature, the atmospheric stratification, the wind speed), the place of the crack, the ammonia storage tank characteristics, the physico-chimcal properties of the ammonia. 5.2.6.1.1. THE EVENT SCENARIO, INTRODUCTION OF DATA INTO THE PROGRAM The scenario of the considered event is a crack in the ammonia storage tank of 15,000 tons ( built capacity of the tank). a) Details of the scenario: the place of the crack: at a height of 3m from the base of the tank; crack as a circle, having a diameter of 3 m; the quantity of ammonia stored in the tank is 12,000 t, corresponding to a degree of filling of approx. 80 %. b) The climate data considered while producing the chemical accident are: Tge air temperature: 15 °C; The atmospheric stratification: neutral; The wind speed: 3 m/s. The necessary data to fix the problem of dispersion of the dangerous substance in the atmosphere are: c) The characteristics of the ammonia storage tank [132] Net volume capacity: 22,000 m3 The tank capacity: 15,000 t Storafe parameters: t = - 34 °C, atmspheric pressure =748 The tank height: 20.0 m 27.6 m. diameter: d) Physico-chemical properties of the ammonia [132] Molecular weight: Physical state: Density at 0C: 17.03 kg/kmol colourless gas with a characteristic odor 0.771 g/L 64 Density in liquid estate (at - 79 C ): 0.817 g/L Melting temperature: - 77,7 C Boiling temperature: - 33,35 C solubility: soluble in water, partial soluble in water, parţial soluble in ether density of vapors in report to the air: flash temperature: 0,589 g/ m3 - 2 C temperature of ignition: 651 C chemical reactivity: in contact with Cl, I, Br, HF lights or even explodes calorical power: 4450 kcal/kg limits of exploison: inferior: 16 % /113,34 g/m3 superior: 79 % /178,34 g/m3 maximum pressure of explosion: 0,588 N/mm2 toxicity: substance with medium toxicity, action according to concentration and time of exposure; group of explosion: II A. Toxic cloud dispersion modeling in case of an accident at the ammonia tank allows emphasizing the impact area and its magnitude. 5.2.6.1.2. DESCRIPTION OF THE SITE S.C. Amurco LLC Bacau is located in the southern part of Bacau county at 46 degrees and 31 minutes north latitude and 26 degrees and 56 minutes east longitude. In figure 5.6. is presented the location description, these location data of latitude and longitude respectively being manually introduced. The location of the geographical area in which the phenomenon can spend can also be given through geographical coordinates of one or more reference points so there can be identified any desired object. 65 Figure 5.6. Description of the location. 5.2.6.1.3. METHEOROLOGICAL SITUATION Metheorological information that are required by the program are entered manually and are given by an environmental monitoring station. In this scenario we took data from Bacau Metrology Station as shown in Fig. 5.7. and 5.8 .: atmospheric stratification: neutral; wind speed: 3 m/s. air temperature: - 9 °C; medium humidity 50%. 66 Figure 5.7. Metheorological situation. Figure 5.8. Temperature and humidity. 5.2.6.1.4. SCENARIOS FOR DETERMINING THE SOURCE The ammonia reservoir characteristics determined by this scenario are: the tank capacity: 15.000 t storing parameters: t = - 34 °C height of the tank: 20,0 m diameter: 27,6 m volume: 12.000.000 l. 67 5.2.6.1.5. THE CHEMICAL DANGEROUS SUBSTANCE a) The substance that presents a possible risk in triggering a major accident is the ammonia - a colorless gas with a pungent odor and strong choking. b) Physical properties [132]: The molecular mass: 17.03 kg/kmol Density to air: 0.597 g/ m3 Point of melting: -77.7 ºC Point of boiling: -33.4 ºC The critical temperature:132.4 ºC The critical pressure: 112.5 atm. Factors of cunvertion: 1ppm= 0.71 mg/m³, 1 mg/m³= 1.41 ppm In the presence of the flame, the ammonia burns into the air according to this reaction: 4NH3 + 3 O2 → 2 N2 + 6 H2O + 300.6 Kcal. The acute intoxication is manifested by feelings of suffocation, strong bouts of coughing, agitation, delirium, uncertainty in walking, blood flow disorders. Death occurs in heart failure and pulmonary edema [132]. Concentrations of 0.25% - 0.45% ammonia in air may cause the acute intoxication. An exposure of about 5 minutes in an environment having a concentration of 0.5% - 1% ammonia in the air can cause death. 5.2.6.1.6. ONE CHOOSES THE SITUATION WHEN THE SUBSTANCE DOES NOT BURN In figure 5.9. is presented the chosing of a situation when the substance does not burn to verify its maximum concentration at different times and distances from the source. 68 Figure 5.9. Chosing the situation when the substance does not burn. ONE CHOOSES THE FORM AND THE DIAMETER OF THE HOLE THROUGH WHICH THE AMMONIA DRAINS (figure no. 5.10.): The place of the crack: at a height of 4 m from the base of the tank; Crack under the form of a circle, having a diameter of 3 m; Figure 5.10. Choosing the form and the diameter of the hole through which the ammonia drains 69 5.2.6.1.7. MATHEMATICAL MODELING AND PRINCIPLES FOR DIGITAL SIMULATION After analyzing data from the scenario, three toxic threatening areas resulted [16]: letal – red colour; of intoxication - orange colour; of pollution - yellow colour. Depending on the speed and the direction of the wind one can establish the measures of intervention, warning and alarming of workers and population about the occurence or imminence of a danger in order to pass in a short time to the application of measures of protection and intervention. 5.2.6.1.8. THE QUANTITY AND TIME OF AMMONIA FLOW In figure 5.11. is presented the graphic for the quantity and time of the ammonia flow. Figure 5.11. The quantity and time of the ammonia flow. From the resulted graphic, one can observe the fact that, in the first minute and a half after breaking the tank, approx. 9,000 t of ammonia leaked, the other 3,000 t being leaked in the other minute and a half. In figure 5.12. is presented the mark of the concentrations of ammonia for different 70 values. Figura 5.12. The print of ammonia concentration for different values. From the graphic one can observe the fact that the dispersing of dangerous substance increases with the decrease of the ammonia concentration due to the wind speed and the leakage, the area affected by the cloud of ammonia is 11,000 m², with different concentrations depending on the distance. In figure 5.13. is presented the graph of ammonia concentration variation at a distance of 500m. . Figura 5.13. Concentration of ammonia at a distance of 500 m. From the resulting graph one can see that the concentration value increases in the first three minutes up to the maximum value of 5000 ppm and then gradually decreases for one hour 71 up to a value of 3000 ppm because of the wind speed which disperses the ammonia in an area increasingly larger with decreasing concentration. In figure 5.14. is presented the graph of the variation of the concentration of ammonia in the distance of 1000m. Figure 5.14. The variation of ammonia concentration at a distance of 1000 m. From the resulting graph one can see that in the first 5 minutes the concentration decreased from a maximum of 1500 ppm to 1000 ppm., while during 55 min with a tendency to decrease according to the distance and due to the wind speed that disperses the ammonia in an area increasingly larger with decreasing concentration. In figure 5.15. is presented the variation of ammonia concentration at a distance of 3000 m. Figure 5.15. The variation of ammonia concentration at a distance of 3000 m. From the resulting graph one can see that, in the first 30 minutes, the concentration decreased from a maximum of 220 ppm to 150 ppm, with a tendency to decrease according to 72 the distance and speed of the wind which disperses the ammonia in an area increasingly larger with decreasing concentration. 5.2.6.1.9. AMMONIA LEAKING FREE ZONE WITHOUT FIRE In figure 5.16. is presented the graph with ammonia leaking free zone without fire. Figure 5.16. Graph with ammonia leaking area without fire. In figure 5.17. is given a first result of simulation, that is the spatial distribution (twodimensional) of the cloud of ammonia in the maximum phase of development, weather conditions and data flow. Figure 5.17. Escape zoning map. 73 If one superimposes the graph in Figure 5.16 over GIS map of Bacau county, figure 5.17. there can be seen that the gas cloud reaches 10,000 m of tank of ammonia in the South - North to Bacau, whose suburbs in the South area re already affected by the cloud of ammonia and there may be established the evacuation zones of the population. Even the city center is very close to the border gas cloud. 5.2.6.1.10. THE FLAMMABLE AREA In figura 5.18. is presented the graph with the flammable area. Figure 5.18. The graph with the flammable area. From the resulting graph one can see that the flammable area is in the vicinity of the tank over an area of about 2500 m2, and where the ammonia is on fire, the fire produced can be followed by a burst of high proportions as shown in Figure 5.20 . 5.2.6.1.11. AREA OF EXPLOSION In figure 5.19. is presented the graph with the area of explosion. Figure 5.19. Graph with the area of explosion. 74 From the resulting graph one can see that, following an explosion, it would cause the destruction of the existing buildings over an area of about 2,500 m², perhaps serious harm on an area of about 4,000 m² and the breaking glass panes at the existing buildings on an area of approximately 10,000 m² which could produce victims of of population in the explosion area. 5.2.6.1.12. DETERMINATION OF EVACUATION ZONES In figure 5.20. is presented the map with the setting of the escaping areas . Figure 5.20. The map with the setting of the escaping areas. Depending on the chart with the leaking of ammonia without it catching fire (Figure 5.16.) and depending on the wind direction and speed, one can determine the evacuation of population , animals and material goods areas, (figure 5.20.) that is the area from the ammonia tank of approximately 11,000 m² to the northern part of Bacau, in a sufficient period of time to save the life of the people being in the fatal poisoning and pollution zone. 5.2.7. EVALUATION OF THE RISK FACTORS IDENTIFIED IN TERMS OF SERIOUSNESS The severity class establishment is done with the tool "Scale for measuring severity and probability of risk factors on the consequences of the action system" [13]. 75 " The Scale for measuring severity and probability of risk factors on the consequences of the action system" is a rubric for grading the severity of consequences classes and classes of probability of their occurrence [12]. Table 5.9. shows the Scala for the listing of the consequences of action severity and probability of risk factors on system [12]. Table 5.9. The Scale for measuring the severity and probability of risk factors on the consequences of the action system [12]. SEVERITY CLASSES SEVERITY OF CONSEQUENCES CONSEQUENCES 1. NEGLIGIBLE 2. SMALL Minor reversible consequences without damaging the environment or employees. Reversible consequences affecting the environment. Reversible consequences with environmental damage and 3. MEDIUM registration of victims among employees - at least one employee. Irreversible consequences affecting the environment and 4. BIG record of casualties among employees - up to five employees. Irreversible consequences affecting the environment and the 5. GRAVE record of casualties among employees - more than five employees. 6. VERY SERIOUS Irreversible consequences affecting the environment and the record of victims among the employees and the public. 5.2.8. EVALUATION AND FREQUENCY OF THE INITIATING EVENTS AND THE CONFIDENCE LEVELS OF BARRIERS Once one has established on a statistical basis, the intervals at which the events may occur, the framing is done in classes of probability. In terms of probability classes, one must be taken into account the following classes [12]: class 1 – the frequency of producinf the event : once at over 10 years; class 2 – the frequency of producing the event: once at 5 - 10 years; class 3 – the frequency of producing the event: once at 2 - 5 years; class 4 – the frequency of producing the event: once at 1 – 2 years; 76 class 5 – the frequency of producing the event: once at 1 year - 1 month; class 6 – the frequency of producing the event: once at least one month. In table 5.10. is presented the grid of risk evaluation based on probability and gravity [12]. Table 5.10. CLASSES OF PROBABILITY 6 VERY SERIOUS VERY FREQUENT P<1 month FREQUENT 6 1 year 1 month<P< A LITTLE FREQUENT 2 years 5 1 year<P< RARE 4 5 ani RARE 10 years 2 ani<P< VERY RARE 3 5 years<P< CONSEQUENCES 2 P> 10 years GRAVITY CLASSES OF EXTREMLY 1 ENVIRONMENTAL DAMAGE AND REGISTRATION OF EMPLOYEES (6,1) (6,2) (6,3) (6,4) (6,5) (6,6) (5,1) (5,2) (5,3) (5,4) (5,5) (5,6) (4,1) (4,2) (4,3) (4,4) (4,5) (4,6) (3,1) (3,2) (3,3) (3,4) (3,5) (3,6) (2,1) (2,2) (2,3) (2,4) (2,5) (2,6) (1,1) (1,2) (1,3) (1,4) (1,5) (1,6) AND POPULATION VICTIMS ENVIRONMENTAL DAMAGE AND 5 SERIOUS REGISTRATION OF VICTIMS AMONG EMPLOYEES OF UP TO 10 EMPLOYEES ENVIRONMENTAL DAMAGE AND 4 BIG REGISTRATION OF VICTIMS AMONG EMPLOYEES OF UP TO FIVE EMPLOYEES 3 MEDIUM 2 SMALL DAMAGE TO THE ENVIRONMENT AND UP TO TWO EMPLOYEES ENVIRONMENTAL DAMAGE 1 NEGLIGIBLE Depending on the risk that may occur, severity class and class probability (likelihood couple - gravity) and under the scenario of the presented accident, one identifies the risk level in the table 5.10. [12]. Being given the frequency with which there can be produced an earthquake in Romania according to the seismic characteristics of the area shown in section 5.2.2.8. ie over 10 years – it is EXTREMELY RARE, according to the Grid risk evaluation presented in Table 5.10. and it is 1. 77 In table 5.11. is presented the Scale to classify the level of risk/security depending on probability - severity scale built on risk evaluation [12] With the help of the scale to classify the levels of risk/security levels there are determined the levels for each risk factor individually. Table 5.11. LEVEL F RISK PROBABILITY – SEVERITY COUPLE LEVEL OF SECURITY 1 - MINIMUM (1,1) (1,2) (1,3) (1,4) (1,5) (1,6) (2,1) 7 - MAXIMUM 2 – VERY SMALL (2,2) (2,3) (2,4) (3,1) (3,2) 6 – VERY BIG 3 - SMALL (2,5) (2,6) (3,3) (3,4) (4,2) (5,1) (6,1) 5 - BIG 4 - MEDIUM (3,5) (3,6) (4,3) (4,4) (5,2) (5,3) (6,2) 4 - MEDIUM 5 – BIG (4,5) (4,6) (5,4) (5,5) (6,3) 3 – SMALL 6 – VERY BIG (5,6) (6,4) (6,5) 2 – VERY SMALL 7 - MAXIMUM (6,6) 1 - MINIMUM Given the risks that may occur at the site S.C. Amurco LLC Bacau identified in subchapter 5.2.3.4., points 1 and 2 may do the evaluation of the frequency initiating events like this: In table 5.12. there is presented the risk evaluation sheet identified in SC Amurco LLC Bacău, depending on the grade of severity presented in Table 5.9. and class probability table shown in table 5.10 [12]. Tabelul 5.12. RISK NATURAL RISKS Earthquake and landslides: Risk Factors: F1 – Chemical accidents F2 – Railway accidents F3 - Explosions F4 - Fires Risc Factors: Falling of cosmic objects F5 – Chemical accidents F6 - Railway accidents F7 - Explosions F8 - Fires CLASS OF GRAVITY CLASS OF PROBABILITY LEVEL OF RISK 6 1 3 5 1 3 4 1 3 4 2 4 1 3 3 1 7 5 5 7 5 1 3 4 1 1 3 4 2 3 3 1 3 3 1 5 7 5 5 7 LEVEL OF SECURITY 78 Continuation Table 5.12. RISK TECHNOLOGICAL RISKS Factors of risk: F9 - Terrorist attack with heavy weapons F10 – Chemical accidents F11 - Railway accidents F12 - Explosions F13 - Fires CLASS OF GRAVITY CLASS OF PROBABILI TY LEVEL OF RISK 2 5 3 5 6 1 3 5 1 3 4 1 3 4 2 3 1 3 3 1 7 5 5 7 LEVEL OF SECURITY According to the scenario of the accident produced at the ammonia tank established in subchapter 5.2.6. namely the death of 25 employees and over 40 people as well as the damage to the environment in case of an earthquake greater than 8º on the Richter scale for which was calculated and constructed the tank, it may crack and even destroy, leading to dispersal of a large quantity of ammonia in the atmosphere, and "irreversible consequences are affecting the environment and record casualties among employees and the public," gravity is 6 class with VERY SERIOUS consequences as shown in table 5.9 If the earthquake is less than 8 º on the Richter scale, as shown in table 5.9 in case of an ammonia tank there are "negligible consequences" severity class is 1. Given the frequency with which there can be produced an earthquake in Romania according to the seismic characteristics of the area shown in section 5.2.2.8. ie annually frequently, according to the Grid risk evaluation, the class probability presented in Table 5.10. is five. In the presented case in the scenario accident, the producing of an earthquake of 8,2º on Richter Scale, where the severity class is 6 and the class probability is 1 in table 5.12. the resulting risk level 3 – SMALL and the security level is 5- BIG. The same is for each risk factor individually. Figure 5.21. presents the variation of partial risk and safety levels, depending on the risk factors [12] 79 7 PARTIAL LEVELS OF RISK AND SECURITY 6 5 4 3 2 1 0 F1 F3 F5 F7 F9 F11 F13 RISK FACTORS Fig. 5.21. Variation of partial risk and safety levels, depending on risk factors [12]. Where: Represents the partial risk level Represents the security level F1 – Chemical accidents; F2 – Railway accidents; F3 -Explosions; F4 - Fires; produced after an earthquake > 8º Richter scale. F5 – Chemical accidents; F6 - Railway accidents; F7 -Explosions; F8 - Fires; produced as a result of falling of cosmic objects. F9 – Terrorist attack with heavy weapons; F10 – Chemical accidents; F11 - Railway accidents; F12 -Explosions; F13 - Fires; produced by technological risks. 80 As can be seen both in Table 5.12. and in the graph from figure 5.21. the level of risk and the security level are the same for risk factors complementary respectively, chemical accidents and fires and also are the same for accidents on communication routes and explosions in the classes of severity and probability differ in some risk factors but fall in the same scale according to the table 5.11. 5.2.9. ESESTIMATING THE DIRECT IMPACT OVER THE ASSETS , THE DATES AND INFORMATION, INFRASTRUCTURE AND THE STAFF While elaborating the accident scenario, there is estimates a direct impact over [132]: goods and values; data and information; infrastructure (telecommunication and systems); general infrastructure; the staff availability; compliance with the laws and procedures in the field. According to the variation of the released ammonia flow, measures of decreasing the impact over the own staff, the population from the impact area, the material goods and the infrastructure: evacuating the staff and the material goods; alerting/alarming the subunits of intervention; implementation of intervention plans; specialized medical assistance; conducting actions of intervention by the specialized forces. 5.2.10. EVALUATION OF THE EXISTING PROTECTION FACTORS , COMPENSATION AND REHABILITATION In order to establish the risk reducing factors, one evaluates 5 categories of measures, respectively [132]: discouraging measures through the actions done by the specialized staff to inform their own staff and the population from the area about the danger of the used hazardous substances; 81 prevention measures: through the activities developed by S.P.S.U. and the specialized staff regarding the control of respecting the installation exploit conditions and the safety at work; measures of protection: by using the imposed systems by technical standards and the special equiping within special installations as well as the population that could be affected; compensatory measures; recovery measures. Prevention and protective measures that can be applied to reduce the risk are: collective protection, personal protection, employee training and preparation for emergency interventions, training and other personnel-alarm notification system. a) The collective protection is achieved by equipping the technological installation with installations, facilities and equipment of labor protection so [137]: pipes through which flow pressurized fluids or which may cause burnings (acids, bases) are provided with protected guard flanged joints; pipes through which flow hot fluids are insulated; pipes through which flow flammable fluids have flanged joints equipotential bridges; electrically operated machines are touched to the ground; all the moving parts of the machines are provided with protective guard; pomps with wich the flammable liquids flow, have an antiexplosive construction and the ones for corosive liquids are made of specific anticorosive materials; machines, devices and installations are equipped with measuring and control aparatus that are supposed to periodic metheorological check; on the AMURCO site smoking and open fire are forbidden. Smoking is allowed only in places specially designed and marked in this sense; for mechanical works with open fire are drawn specific work licences for every job and work place; the installations where accidental releases of polluants ( gases, vapors or dust) are possible, are equipped with ventilation systems; for all workplaces are drawn and displayed work instructions which show the way of correct and not dangerous for the execution of each operation, manipulation, control, risk factors and measures of prevention etc. so as to eliminate as much as possible the accidents at work and/or professional illnesses. 82 b) The individual protection – is realised by using the individual protection equipment which means all the individual ways of protection that the worker wears during the working hours for[137]: the current operations the equipment iconsists of: helmet, glasses for protection, overalls, gloves, boots, gas mask with filter cartridge against the corresponding toxic substance; the interventions in case of breakdowns at the society , there are autonomous insulating devices ( with compressed air), masks with adduction hose and isolalating. c) The training for the employees and the preparation in case of emergrncy intervention. The company management allows the access to training and ensures the raising of the level of training for the whole staff in different domains of activity through participation at different specialised courses. The practical training of the staff of each department will be simulated through possible accidents involving dangerous substances. At these simulations all the company employees with responsibilities in the field of emergency management will participate, namely: the members of emergency cell, the medical personnel from the dispensary unit, the staff of civil protection, the private service for emergencies of the society provided with logisticsand dispatcher [132]. The simulations are based on scenarios of possible accidents that may occur because of their current activities that have the potential to manifest themselves outside the establishment. These exercises are performed in collaboration with security forces and supporting intervention from outside, if the response capacity of the company is exceeded. Preparing for emergencies is executed in accordance with the following documents: the preparation and main activities for the current year approved by I.S.U.J. the Order of the county prefect, the internal emergency Plan, the external emergency Plan drawn up by I.S.U.J. for Amurco site, the fire intervention Plan. d) The training of other staff: new employees, visitors, delegates, teams of workers of the companies that have contracts for temporary work in unity, it is made permanently for each field of training (safety of work , emergency situations) recorded in Registries for preparation and are materialized through individual evaluation tests [137]. e) The notification and alarming system is organized as to allow the reception and transmission of the notification and alarming civil protection, warning the population in case of 83 a major accident involving dangerous substances, or, in case of disasters and exchange of information, necessary knowledge about the reality on the ground, analysis of situations that may occur, decisions to manage and coordinate the response actions [132]. The alarm system provides a coverage of ~ 80% of the perimeter of S.C. AMURCO LLC and it is composed of a siren of 5.5 kW connected to the centralized system of Bacău, 3 sirens of 3 kW, two sirens of 75W, one horn steam. The audibility of the siren installed at 5.5 kW reaches 800m to the central station platform outside, inside it is vitiated by: the noise, density and height of installations. 5.2.11. PERFORMANCE EVALUATION OF SAFETY BARRIERS After identifying the potential accident scenarios, there must be identified major security barriers that allow the reducing of the severity of the potential accident [133]. Reducing the probability of a major accident requires the adoption and implementation of procedures and instructions for the safe operation of installations, processes, equipment, as well as maintenance activity and temporary stop [132]. All the facilities are provided with equipment for monitoring technological parameters, automatic alarm systems in case of emergencies and safety systems, these systems being specified for each installation site in the site Report [132]. In order to prevent the technological accidents, the ensurance of the security operation of machinery, equipment, devices, systems, there must be carried out, systematically, preventive control of the technical conditions of machinery, installations, equipments [137]. The preventive monitoring of the technical condition of machinery, facilities and equipments is carried out only by authorized personnel and at the terms established and imposed by the specific norms. Periodically there must be controlled the technical condition of the installations and must be checked the dynamic equipment, the technical condition of equipment and electrical installations and the automation for pouring ammonia tank in cisterns. One must be periodically tested the technical condition of the equipments, appliances, power installations and automation operating in potentially explosive environment and the existence of the checking bulletins. One must be checked [137]: the existence and the status of the first intervention means against fire; the existence and the technical status of the protection equipments against atmospheric electrical discharges; the instrumental air quality (dewpoint, mechanical impurities), in order to prevent the shutdown of the measure and control aparatus; 84 the way of respecting the instructions regarding the activity of lubricating the dynamic machinery; periodically, the equipment and machinery functioning is checked by making measurements of vibrations and the diagnosis of the dynamic machinery as well as the dynamic local balancing of the moving elements and the dynamic machinery. The purpose of these checks is for [137]: the functioning in safety conditions; detection of discontinuities, the unadmitted malfunctions at the elements and welds of machinery; anticipating the machinery reparation; prevention for the accidental stops opririlor accidentale, damages and serious accidents; prolonging the life of the equipment; functioning of the machinery in safety conditions. Every accidental stop of the dynamic machinery, the energetic and automation equipments is analysed. The purpose of these controls is to discover in time the damages, before affecting the safety of machinery installations and equipments functioning and to take decisions regarding the repairs or replacement of machinery or faulty equipment. After the step by step implementing of the sequencing method CARMIS / DS, there was drafted the Safety Report for S.C. Amurco LLC BACĂU which is the last step of the method and its result is presented in electronic format in Appendix 4. CHAPTER 6. EXPERIMENTAL OBTAINED RESULTS 6.1. EXPERIMENTAL OBTAINED RESULTS AND THEIR INTERPRETATION The scenarios considered in the two case studies draw a combined emission of ammonia and chlorine in liquid and gas. Both liquid ammonia and chlorine in a first phase flow in the vat 85 of the tank, some of them even turning into gas during the discharge, with the following effects. 6.1.1. For the ammonia The ambient air is rapidly entrained in the evaporation of liquid ammonia, leading to a significant cooling of the gas-air mixture and the formation of a dense cloud. The appearance of this event leads to the following possibilities: once with the increasing distance from the ammonia tank, the concentration of the ammonia decreases both in atmosphere and in that space, figures 5.13. 5.15., at 2000 m, after 45 minutes, the maximum concentration being 220 ppm, in air outdoor, figure 5.15.; the variation of the printing of some areas of concentrations of the ammonia depending on the distance from the tank, is presented in figures 5.13. 5.15.; the concentration of 750 ppm, at which, for a short exposure, death occurs rapidly, reaching approx. 1800 m away from the source after about 1.5 min. from the accident, figure 5.13. şi 5.14. According to the presented accident scenario, after identifying the risk level, in table 5.12. where the consequences are ireversible, affecting the environment and implying victims among the employees and population, this simulation shows the fact that the risk level is 3 – MIC, and thne level of security is 5- BIG and at a distance of 11000 m. from the ammonia deposit there may occur: significant polution of the atmosphere with ammonia, both inside the platform and in its impact area; risk over the health of its own employees and the staff from the impact area; risk of fatalities over an area of 1530 m² around the reservoir; risk of the possibility of functioning of the neighboring installations. 6.1.2. For the chlorine The air is mixed with the chlorine gas, the system is cooling being based on energy consumption for the evaporation of the chlorine, thus forming a cloud of chlorine which is much heavier than the surrounding air, tending to remain at the ground level. The aparition of this event leads to the following possibilities: 86 the mark of dispersing chlorine increases with the decreasing concentration due to the wind speed and the phenomenon of dispersion, the affected area by the chlorine being 10,000 m², with different concentrations according to the distance, figure 5.28.; one can find the values of chlorine concentration at a certain point, figures: 5.29. şi 5.30; in the first five minutes the value of concentration increases up to the maximum value of 3,5 ppm and then it gradually decreases for one hour up to a value of 1 ppm, thanked to the wind speed which disperses the chlorine over a distance of 3 Km from the place where the accident is produced, figure 5.30. According to the scenario of the presented accident, after identifying the risk level in table 5.12. the consequences are irreversible for the environmental damage and registration of victims not only among the employees, but also among population where the risk event resulting 3 - MIC, and the security level is 5 MARE, and at a distance of 200 m from the reservoir, there could be produced: significant polution of the atmosphere with chlorine vapors not only inside the platform, but also in its impact area; risk regarding the health of the population and its own employees; risk of fatalities on a distance of 200 m² around the reservoir; If, however, an accident would occur on the studied sites, different procedures are implemented drawn up by the economic operator and established through CARMIS method (listed in section 3.6.1.) with minimum work required to be carried on the site and outside it for the management, limitation and removing of the consequences of the accident, the evacuation of the people, saving lives and material goods. After implementing step by step the stages of method CARMIS, the economic operator will be able to draw, by specialized persons, the Safety Report that represents precisely the proposed and obtained result. 6.2. DRAFTING SECURITY REPORT- THE MAIN DOCUMENT OF THE MANAGEMENT OF SECURITY SYSTEM The final result of the implementation of the method CARMIS is represented by the preparation of the Security Report. According to H. G. 804/2007 as amended and supplemented, on the control of major accident hazards involving dangerous substances, the Security Report will be prepared for S.C. 87 Amurco LLC Bacau, respectively S.C. CHIMCOMPLEX S.A. ONEŞTI by the economic operators classified Seveso who "produce, handle, use, store substances: toxic, dangerous, explosive, flammable, which, by their nature, in abnormal operation of installations, generates situations of serious risk with serious effects on employees, population and the environment". It will be prepared in accordance with GD 804/2007 "on the control of major accident hazards involving dangerous substances" and constantly updated according to changes in the economic operator. The Activity Report sets out measures to control the activities presenting majoraccident hazards involving dangerous substances, to prevent and limit the consequences for the safety and health of population and on the quality of the environment. The safety report specifically treats the events resulting from the uncontrolled developments during exploitation, events that lead to serious danger of immediate or delayed establishment or outside it because of their activity profile, the occurrence of natural disasters (earthquake, landslides ) the occurrence of terrorist attacks and/or cosmic objects falling from the atmosphere. The Safety Report is a reference document for organizing, training, equipping and intervention in situations of serious risk, considered emergencies that require activities of noyification-alarm and specific intervention. The Safety Report will be drawn for the specific of organizing economic operator and has the following features: it is applied on the whole area of the chemical platform; it is applied to the societies that develop their activity on the emplacement; the foreknoledgements are mandatory for all the staff on the platform, considered an area of emergency planning including all the operators outside the society who develop work under contracts on the site. In the case of a major accident, which can not be limited at the site, some specific foreknoledgements of the safety report are applied to the economic operators in the neighborhood and nearby communities that may be affected. For the immediate settlements, in the event that an alarm disaster is produced, due to a chemical accident at an economic operator from the zone of responsibility, the administrative staff management with roles and responsibilities in emergency situations (mayor, deputy secretary of the village) will act according to the plan analysis and will cover the risks for each locality. 88 The major accidents potential danger that is present in both locations, justifies the need for drawing up the safety report, the internal emergency plan and a policy of prevention, for the following reasons: the existence of some technologies and installations which produce, use, manipulate and deposit dangerous substances; the existence of some large quantities of dangerous substances at a given moment; the affecting of neighborhood with serious consequences when there are massive emissions of dangerous substances; the pollution of surface waters; The location and technological specific may favor simultaneous expression of multiple risk factors that can facilitate training in "domino effect" of more installations causing worsening consequences of an accident involving dangerous substances. The requirements set out in the document regarding major accident prevention policies are changed or updated and supplemented by major-accident dangers presented by each economic operator and they contain the following elements: 1. major accident prevention policy – document including the economic operator’s objectives and the action principles with respect to major accident dangers; 2. security management - comprising organization, responsabilities, procedures, processes and ressources for determining and applying the prevention policy of major accidents, namely: a) organization and staff; b) identification and evaluation of major dangers; c) operational control; d) management for mordenisation; e) plans for mergency situations; f) monitoryng the performance, checking and eview. GENERAL CONCLUSIONS This paper contributes to the ellaboration of a method of analysis and evaluation of risks that may be produced at the economic operators that use in the production process dangerous substances, reffered to as SEVESO operators and has a great advantage regarding the existent methods, namely at international level, it covers the weakpoints and their threatenings and allows the economic operator to establish the safety report after the implementation of the method. 89 Regarding the opportunity of the thesis 1. In many European countries there exist well established methodologies for risk evaluation when producing major accidents involving dangerous substances. In Romania, after joining the European Union, there does not exist a unique methodology yet to be accepted by the evaluators of risk on sites where there is the possibility of producing a major accident, as well as the danger to amplify it by the "Domino" effect, because the location conditions and the existence nearby of some installations or economic operators. 2. Based on the study of the existing documents in the international literature about the existence of methods of risk analysis and industrial safety within an operator who uses in the production process dangerous substances and given the fact that in Romania there is no such method, it is necessary to investigate the status of existing risks, the accidents and their consequences at the objectives SEVESO in ourcountry, the security measures implemented and to identify new solutions for the prevention of major accidents involving dangerous substances and to increase the existing security level. 3. From the experience of the disasters in our country, the specialists in the field have determined that natural disasters are unpredictable and almost impossible to avoid, while technological disasters can be avoided to produce systematically. For each type of risk that may trigger a disaster, there must be realized management systems to prevent or minimize negative impacts and the damages of any kind. 4. The system of security management in all areas must identify all the important functions at all levels of the organization, to define clearly and explicitly the roles, tasks, responsibilities, authorities and resource availability in order to prevent and limit the impact of possible emergencies in the area of competence. 5. After the implementation in our country of European legislation, harmonized and transposed into Romanian legislation in Bacau County in 2015 there were identified five economic operators classified SEVESO high risk, and six minor risk, the sites being located near areas with high vulnerability for the population or the environment. In these locations the development of risk studies is to prevent technological accidents (which were produced in some locations) and emergency planning. Based on these studies, the population can be informed, trained and prepared regarding the behavior during accidents, which can lead to saving many lives. These issues led to the decision to study some of the methods of risk evaluation and security of existing industrial at an international level, to identify a new method to answer to the needs of covering the existing risks within the territory of economic operators from Romania who use dangerous substances in the production process. 90 Regarding the theoretical substantiation of the ellaborated CARMIS method 1. The new method of risk evaluation and industrial safety identified and named METHOD CARMIS (Combined Analysis and Assessment Method of Risks and Industrial Safety Method Combined of Analysis and Risk Evaluation and Security Industrial) resulted from combining the strengths of the studied methods, the coverage of weaknesses and threats and it is aimed at qualitative and quantitative determination of the level of risk/security for the installations/technologies of the economic operators who use in the production process dangerous substances and can cause major accidents with serious implications on population, material goods and the environment. 2. The defining characteristic of the studied risk evaluation methods is represented by their high degree of complexity. 3. The representation of accident scenarios using the butterfly node which associates a tree of failures with a tree of events through ARAMIS method, should be taken in regulations governing the drafting of safety reports. 4. The methods studied and presented being methods of analysis and evaluation do not establish measures/intervention actions necessary to limit and remove the consequences of a possible major accident. 5. From the point of view of security objectives SEVESO, the studied analysis methods of risk evaluation is necessary both in terms of the way of identification of stages in risk evaluation and the establishment of prevention, protection and intervention measures on a given site, in one combined method. 6. The use of the studied risk evaluation methods presents some drawbacks, which, due to their complexity, are difficult to apply in practice, are expensive, require a large volume of work and involves a particular specialization and competence of analysts who realise the risk evaluation. Regarding the implementation of the method CARMIS 1. The new method developed by combining strengths and weaknesses and threats coverage of the studied integrated and selected methods, called CARMIS realizes a full risk evaluation and has the following main benefits: a. it derermines both qualitatively and quantitatively the level of risk/security for the installations/technologies of the economic operators who use dangerous substances in the production peocess and can produce major 91 accidents with serious implications on population, material goods and the environment; b. it establishes measures/actions of protection/intervention necessary for lumiting and removing the consequences of a possible major accident on the site or outside it; c. it contains the data and information necessary for the economic operator to make the Security Report. 2. To achieve the identification of major dangers, resulting from normal and abnormal operation as well as the evaluation of their likelihood and their severity, one tried to approach the method in the team for the systematic identification of risk and safety in order to adopt and implement the most appropriate intervention procedures to limit and remove the consequences of a major accident. 3. The potential danger which the chemical platform represents, (using dangerous substances in the production process) both for the site and off the site, for the population, is determined by the coexistence and the possibility of manifestation of several risk factors: a. the hazard properties of dangerous substances; b. the occurrence of damages to the equipment at the site. 4. From the implementation of the new identified methods of risk evaluation, it is clear that the likelihood of emergencies on the site is reduced by equipping the facilities with safety systems, automation and control of the risk parameters, the training and education of the operating stafff will possibly limit the consequences of a potential major accident through the implementation of procedures for emergency management established in the new method. Regarding the original character of the work 1. Under the new method of risk evaluation proposed, there were studied and analyzed as novelty and originality elements towards the existing studied methods, the most serious cases in which, however, could be produced major accidents and it allows for the implementation of steps to draw up the Safety Report. 2. Making the SWOT analysis of the studied methods and selecting strengths, which were taken up in the new method of risk evaluation as well as eliminating the weaknesses and threats has enabled a new method and completing it so that any economic operator, after the implementation of the method, to be able to draw up the Safety Report established by the law specialists, without having to implement several methods in the field. 92 3. After the checking and the implementation of the method, the economic operator will prepare concrete procedures to establish clear links between the data of the production of a major accident and the measures required to be taken to limit and remove the consequences of its on-site or off-site. 4. The simulation of accidents scenarios involving dangerous substances, using the program ALOHA, allows the authorities concerned in the National System for Emergency Situations Management to order, in time, planned measures needed to establish safety distances, to protect and save the lives of the population and their goods from the areas potentially to be affected by a possible accident; 5. The method of risk evaluation, CARMIS, proposed in this thesis is a complete method which establishes, after following the steps of risk, assessment activities to be carried out on site and off site for the management, limitation and removing the consequences of an accident and, what is most important, it enables the achievement of the Report of Security; 6. Some of the results were presented at various scientific conferences and published in specialty magazines. Regarding the ways to further develop the research 1. As in Romania there is no single accepted methodology to be used by assessors of risk on sites where there is the possibility of a major accident involving dangerous substances, you still need to study and to identify new methods of evaluating risks. 2. The theoretical basis and the results of simulations performed by the selected programs may constitute a useful material in identifying other methods of risk assessment or even for for completing the method CARMIS / DS with other steps and measures imposed by the new technologies of plants on existing sites or those that will be realized. 3. As there was used only the simulation program ALOHA to assess the identified risk factors and to estimate the direct impact on supplies, staff and infrastructure, it is necessary to continue and extend the experimental research and other programs of the existing ones, on an international level, for improving and complementing them. 4. In this paper we studied the behavior of two dangerous substances, namely ammonia and chlorine stored in tanks of large capacity which can produce the biggest chemical accident in Romania, without taking into account other dangerous substances in the production of our country's industry. This aspect can lead to future diversity of research topics to identify new methods of risk evaluation, the most important dangerous substances on the site of the economic operators that use, in the production process, dangerous substances such as sulfuric acid, hydrochloric acid, petrol, diesel, radioactive substances etc. 93 The exploitation of the realised researches The realised researches in this paper were published in articles and presented at conferences, or are awaiting to be published: Papers published in ISI: 1. Daniel-Cătălin Felegeanu, Valentin Nedeff, Radu Cristian, Mircea Horubeţ, Risk management for ammonia tank failure at ,,S.C. SOFERT S.A.” Bacau, Environmental Engineering and Management Journal, vol. 13, No. 7, pp. 1587-1594, July 2014; 2. Doina Capşa, Mirela panainte, Dana Chiţimuş, Marius Stănilă, Daniel-Cătălin Felegeanu, Accidental pollution with ammonia. Influence of meteorogical factors, Environmental Engineering and Management Journal, vol. 13, No. 7, pp. 1573-1580, July 2014; 3. Daniel-Cătălin Felegeanu, Gigel Paraschiv, Mirela Panainte-Lehaduş, Mircea Horubeţ, Mihai Belciu, Mihai Radu, Ovidiu Leonard Turcu, A Combined Method for the Analysis and Assessment of Risks and Industrial Safety, Environmental Engineering and Management Journal, vol. 15, No. 3, pp. 553-562, March 2016. Papers published BDI 1. Daniel-Cătălin Felegeanu, Valentin Nedeff, Mirela Panainte, The prevention of hazardous substances major accidents, Journal of Engineering Studies and Research, vol. 18, No. 3, 61-68, July – September 2012; 2. Daniel-Cătălin Felegeanu, Valentin Nedeff, Mirela Panainte, Analiysis of technological risk assessment methods in order to identify definitory elements for a new combined/complete risk assessment method, Journal of Engineering Studies and Research, vol. 19, No. 3, 32-43, July – September 2013. Papers published in Proceeedeingurile international or national conference 1. Daniel-Cătălin Felegeanu, Valentin Nedeff, Prevent major accidents involving hayardous substances, First International Conference on MOLDAVIAN RISKS – FROM GLOBAL to LOCAL SCALE, 16-19 May 2012, Bacău, România, pp.86; 2. Daniel-Cătălin Felegeanu, Valentin Nedeff, Panainte Mirela, Security management in the context of integrated management at S.C. SOFERT S.A. Bacău. Caze stuy – the dammageof the ammonia tank from ,,S.C. SOFERT S.A.” Bacău, The X th International Conference CONSTRUCTIVE AND TECHNOLOGICAL DESIGN OPTIMIZATION IN THE MACHINES BUILDING FIELD – OPROTEH, 23-25 May 2013, Bacău, România, pp.55; 3. Daniel-Cătălin Felegeanu, Valentin Nedeff, Panainte Mirela, Study of the methods assessment of the technological risk for identification a combined-complete method 94 assessement of risk, The X th International Conference CONSTRUCTIVE AND TECHNOLOGICAL DESIGN OPTIMIZATION IN THE MACHINES BUILDING FIELD – OPROTEH, 23-25 May 2013, Bacău, România, pp. 55; 4. Panainte Mirela, Valentin Nedeff, Moşneguţu Emilian, Felegeanu Daniel-Cătălin, An analyze of the occupational health, safety and security system at the „Vasile Alecsandri” University of Bacau, EEA&AE’2013 – International Scientific Conference, 17-18.05.2013, Ruse Bulgaria, pp. 322-329. 5. Daniel-Cătălin Felegeanu, Valentin Nedeff, Mirela Panainte-Lehaduş, Mircea Horubeţ, Marius Stănilă, Mihai Radu, An analysis of the risk assessment methods in establisments where dangerous substances are used in the processing activities, Second International Conference on Natural and Anthropic Risks ICNAR 2014, (04-07 iunie 2014) Bacau, Romania – poster. Referate: 1. Felegeanu Daniel-Cătălin, Studii şi cercetări cu privire la factorii care influenţează riscul şi securitatea industrială , Universitatea ,,Vasile Alecsandri” din Bacău; 2. Felegeanu Daniel-Cătălin, Referatul nr.1, Stadiul actual privind managementul riscurilor şi securităţii industriale, Universitatea ,,Vasile Alecsandri” din Bacău; 3. Felegeanu Daniel-Cătălin, Referatul nr.2, Stabilirea bazei tehnice de cercetare a riscurilor şi securităţii industriale, Universitatea ,,Vasile Alecsandri” din Bacău; 4. 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