“Rehabilitation of Sites Contaminated with Petroleum Hydrocarbon by Using Sustainable Remediation Approach in Lower and Middle-Income Countries: Libya as a case Study”
From the Faculty of Georesources and Materials Engineering of the RWTH Aachen University
Submitted by Salahadein Ahmed Alzien-Master of Science of Civil Engineering
From „Sabha, Libya“
In respect of the academic degree of Doctor of Engineering
Approved thesis
Advisors: Univ.-Prof Dr. rer. nat. Dr. h. c. (USST) Rafig Azzam Univ.-Prof. Dr. rer. nat. Holger Weiß
Date of the Oral examination: 23.November 2018
This thesis is available in electronic format on the university library’s website
Abstract Contamination with petroleum hydrocarbon (PHC) is found in many countries and can cause widespread problems. Petrochemical contaminated land is often found on oilfields, refineries, terminal and fuel stations and other facilities. Unfortunately, PHC can easily leach into the environment resulting in many negative consequences for humans, animals and plants as well as entire ecosystems including soil and water resources. In addition, PHC-contamination might cause severe problems for national or regional economies. Therefore, several contaminated land management methods have been developed that have proven beneficial to the restoration of contaminated sites. However, not all countries have managed such progress. In many Lower and Middle-Income Countries (LMICs), such as Libya, these lands are inadequately managed, if at all. Petrochemical contaminated lands can pose significant risks to human health and the environment. In recent years the concept of sustainability has become a point of attention as a criterion for the decision-making in management processes. Sustainability pillars involve environmental, economic and social outcomes of risk-management operations. In most developed economies the principles of sustainability and risk-based decision making determine the choices made about contaminated land and how it should be developed. The principles include the protection of human health and the environment by remediation and safe work locations. The remediation decisions should be transparent for the stakeholders and based on sound science.
These frameworks optimize the use of resources, minimize harm and ensure that attention is paid to the most serious problems. However, such frameworks do not exist in Libya. Yet, the benefits of optimizing land management are even more important in countries where economic resources are limited. The implementation of a sustainability approach in remediation projects should be based on sustainability assessments in order to support the corporate decision-making.
This study aims to develop a comprehensive risk-based land management framework including screening values to identify the contamination in a sustainable manner. Therefore, comprehensive guidelines are deduced to develop and implement an effective regulatory system in a systematic process in order to improve living conditions in Libya. The study aims also to use of fuzzy logic for assessing criteria in risk prioritization and remediation options selection. Thus different approaches used to demonstrate the decision making criterion and processes.
The results showed that it is important for Libya to adopt a comprehensive contaminated land management framework which should be designed to comprise effective regulations, developed risk management procedure, soil standards system and principles of sustainable remediation. Soil screening values are influenced by climate parameters and soil properties. The fuzzy logic method can effectively rank various contaminated sites according to different priorities of classifications and in agreement with scientific criteria. The fuzzy logic approach returns significant results and is used successfully as an evaluation tool to classify different remediation options related to the sustainability criteria or other measures.
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Abstract
Eine Verschmutzung der Umwelt durch erdölbasierte Kohlenwasserstoffe tritt in vielen Ländern auf und verursacht oft weitreichende Probleme. Besonders sind Kontaminationen im Bereich von Ölfeldern, Anlagen der erdölverarbeitenden und petrochemischen Industrie aber auch Tankstellen anzutreffen. Erdölbasierte Kohlenwasserstoffe können bei ihrer Förderung und Verarbeitung sowie der Anwendung von Endprodukten leicht in die Umwelt gelangen und dort zu vielfältigen negativen Folgen für Menschen, Pflanzen, Tiere, gesamte Ökosysteme sowie Boden- und Wasserressourcen führen. Dadurch können auch z.T. erhebliche Probleme für die lokale und regionale Wirtschaft entstehen.
Im Zuge der Sanierung kontaminierter Standorte wurden verschiedene Managementansätze und –methoden entwickelt und erfolgreich eingesetzt. Allerdings waren nicht alle Länder in diesem Bereich gleich erfolgreich. In vielen Ländern mit mittleren Einkommen im geringen und mittleren Bereich (LMIC), wie z.B. Libyen werden kontaminierte Standorte wenn überhaupt, meist nur unzureichend gemanagt, trotz der negativen Effekte für die menschliche Gesundheit und die Umwelt. In den letzten Jahren wurde und wird dem Konzept der Nachhaltigkeit auch im Bereich der Sanierung kontaminierter Standorte eine immer größere Bedeutung beigemessen, hier besonders im Zuge der Entscheidungsfindung. Dieses Nachhaltigkeitsprinzip beinhaltet für kontaminierte Standorte u.a. die Beachtung der drei Säulen Ökonomie, Ökologie und Soziales im Bereich Risikoanalyse und Risikomanagement und in vielen entwickelten Ländern bestimmen Risikomanagement und Nachhaltigkeit die Entscheidungsfindung im Zuge von Sanierungs- und Entwicklungsmaßnahmen. Dazu gehören auch Schutz der Umwelt und der Gesundheit, weshalb die Bestimmung von screening values im Zuge des Risikomanagements von besonderer Bedeutung ist. Die Entscheidungsfindung im Zuge der Standortsanierung sollte transparent für alle Beteiligten sein und auf wissenschaftlich fundierten Daten beruhen. Managementansätze sollten eine optimale Verwendung der Ressourcen sicherstellen sowie negative Effekte minimisieren. Jedoch werden in Libyen im Rahmen der Sanierung kontaminierter Standorte weder Nachhaltigkeit und Risikomanagement im Zuge der Entscheidungsfindung beachtet.
Diese Arbeit hat das Ziel, für Libyen einen ganzheitlichen Ansatz und nachhaltigen Managementansatz für PHC- kontaminierte Standorte zu entwickeln. Dieser Ansatz soll Risikoanalysen und insbesondere die Definition von screening values beinhalten. Dies geschieht zum einen durch die Erstellung einer Richtlinie, die darstellt, wie ein effektives Regulierungssystem für Libyen systematisch aufgebaut und implementiert werden könnten. Zum anderen zeigt diese Arbeit auf, wie Fuzzy Logic im Bereich der Risiko-Priorisierung und zur effektiveren Auswahl von Sanierungsoptionen eingesetzt werden kann. Verschiedene Optionen werden also verwendet, um Entscheidungsfindungsprozesse aufzuzeigen.
Ergebnisse zeigen die Wichtigkeit der Einführung eines übergreifenden und umfassenden Managementsystems für PHC-kontaminierte Standorte in Libyen, welches effektive Regeln und Verordnungen, Risikomanagementprozeduren sowie allgemeingültige Standards für Boden beinhaltet und sich am Nachhaltigkeitsprinzip orientiert. Boden-screening values werden besonders durch Bodeneigenschaften und klimatische Bedingungen beeinflusst. Fuzzy-Logic kann zur effektiven Klassifizierung (ranking) verschiedener kontaminierter Standorte anhand von verschiedenen Charakteristiken verwendet werden. Fuzzy-Logic kann so erfolgreich als Evaluierungstool zur Auswahl adäquater Sanierungsoptionen verwendet werden. Nachhaltigkeit basiert auf der Verwendung von Indikatoren, um eine möglichst korrekte Entscheidungsfindung zu ermöglichen. Da Nachhaltigkeit an sich oft ein sehr vages Konzept darstellt, scheint Fuzzy-Logic geeignet zu sein, die damit einhergehenden Unsicherheiten in der Entscheidungsfindung zu berücksichtigen.
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Acknowledgements
I would like to thank everyone who contributed to the completion of this thesis. But first I must thank my God for giving me guidance and protection every day so that I managed to overcome all the difficulties I encountered. I will lay my trust in You forever.
I would like to express my special and sincere thanks to my supervisor, Professor Rafig Azzam who encouraged and directed me. It was under his direction that this thesis was conceived and his help and support brought it to its completion. I would also like to thank my supervision committee member, Professor Holger Weiß for serving as my co-supervisor even at short-time notice and in limited time. He also deserves special thanks for letting my defense be such an enjoyable moment, and for his brilliant comments and suggestions. Furthermore, my profound gratitude goes to Dr. Uwe Schneidewind and Dr. Claudia Post for thier continuous support and guidance in the years of my PhD. study and for keeping me motivated throughout the writing of this thesis. I give deep thanks to the professors and lecturers at the Institute of Engineering Geology and Hydrogeology, the librarians, and other employees of the institute.
I would especially like to thank Professor Paul Bardos from the UK, I acknowledge and appreciate his help and transparency during my research. His information helped me complete this thesis. I hope that there will be further collaborations between us in the time to come. Special thanks to all of My Brothers and my friend Dr. Wahab Ehmid who have been tremendous mentors for me. I would like to thank them for encouraging my research and for allowing me to grow as a research scientist. Their advice on both research as well as on my career have been invaluable. I am very grateful to the Ministry of Education, Libya for making it possible for me to study here. I would like to acknowledge Mr. Mohammed Samir Al Gharaeri, the Health, Safety and Environmental department manager of Mabrouk Oil Operations Company, Libya for his technical support and for always being available to give extra information about the oil industry in Libya.
And finally, very special thanks to my family; words cannot express how grateful I am to my Mother and Father for all of the sacrifices that they made on my behalf. They raised me with a love of science and supported me in all my pursuits. Their prayers have always sustained me. I must express my heartfelt gratitude to my beloved wife Mona whose faithful help , and continued support and encouragement during the writing of this Ph.D. was much appreciated. To my beloved daughter Malak and my sons Almuatasembellah, Mohammed, Almontaserbelaah and Musa, I would like to express my thanks for being such excellent children who always managed to cheer me up. I would like to thank my Brothers and Sisters for all their love and support. To all: Thank you.
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إهدإء
بدإان بأ كرث من يد وقاسينا أكرث من مه وعانينا إلكثري من إلصعوابت وهاحنن إليوم وإمحلد هلل نطوي سهر إلليايل وتعب إ لايم وخالصة مشوإران بني دفيت هذإ إلعمل إملتوإضع.
إىل إلينبوع إذلي ل ميل إلعطاء إىل من حاكت سعاديت خبيوط منسوجة من قلهبا إىل وإدليت إحلبيبة إلعزيزة.
إىل من سعى وشقى لنعم ابلرإحة وإلهناء إذلي مل يبخل بشئ من أجل دفعي يف طريق إلنجاح إذلي علمين أن أرتقي سمل إحلياة حبمكة وصرب إىل وإدلي إحلبيب إلعزيز.
إىل من رسان سو ااي وحنن نشق إلطريق مع ا حنو حياة مشرتكة مليئة ابلنجاح وإ لبدإع إىل من تاك تفنا يد اإ بيد وحنن ن سقي زه ور أ رستنا إحلبيبة زوجيت إحلبيبة.
إىل من حهبم جيري يف عرويق ويلهج بذكرإمه فؤإدي إىل أخوإيت و أخوإين الاعزإء.
إىل من علموان حروفا من ذهب ولكامت من درر وعبارإت من أمسى و أجىل عبارإت يف إلعمل إىل من صاغوإلنا علمهم حروفا ومن فكرمه منارة تنري لنا سرية إلعمل وإلنجاح إىل أساتذتنا إلكرإم
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List of Contents Abstract ...... i Acknowledgements ...... iii List of Contents ...... v List of Figures ...... ix List of Tables ...... xii List of Abbreviations ...... xiv 1 Introduction ...... 1 1.1 Problem of PHC contamination ...... 1 1.2 Thesis objectives ...... 2 1.2.1 Developing a model guideline for the management of PHC-contaminated sites in Libya, including a priority ranking approach for site selection ...... 2 1.2.2 Determining screening values (threshold values) of soil and groundwater contaminated with PHC for Libya based on a number of existing international methods taking into account the specific conditions in Libya ...... 3 1.2.3 Developing and applying a fuzzy logic approach to rank contaminated sites and to choose the remediation option most appropriate for PHC-contaminated site clean-up ...... 3 1.3 Thesis structure ...... 3 2 Petroleum hydrocarbons and contamination ...... 5 2.1 Composition of petroleum hydrocarbons ...... 5 2.2 Sources of environmental contamination ...... 5 2.2.1 Impact of exploration, drilling, and extraction ...... 5 2.2.2 Impact of oil transport ...... 6 2.2.3 Impact of oil refining...... 6 2.2.4 Impact of oil consumption ...... 6 2.3 General physical and chemical properties ...... 6 2.3.1 Physical and chemical properties of PHC ...... 7 2.3.2 Biological processes ...... 7 2.3.3 Fate, transport and attenuation processes of PHCs...... 7 2.4 Impacts of PHC on human life and the environment ...... 8 2.4.1 The Total Petroleum Hydrocarbon Criteria Working Group (TPHCWG) approach...... 8 2.4.2 Massachusetts Department of Environmental Protection (MADEP) approach ...... 9 2.5 Total petroleum hydrocarbon (TPH) ...... 9 2.6 Sampling and analytical methods to delineate PHC ...... 10 2.7 Subsurface characteristics and forms of PHC contamination ...... 10 2.7.1 Geological material properties ...... 10 2.7.2 Subsurface water properties ...... 10 2.7.3 Groundwater flow and aquifers ...... 11 2.7.4 Forms of PHC contamination ...... 11 2.8 Examples of selected important PHC ...... 11
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2.8.1 Crude oil ...... 11 2.8.2 Petroleum fuel mixture production ...... 12 2.8.3 Metals ...... 12 3 Management of PHC contaminated sites...... 12 3.1 Land use ...... 13 3.2 Risk assessment and management approaches ...... 13 3.3 Priority and ranking approach ...... 16 3.4 Risk management options and Remediation Technologies ...... 17 3.5 Natural attenuation (NA) ...... 19 3.6 Ecological assessment of petroleum hazards ...... 20 3.7 Sustainable remediation approach ...... 22 3.7.1 Managing sustainable remediation method ...... 22 3.7.2 Assessment of the sustainable remediation method ...... 23 3.8 Decision-making process in management and assessing sustainable remediation ...... 23 3.8.1 Use of Fuzzy Logic in decision making ...... 23 3.8.2 Fuzzy sets and membership: ...... 24 3.9 Uncertainty and variability associated with a risk-based management of contaminated sites ...... 24 3.10 Uncertainty in decision-making process ...... 25 4 Development of sustainable risk-based management of PHC contamination framework for “Libya” ...... 26 Proposed sustainable remediation framework for Libya ...... 26 4.1 Libya ...... 27 4.1.1 The climate of Libya ...... 27 4.1.1.1 Climatic components (temperature, precipitation, relative humidity, cloud amount) ...... 28 4.1.1.2 Characteristics of the Libyan climate ...... 28 4.1.2 The Libya’s oil and gas industry ...... 28 4.1.3 Environmental problems of the Libyan oil & gas sector ...... 28 4.1.4 Management of water resources in Libya ...... 29 4.1.5 Soil classification in Libya ...... 30 4.2 Proposed risk-based land management framework for Libya ...... 31 4.3 Stakeholder engagement method for Libya ...... 31 4.4 Management and assessment of sustainable remediation method for Libya ...... 34 4.5 International methods of contaminated sites management ...... 37 4.5.1 Management of contaminated sites in the Germany ...... 37 4.5.2 Model procedures in The United Kingdom (UK) ...... 37 4.6 Discussion & conclusion ...... 37 5 Determining Screening Values (SVs) for Libya ...... 39 5.1 Screening (threshold) approach ...... 39 5.2 Toxicity assessment (effect assessment)...... 39
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5.3 Dose-response assessment relationship ...... 40 5.4 Exposure assessment ...... 40 5.5 Selection of Screening Values (SVs) for “Libya” from international methods ...... 41 5.5.1 International soil screening levels approaches ...... 42 5.5.2 Factors affecting on SVs calculation ...... 43 5.5.2.1 The scientific parameters of SVs in the USA ...... 43 5.5.2.2 The political parameters of SVs in the USA...... 43 5.5.2.3 The geographical parameters of SVs in the USA ...... 44 5.5.3 Selecting the criteria & parameters ...... 44 5.5.4 Application & calculation & results ...... 44 5.5.5 Screening values (SVs) for Libya ...... 45 5.6 State of the art “Risk assessment, Toxicity assessment, Exposure assessment” ...... 76 5.6.1 The exposure to the human body and the environment ...... 76 5.6.2 General concepts ...... 78 5.6.3 Exposome ...... 80 5.7 Discussion & Conclusion ...... 82 6 Sustainability assessment: Al-Wahat region, Libya ...... 84 6.1 Introduction of assessment ...... 87 6.2 Site context ...... 87 6.3 Conceptual site model ...... 90 6.4 Risk assessment & remediation investigation and plan ...... 92 6.4.1 Risk assessment process ...... 92 6.4.2 Ranking of risk ...... 94 6.4.3 Screening remediation options process ...... 96 6.4.3.1 Soil medium ...... 97 6.4.3.2 Groundwater medium ...... 98 6.4.4 Screening remediation technologies options process for the Al-Wahat site by using Fizzy logic technique ...... 111 6.4.5 Detailed analysis of alternatives recommended by (USEPA, 1988a) ...... 116 6.5 Sustainable remediation approach recommended by SURF-UK ...... 121 6.5.1 General ...... 121 6.5.2 Objectives of the sustainability assessment ...... 121 6.5.3 Stakeholder engagement ...... 121 6.5.4 Scope ...... 122 6.5.5 Boundaries & Limitation ...... 122 6.5.6 Options considered ...... 123 6.5.7 Sustainability assessment process ...... 125 6.5.8 Uncertainties ...... 126 6.6 The sustainability assessment summary ...... 127
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7 Summary ...... 134 8 Outlook ...... 136 8.1 Short-term management program (1.5 to 2 years) ...... 136 8.2 Mid-term management program (2 to 3 years) ...... 136 8.3 Long-term management program (after 4 to 5 years) ...... 137 8.4 Knowledge and experience base ...... 137 8.5 Financing, investment, and funding method ...... 137 8.6 Information management system ...... 138 8.7 Sustainable development indicators ...... 138 8.8 Awareness and training of stakeholders ...... 138 8.9 Different opinions inputs “public stakeholder perspective” ...... 138 References ...... 139 Appendix A ...... 157 Appendix B ...... 177 Appendix C ...... 191 Appendix D ...... 193 Appendix E ...... 202 Appendix F...... 221
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List of Figures Figure 1-1 Structure of thesis: ...... 4 Figure 2-1 General chemical classification and structure of PHC (Sara J. McMillen et al. 2001) ...... 5 Figure 2-2 The role of fate and transport in risk assessment of contaminated sites (Ferguson et al. 1998) ...... 8 Figure 2-3 The subsurface water profile (MENZ 1999) ...... 11 Figure 3-1 The pollutant linkage (source, pathway, receptor) (E.A. Vik et al. 2001) ...... 13 Figure 3-2 Risk assessment and risk management framework of NRC 1983 (NRC 1983) ...... 14 Figure 3-3 U.S. EPA framework for human health risk assessment to inform decision making ...... 15 Figure 3-4 The collective process for implementing environmental evaluation (Suter and Cormier 2011) ...... 16 Figure 3-5 Remediation technologies for vadose zone (Krishna R. Reddy et al. 1999) ...... 18 Figure 3-6 Process of natural attenuation of contaminants dissolved in groundwater (CONCAWE 2003)...... 19 Figure 3-7 Ecological risk assessment framework (USEPA 1997a) ...... 21 Figure 3-8 The main steps of the ecological risk assessment process for contaminated sites (USEPA 1997a) ... 22 Figure 3-9 Example of linguistic values of Figure 3-10 Example of linguistic values and a basic indicator fuzzification of input variable ...... 24 Figure 3-11 General overview of a fuzzy system (Dernoncourt 2011): ...... 24 Figure 4-1 Map of Libya (GSDRC 2014) ...... 27 Figure 4-2 Types of climate in Libya (El-Tantawi 2005) ...... 28 Figure 4-3 The five water regions of Libya (Nwer 2005) ...... 30 Figure 5-1 Conceptual risk management spectrum for contaminated soil (USEPA 1996a) ...... 39 Figure 5-2 Exposure process and its results from source-receptor (WILLIAMS et al. 2010)...... 41 Figure 5-3 Method for selecting SVs for Libya from International SV approaches ...... 42 Figure 5-4 Climatic conditions in Libya (El-Tantawi 2005) ...... 45 Figure 5-5 Climatic conditions in the USA (Köppen-Geige 2006) ...... 45 Figure 5-6 Stages of exposure process ...... 76 Figure 5-7 The exposure assessment process in the comprehensive risk assessment method according to NRC 2009 (USEPA 2016) ...... 76 Figure 5-8 The exposure assessment method (USEPA 1989) ...... 77 Figure 5-9 Exposure science as the basic foundation of sustainability, risk analysis and human and environmental protection (Cohen Hubal et al. 2011) ...... 78 Figure 5-10 REACH method of hazard assessment process (NRC 2012) ...... 79 Figure 5-11 The classic environmental-health continuum (NRC 2012) ...... 79 Figure 5-12 Core elements of exposure science (NRC 2012) ...... 80 Figure 5-13 Modeling exposure at different levels from source to dose (NRC 2012) ...... 80 Figure 5-14 Three different domains of the exposome (Wild 2012b) ...... 81 Figure 5-15 The exposome would require measurement of exposures over time across the lifespan of an individual (Wild 2012b) ...... 81 Figure 5-16 Characterizing the exposome for an individual over life course from external and internal sources (Wild et al. 2013) ...... 82 Figure 6-1 Location of Al-Wahat region in Libya (Bauer et al. 2017)...... 85 Figure 6-2 Locations of the PW lagoons to the three Oasis (Jalu, Awjila, and Jakharrah) ...... 85 Figure 6-3 lagoon of PW at Al-Wahat ...... 86 Figure 6-4 lagoon of PW at Al-Wahat ...... 86 Figure 6-5 lagoon of PW at Al-Wahat ...... 86 Figure 6-6 Disposal of oil wastes at Al-Wahat ...... 87 Figure 6-7 lagoon of PW at Al-Wahat ...... 87
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Figure 6-8 Cross-sections through the post-Eocene succession of Al-Wahat region (from Awjila to Jalu): There are two aquifer systems which have maximum thicknesses in the order of 1000 m but the post-Eocene sequence is distinguished by a wide variable lithology ranging from sands and clays. (after (E. P. Wright et al. 1982)) ... 89 Figure 6-9 The main directions of groundwater flow in the Al-Wahat site (E. P. Wright et al. 1982) ...... 89 Figure 6-10 CSM of the Al-Wahat site (many oilfields surround the three oases) (KeyCSM2-Keynetix) ...... 90 Figure 6-11 CSM of the Al-Wahat site (KeyCSM2-Keynetix) ...... 90 Figure 6-12 Pollution linkage on the Al-Wahat site (source of contaminants, pathways and receptors) (KeyCSM2-Keynetix) ...... 91 Figure 6-13 Matrix samples of source of contaminants to receptors (KeyCSM2-Keynetix) ...... 91 Figure 6-14 Zoning of contamination resources and contaminated sites at the Al-Wahat region ...... 95 Figure 6-15 Input and output method for ranking contaminated sites by using fuzzy technique (MATLAB R2015a) ...... 95 Figure 6-16 Rules of fuzzy logic (MATLAB R2015a) ...... 96 Figure 6-17 Rules of fuzzy technique to find out values of Z1, Z2 and Z4 (MATLAB R2015a) ...... 96 Figure 6-18 Input & Output of assessment of effectiveness and cleanup time of In Situ Physical/Chemical Treatment: Solidification/Stabilization (In Situ Vitrification) remediation technology for treatment of contaminated soil by PHC, Inorganics and Radionuclides ...... 112 Figure 6-19 Input & Output of assessment of effectiveness and cleanup time of Ex Situ Physical/Chemical Treatment (assuming excavation): Solidification/Stabilization (Vitrification) remediation technology for treatment of contaminated soil by PHC, Inorganics and Radionuclides...... 112 Figure 6-20 Input & Output of assessment of effectiveness and cleanup time of In Situ Physical/Chemical Treatment: Electrokinetic Separation (Electrokinetics; Electromigration) remediation technology for treatment of contaminated soil by PHC and Inorganics ...... 113 Figure 6-21 Input & Output of assessment of effectiveness and cleanup time of In Situ Physical/Chemical Treatment: Solidification/Stabilization (In Situ Vitrification) remediation technology for treatment of contaminated soil by PHC and Inorganics...... 113 Figure 6-22 Input & Output of assessment of effectiveness and cleanup time of Ex-Situ Physical/Chemical Treatment (assuming excavation): Chemical Extraction (Acid Extraction) & (Solvent Extraction) remediation technology for treatment of contaminated soil by PHC and Inorganics ...... 114 Figure 6-23 Input & Output of assessment of effectiveness and cleanup time of Ex-Situ Physical/Chemical Treatment (assuming excavation): Chemical Reduction /Oxidation remediation technology for treatment of contaminated soil by PHC and Inorganics ...... 114 Figure 6-24 Input & Output of assessment of effectiveness and cleanup time of Ex-Situ Physical/Chemical Treatment (assuming excavation): Separation remediation technology for treatment of contaminated soil by PHC and Inorganics ...... 115 Figure 6-25 Input & Output of assessment of effectiveness and cleanup time of Ex-Situ Physical/Chemical Treatment (assuming excavation): Soil Washing remediation technology for treatment of contaminated soil by PHC and Inorganics ...... 115 Figure 6-26 Input and output method for evaluation remediation technologies for contaminated soil at Al-Wahat site by using fuzzy technique ...... 116 Figure 6-27 Rules of fuzzy technique to find out values of different remediation alternatives ...... 117 Figure 6-28 Input & Output of assessment of effectiveness and cleanup time of In Situ Physical/Chemical Treatment: In Wells Air Stripping remediation technology for treatment of contaminated soil by PHC and Inorganics ...... 118 Figure 6-29 Input & Output of assessment of effectiveness and cleanup time of In Situ Physical/Chemical Treatment: Passive/Reactive Treatment Walls (Permeable reactive barrier walls; In place bioreaction; In-situ chemical filters) remediation technology for treatment of contaminated groundwater by PHC and Inorganics 118 Figure 6-30 Input & Output of assessment of effectiveness and cleanup time of Ex Situ Physical/Chemical Treatment (assuming pumping): Adsorption/ Absorption (Liquid phase adsorption) remediation technology for treatment of contaminated groundwater by PHC and Inorganics...... 119
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Figure 6-31 Input & Output of assessment of effectiveness and cleanup time of Ex Situ Physical/Chemical Treatment (assuming pumping): Separation remediation technology for treatment of contaminated groundwater by PHC and Inorganics ...... 119 Figure 8-1 A proposed time period frame to apply sustainable risk-based contamination management in Libya ...... 137 Figure 0-1 Stakeholders in the contamination management process (ITRC 2015b) ...... 181 Figure 0-2 A spectrum of involvement measures for stakeholder engagement ...... 182 Figure 0-3 The key components of green remediation ...... 183 Figure 0-4 The phases of framework for Integrating Sustainability ...... 183 Figure 0-5 The management framework of sustainable remediation from SuRF-UK ...... 184 Figure 0-6 Tiered sustainable remediation assessment framework SURF-USA ...... 185 Figure 0-7 Sustainability assessment framework-SuRF-UK ...... 186 Figure 0-8 Sustainability assessment pyramid SuRF-UK ...... 186 Figure 0-9 The key steps in sustainability assessment framework-SuRF-UK ...... 186 Figure 0-10 Illustration of how indicators guide the process (IISD 1999) ...... 187 Figure 0-11 The elements of the life cycle framework for the assessment of remediation options of contaminated sites` ...... 189
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List of Tables Table 2-1 Preliminary TPHCWG toxicology (D.A. Edwards et al. 1997) ...... 9 Table 2-2 Important metals and radioactive hazardous substances found in groundwater ...... 12 Table 4-1 Some selected significant natural resources and environmental laws and legislations in Libya (Ali et al. 2011)...... 29 Table 4-2 The most important soil types in Libya ...... 30 Table 4-3 Influence and relevance of Libyan oil industry stakeholders (AHMED 2016, Ibrahim Eldanfour et al. 2014) ...... 31 Table 4-4 Proposed Libyan stakeholder categories in the oil sector according to (Norrman et al. 2016) ...... 33 Table 4-5 The Main objectives of sustainable remediation & proposed procedures and guidelines ...... 34 Table 4-6 The proposed frameworks & guidelines & roadmaps to achieve sustainable remediation aims ...... 35 Table 4-7 The overall process of sustainability approach in risk management of land contamination ...... 36 Table 4-8 The decision-making process in management of land contamination ...... 36 Table 5-1 Parameters used for calculating PEF ...... 46 Table 5-2 Parameters used for calculating VF ...... 46 Table 5-3 Parameters used for calculating carcinogens GSV ...... 47 Table 5-4 Parameters used for calculating non-carcinogens GSV ...... 47 Table 5-5 Parameters used for calculating carcinogens SSV ...... 47 Table 5-6 Parameters used for calculating non-carcinogens SSV ...... 48 Table 5-7 Parameters used for calculating VF ...... 48 Table 5-8 Parameters used for calculating SSV-leachability ...... 49
Table 5-9 Parameters used for calculating Csat ...... 49 Table 5-10 PHC properties...... 50 Table 5-11 PHCs toxicity ...... 52 Table 5-12 PHC toxicity (Florida approach) ...... 53 Table 5-13 site-specific screening values for carcinogens in groundwater ...... 54 Table 5-14 Deriving site-specific screening values for non-carcinogens in groundwater...... 55 Table 5-15 Freshwater or marine surface water cleanup target levels ...... 56 Table 5-16 Deriving site-specific screening values for non-carcinogens in groundwater...... 57 Table 5-17 Freshwater or marine surface water screening values ...... 58 Table 5-18 Particulate Emission Factor (PEF) ...... 59 Table 5-19 Volatilization Factor (VF) ...... 60 Table 5-20 Volatilization Factor (VF) ...... 60 Table 5-21 Parameters used for calculating VF:Non-carcinigens ...... 61 Table 5-22 VF values of aggregate resident ...... 62 Table 5-23 VF values of Children resident ...... 63 Table 5-24 VF values of workers ...... 64 Table 5-25 Volatilization Factor (VF) of different land use ...... 65 Table 5-26 Soil screening values for carcinogens SCTL ...... 65 Table 5-27 Soil screening values for non-carcinogens (child) ...... 66 Table 5-28 Soil screening values for non-carcinogens (child) ...... 66 Table 5-29 Soil screening values for non-carcinogens (aggregate resident) ...... 67 Table 5-30 Soil screening values for non-carcinogens (worker) ...... 69 Table 5-31 Soil screening values for non-carcinogens (child, aggregate, worker) ...... 71 Table 5-32 Comparison between calculated SSVs for Libya and SCTLs for Florida-USA ...... 72 Table 5-33 Soil screening values (SSVs) based on leachability ...... 73 Table 5-34 Parametrs used for determining soil saturation concentration (Csat.) (mg/kg) ...... 74 Table 5-35 Q/C values : VF values (Carcinogens) ...... 75
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Table 5-36 Q/C values : VF values (Non-carcinogens) ...... 75 Table 6-1 General characterization of some produced water lagoons at AlWahat region (JWC 2012) ...... 92 Table 6-2 History of the most of oil and gas fields in Libya (Hallett 2002) ...... 93 Table 6-3 Different zones with their characteristics at the Al-Wahat region ...... 94 Table 6-4 The result of ranking for the contaminated sites at Al-Wahat region by using Fuzzy logic method .... 96 Table 6-5 Screening matrix of Remediation technologies used for Soil (vadose zone), Sediment, Bedrock, and Sludge (https://frtr.gov/) ...... 100 Table 6-6 Screening matrix of Remediation technologies used for Ground Water, Surface Water, and Leachate (https://frtr.gov/) ...... 103 Table 6-7 Screening and development of remediation technologies options of Soil medium ...... 106 Table 6-8 Screening and development of remediation technologies options of Groundwater medium ...... 107 Table 6-9 Screening and development of remediation technologies options of Liquid wastes ...... 108 Table 6-10 Soil of contaminated by PHC, Inorganics and NORM (Radionuclides): ...... 109 Table 6-11 Soil contaminated by PHC and Inorganics: ...... 109 Table 6-12 Groundwater contaminated by PHC, Inorganics and NORM: ...... 110 Table 6-13 Groundwater contaminated by PHC and Inorganics:...... 110 Table 6-14 Application of 1st step (preliminary analysis) of alternatives recommended by (USEPA 1988a) .... 111 Table 6-15 1st group of In Situ Physical/Chemical Treatment Technologies: ...... 112 Table 6-16 The 2nd group of Ex Situ Physical/Chemical Treatment Technologies: ...... 114 Table 6-17 2nd step, a- Detailed analysis of alternatives recommended by (USEPA 1988a) ...... 116 Table 6-18 The result of assessment by using fuzzy technique to evaluate remediation technologies alternatives for contaminated soil at Al-Wahat region ...... 117 Table 6-19 1st step of preliminary assessment of two options ...... 117 Table 6-20 1st step of preliminary assessment of two options ...... 118 Table 6-21 1st step of preliminary assessment of two options ...... 120 Table 6-22 2nd step, a- Detailed analysis of alternatives recommended by (USEPA, 1988a) ...... 120 Table 6-23 The result of assessment by using fuzzy technique to evaluate remediation technologies aternatives for contaminated soil at Al-Wahat region ...... 120 Table 6-24 The scenarios considered within the assessment ...... 122 Table 6-25 Technology identified for treatment of bottom soils of PW lagoons at the Al-Wahat site ...... 123 Table 6-26 Technologies screened for treatment of soils of PW lagoons banks ...... 123 Table 6-27 Technologies screened for treatment of groundwater at the Al-Wahat site ...... 124 Table 6-28 Remediation options and time scenarios for contaminated soil ...... 125 Table 6-29 Remediation options and time scenarios for contaminated groundwater ...... 125 Table 6-30 The SuRF-UK indicators (Assessment criteria) and the proposed related weightings for remediation options at Al-Wahat site ...... 126 Table 6-31 Scoring summary scenario 2 (Mid-term (3-6 years)) of contaminated soil ...... 128 Table 6-32 Scoring summary scenario 3 (Long-term (6 & >10 years)) of contaminated soil...... 129 Table 6-33 Scoring summary scenario 5 (Mid-term (3-6 years)) of contaminated groundwater ...... 130 Table 6-34 Scoring summary scenario 6 (Long-term (6 & >10 years)) of contaminated groundwater ...... 131 Table 6-35 The output score for contaminated soil remediation technologies of scenario 2 ...... 132 Table 6-36 The output score for contaminated soil remediation technologies of scenario 3 ...... 132 Table 6-37 The output score for contaminated groundwater remediation technologies of scenario 2 ...... 133 Table 6-38 The output score for contaminated groundwater remediation technologies of scenario 3 ...... 133
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List of Abbreviations Abbreviation Meaning
AOP Adverse Outcome Pathways API American Petroleum Institute BMP Best Management Practice BTEX Benzene, Toluene, Ethylbenzene, and Xylenes C Carbon CBA Cost-Benefit Analysis CERCLA Comprehensive Environmental Response and Contingency Liability Act () CMDM Complex Model of Decision-Making CSM Conceptual Site Model DNAPLs Dense, Non-Aqueous-Phase Liquids EC Equivalent Carbon EGA Environment General Authority EIA Environmental Impact Assessment E&P Exploration and Production EPH Extractable Petroleum Hydrocarbon GAC Granulated Activated Carbon GC Gas Chromatography GPCIC General People’s Committee for Inspection and Control GPCPF General People’s Committee for Planning and Finance GWA General Water Authority H Hydrogen IOCs International Oil Companies IR Infrared Spectrometry LCA Life cycle assessment LCF Life Cycle Framework LCI Life Cycle Inventory LCM Life-Cycle Management LCSM LNAPL Conceptual Site Model LiPetCo Libyan Petroleum Company LMM Lower and Middle Miocene LNAPL Light Non-Aqueous Phase Liquids LPI Libya Petroleum Institute MADEP Massachusetts Department of Environmental Protection MCDA Multi-Criteria Decision Analysis MCDM Multi-Criteria Decision Making MAHs Monocyclic aromatic hydrocarbons MCLS Maximum contaminant levels MCP Massachusetts Contingency Plan MNA Monitored Natural Attenuation NA Natural attenuation NIEHS National institute of EnvironmentHealth Science NOC National Oil Corporation NORM Naturally Occurring Radioactive Material NPs Nanoparticles NRC National Research council PAHs Polycyclic Aromatic Hydrocarbons PCBs Polychlorobiphenyls PEF Particulate Emission Factor PHC Petroleum Hydrocarbon PMM Post-Middle Miocene
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PRB Permeable Reactive Barrier PRGs Preliminary Remediation Goals PT Pump-and-Treat PVI Petroleum Vapor Intrusion PW Produced Water Q/C Air dispersion factor RBLM Risk-Based Land Management RBCA Risk-Based Corrective Action REACH Registration, Evaluation, Authorisation and Restriction of Chemicals RoD Record of Decision RSLs Regional Screening Levels RfCs Reference Concentrations () RfDs Reference Doses SA Sustainability Assessment SD Sustainability Development SD S/G Values Screen/Guideline Values SI Sustainability Indicators SMDPs Scientific/Management decision Points SMPs Sustainable Management Practices SR Sustainable Remediation S/S Solidification/Stabilization SSG Soil Screening Guidance SSLs Soil Screening Levels SuRF Sustainable Remediation Forum SSVs Soil Screening Values SVs Screening Values SVOCs SemiVolatile Organic Compounds TPH Total Petroleum Hydrocarbon TPHC Total Petroleum Hydrocarbon Concentration TPHCWG Total Petroleum Hydrocarbon Criteria Working Group TVs Thresholds Values VF Volatilization Factor VOCs Volatile Organic Compounds VPH Volatile Petroleum Hydrocarbon
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1 Introduction “SITES CONTAMINATED WITH PETROLEUM HYDROCARBON” Crude oil or petroleum is a complex mix of a large number of organic compounds that where chemically transformed over time and in varying geological settings. The main components of petroleum are hydrogen and carbon but small quantities of oxygen, sulfur, trace values of nitrogen, and metals may also be contained in crude oil (Zhendi Wanga et al. 1999 ). Commonly, petroleum is located beneath the Earth’s and can only be extracted by drilling (Nadim et al. 2000). The physical and chemical properties of crude oil and its derivatives vary depending on the origin of the crude oil and on the nature of the refining operations for the derivatives (MENZ 1999). Petroleum hydrocarbon (PHC) are described as a mixture of a large number of organic compounds and include e.g. crude oil, bitumen, petroleum solvents, lubricant base oils, greases, and waxes. They are found as contaminants in or extracted from geological materials. Some of them like crude oil, gasoline, and jet fuel are continuously released into the environment in varying proportions (Environment-Canada 2008). When PHC are released at a site, their composition is affected by many factors such as the source type (e.g., crude oils, petroleum solvents), site settings (e.g., soil texture and type, climate) and the period of release. Therefore, knowledge of the multiplicity and classification of PHC types is essential for comprehensive site management (Environment-Canada 2008).
1.1 Problem of PHC contamination Contamination of soil and water resources by petroleum hydrocarbons (PHC) is a widespread environmental problem (Dominguez et al. 2012). Sites contaminated with PHC can be found in many countries. The number of estimated suspected contaminated sites is more than 2.5 million in Europe and the identified contaminated sites around 342 thousand. Municipal and industrial wastes contribute most to soil contamination (38%), followed by the industrial/commercial sector (34%).Mineral oil and heavymetals are themain contaminants contributing around 60% to soil contamination (Panagos et al. 2013, EEA 2014). These sites are often found in downstream phases of the oil industry, such as oil fields and in upstream phases such as refineries, fuel stations and other facilities (O'Rourke and Connolly 2003). Why are PHC in the environment subject of attention? a. The impact of PHC on the environment are manifold b. To a certain degree PHC constituents are toxic c. Lighter hydrocarbon are movable and have the ability to cause a problem in the ground, water or air; d. They pose a fire/explosion hazard due to their reduced nature and volatility; e. Larger and branched-chain hydrocarbon are constant in the environment; f. PHC may produce nasty odors or tastes when they occur in the environment; g. PHC sometimes degrade the soil quality by interfering with water and with nutrients. Due to their chemical characteristics, PHC can often cause adverse effects on human health; e.g. many of them are carcinogenic (ITRC 2008a), because of their serious toxicological characteristics. As such, they might also cause severe problems for the regional or national economy (Agency 2003, Cunningham 2012, Istrate et al. 2018). Additionally, PHC can negatively affect the environment by potentially threatening ecosystems (Cunningham 2012, Gogoi et al. 2003, Rayner et al. 2007). A variety of remediation technologies exist to deal with the problem of PHC in soil and groundwater. Classical remediation techniques include biological treatment, physical, and chemical technologies (Dadrasnia et al. 2013, Khan et al. 2004a). These techniques include bioventing, enhanced bioremediation, soil vapor extraction, land farming, soil washing, thermal treatment, solidification/stabilization, groundwater pumping/pump and treat, and passive/reactive treatment walls (https://frtr.gov/). Lately, approaches based on nanotechnology, which make use of nanoparticles (NPs) (Bardos et al. 2012). such Nano-Scale Zero-Valent Iron (nZVI) (Stephan Bartke and Bardos 2015) have been introduced for the remediation of PHC-contaminated sites (Rajan 2011, Bardos et al. 2015). Also, several contaminated site management approaches have been developed, all of which include some form of site investigation, risk assessment, modeling and the selection of sound remediation technologies (ITRC 2008a, Luo et al. 2009). These approaches are often founded on risk-based land management concepts (Luo et al. 2009). Comprehensive guidelines deduced from field studies that include steps for assessment, remediation, spatial
1 planning, aftercare and monitoring have, in general, proven beneficial for the restoration of contaminated sites (Luo et al. 2009), which has led to their adoption in many countries (Luo et al. 2009); However, in Libya and other developing countries such guidelines as well as adequate management systems for contaminated land do either not exist or are not properly implemented. However, the development and implementation of effective regulatory procedures in a systematic manner is essential to improve living conditions and deal with PHC contamination. In most developed economies the principles of sustainability and risk-based decision making determine the choices made regarding contaminated site remediation and brownfield redevelopment.These choices should be adequately reflected in guidelines newly developed for developing countries such as Libya, by also taking into account their distinct local geological and geographical characteristics as well as their local economic and cultural traditions. In recent years, sustainability has become an integral part of many remediation studies. The idea behind sustainable remediation is to perform contaminated site management in a sustainable manner; i.e. by applying a sustainability concept that could, for example, be based on a strategic risk-based approach (NICOLE 2010). Sustainable remediation is defined also as the wise and ideal utilization of resources during the risk management process with respect to human life, costs, ecology and the neighboring society (Dunmade 2013). Sustainability assessment and thus also sustainable remediation is based on a variety of so-called Sustainability Indicators (SI). These are grouped according to the three pillars of sustainability, i.e. environmental, economic and social indicators (CL:AIRE 2010). In general, “Indicators are observable characteristics or impacts that can be measured or valued in determining the performance of alternatives according to the criteria in question” (Beames et al. 2014). Some of these indicators are qualitative whereas others are quantitative. Quantitative SI are based on quantitative data and reflect information quantitatively (numerical manner), while qualitative SI are based on qualitative data and reflect information qualitatively (non-numerical type) (Waas et al. 2014). Experts favor quantitative indicators known as a top-down approach, whereas a bottom-up approach commonly utilizes qualitative indicators (Waas et al. 2014). When comparing the relative sustainability of remediation technologies from site to site (David E. Ellis et al. 2009), a certain degree of uncertainty can always be encountered, because there is no definite unit of remediation (David E. Ellis et al. 2009). A qualitative approach for assessing sustainability in remediation projects is preferable at the beginning of a project (David E. Ellis et al. 2009), and qualitative assessment methods are mostly based on some kind of scoring to allow a trade-off between remediation and redevelopment options (David E. Ellis et al. 2009). However, scoring is to a large degree subjective. Here, tools and methodologies are needed that to deal with this subjectivity and aid in the general decision-making process. One option could be the application of fuzzy logic techniques. The fuzzy logic approach is widely used in different areas of scientific research and has proven to be a strong tool in different fields of sustainability studies including sustainability indicator analyses , multi-criteria decision making, system dynamics, fuzzy logic, and environmental or extended cost-benefit analyses (Flour et al. 2014). Its high capacity of simulating human reasoning and of predicting unexpected outcomes is one of the main reasons why it is extensively used in many types of research. In addition, it has also been found that fuzzy logic can treat very complicated systems where mathematical representations do not make sense (Flour et al. 2014). Fuzzy methods are extremely helpful in situations that include highly complicated systems or where an approximate, but fast, solution is required. A fuzzy system can aggregate models of orders or uncertainty because it tries to realize a system for which no model exists. Thus, a fuzzy method potentially understands uncertain, vague, ambiguous, or imprecise information and can deal with the case in which information is altogether missing (Ross 2004).
1.2 Thesis objectives Based on the problem definition this thesis considers the following three main objectives:
1.2.1 Developing a model guideline for the management of PHC-contaminated sites in Libya, including a priority ranking approach for site selection This is done by comparing and analyzing existing guidelines and approaches from various countries. It is based on a sustainability approach and includes risk assessment. The issue of screening values of soil and groundwater contaminated with PHC is especially considered since it is a fundamental part of any process evaluating risks to human health and the environment
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1.2.2 Determining screening values (threshold values) of soil and groundwater contaminated with PHC for Libya based on a number of existing international methods taking into account the specific conditions in Libya Determiing screening values for the PHC-contaminated sites in Libya from international standards need also knowledge of site soil characteristics, size of the site and local climatic conditions, because such information greatly impacts factors used in derivation equations
1.2.3 Developing and applying a fuzzy logic approach to rank contaminated sites and to choose the remediation option most appropriate for PHC-contaminated site clean-up This fuzzy logic approach discusses and considers the specific contaminant types, the geological settings and is based on sustainability indicators founded on the three pillars of sustainability. Sustainability assessment and the fuzzy logic approach are applied on Al-Wahat, Libya, to study several local PHC-contaminated sites and make suggestions on how to decide on proper remediation options
1.3 Thesis structure The structure of this thesis pursues a solution-oriented approach (item 1.2). Chapter 2 provides an in-depth investigation into the problem and characterizes the major reasons for the issue (PHC). Chapter 3 demonstrates an authentic solution to the problem and discusses the management approaches to PHC-contamination. It describes also the current methods for addressing such problems by applying a sustainability development approach in the management of PHC-contaminated sites. Such a method is especially important in countries with limited economic resources. In this context, the main characteristics of Libya linked to a sustainable remediation approach are described. Chapter 4 outlines a proposal for a sustainable risk-based land management framework in Libya. Chapter 5 explains a potential method to determine soil screening values for Libya with respect to the core of the risk assessment process. Chapter 6 describes remediation tools for reducing PHC contamination. A sample of contaminated earth from Libya is taken as a case study to demonstrate how fuzzy logic is used to assess risks and sustainability remediation. Chapter 7 provides a conclusion of the thesis. Finally, Chapter 8 demonstrates outlooks for Libya to solve contamination problems and to improve and protect the human health and the environment.
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Figure 1 -1 Structure of thesis:
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2 Petroleum hydrocarbons and contamination
2.1 Composition of petroleum hydrocarbons The name “Petroleum HydroCarbon” (PHC) consists of two parts: petroleum originates from two Latin words: ‘petra’ meaning rock, and ‘elaion’ meaning oil. Hydrocarbons refer to chemical substances formed exclusively from carbon and hydrogen (UNEP 2011). PHC are composed of carbon (C) and hydrogen atoms (H) organized in different structural arrangements and simply sorted into two main groups which are known as aliphatics and aromatics Figure 2-1. The aliphatics may be further subdivided into four groups: alkanes, alkenes, alkynes, and cyclic alkanes (see Figure A-2 & A-3). As a variety of PHC product fractions results from the distillation of crude oil PHC are commonly classified on the basis of approximate carbon numbers and their boiling points. However, TPH fractions are classified based on “equivalent carbon” (EC) numbers rather than “carbon numbers.” ECs are related to the boiling point of individual compounds in a boiling point GC column (see Figure A-1), normalized to the boiling point of a normal n-alkane (WHO 2008). Thus, for compounds where only a boiling point is known, the EC can be readily calculated. The Total Petroleum Hydrocarbon Criteria Working Group (TPHCWG) decided to select the concept of EC numbers because these values are more logically related to compound mobility in the environment than carbon numbers (Sara J. McMillen et al. 2001).
PHC are interesting for many reasons, for example because of their volatility, which makes them a fire and explosion hazard and additionally may cause aesthetic and environmental problems, such as offensive odors and taste and pollute the environment. PHC are considered toxic or have a certain degree of toxicity. Their mobility induces problems at large distances from their release source (Environment-Canada 2008).
Figure 2 -1 General chemical classification and structure of PHC (Sara J. McMillen et al. 2001)
2.2 Sources of environmental contamination Oil is pivotal for the functioning of modern societies. There is no doubt that oil serves a wide range of life sectors, such as power generation, transportation, heating, and many industrial purposes. It is a multifaceted raw material for many end user products. Its advantages of easy transportation and storage are reasons for its increased use as an energy fuel (O'Rourke and Connolly 2003, UNEP 2011). Oil also has a significant and wide- ranging negative impact on human health, cultures, and the environment from oil industry operations as is outlined below.
2.2.1 Impact of exploration, drilling, and extraction Exploration, drilling and extraction are the first phase or upstream phase in the oil industry operations. The activities in this phase both on- and off-shore can have a detrimental influence on human health, ecosystems, and local life. The contaminations during these operations include the use of considerable quantities of water, which becomes contaminated with drilling muds and cuttings (drilling wastes and associated wastes) before it is
5 discharged into the environment (O'Rourke and Connolly 2003, Paul R. Epstein and Selber 2002, Chintan Pathak and Mandalia 2012). However, the main hazardous and toxic effluent which comprises the majority of the waste is known as produced water. This is brackish water produced during oil and gas production that includes quantities of toxins such as benzene, xylene, toluene, and ethylbenzene (BTEX-group). Additionally, produced water potentially contains heavy metals such as cadmium, barium, arsenic, chromium, and mercury (Chintan Pathak and Mandalia 2012) (O'Rourke and Connolly 2003, Paul R. Epstein and Selber 2002). Every stage in the production of oil on oilfields has a waste pit. During drilling, various muds, oily fluids, lubricants, and other chemicals are accumulated. These fluids and additives accumulate in large quantities during the drilling process and are often stored or finally disposed of in waste pits. These waste pits pose a danger to the local groundwater and ecosystems. In addition to operational leaks, oil spills also occur during the extraction and production of oil (O'Rourke and Connolly 2003, Paul R. Epstein and Selber 2002). Oil production activities not only disrupt sensitive environments but also threaten the survival of indigenous people that live in these ecosystems. As a result, oil exploration, drilling, and extraction lead also to a range of acute and chronic health impacts (O'Rourke and Connolly 2003, Paul R. Epstein and Selber 2002, Chintan Pathak and Mandalia 2012).
2.2.2 Impact of oil transport Oil is transported by various means, such as supertankers, barges, trucks, and pipelines. Currently oil tankers are the main means of oil transportation. However, oil is increasingly being transferred through pipelines. The amount of waste generated during transport by pipelines, railcars or trucks is unknown and unscaled. This waste includes contaminated water from storage tanks, tank bottom sludge, oil/water separator sludge, used oil, solvent degreasers, lubricants, spent antifreeze, contaminated products, clay filtration elements and unspecified products. Pipelines are highly susceptible to corrosion and are therefore also a source of spills, leaks, and fires. Oil spills also threaten human health through disease and injury during the spill, during cleanup, and through consumption of contaminated from e.g. nearby agricultural or fishing activities. Drinking water sources may also be contaminated via spills (O'Rourke and Connolly 2003, Paul R. Epstein and Selber 2002).
2.2.3 Impact of oil refining Oil must be separated, distilled, refined and converted into usable products such as gasoline, kerosene (jet fuel), heating oil, and raw material for the petrochemical industry. As a result, some crude oil constituents that are not converted into useful and usable products during the distillation process, or retained by pollution-control technologies, are emitted into the environment. Generally, refineries produce large volumes of air, water, solid, and hazardous waste containing toxic substances such as benzene, heavy metals, hydrogen sulfide, mercury, and dioxin (O'Rourke and Connolly 2003, Paul R. Epstein and Selber 2002) Refineries also utilize large amounts of water per day for production and cooling processes. Treatment of liquid effluent does usually not completely retain contaminants such as aromatic hydrocarbons that enter e.g. water routes used by humans, fish, and wildlife (O'Rourke and Connolly 2003, Paul R. Epstein and Selber 2002).
2.2.4 Impact of oil consumption The combustion of petroleum products contributes greatly to environmental issues, such as air and water pollution from gasoline and gasoline additives, as well as global warming. Gasoline is a hydrocarbon, which includes a number of carcinogenic compounds. Additionally, substances such as alkyl lead oxygenate, and additional aromatic hydrocarbons (which include benzene, xylene, and toluene) are added to gasoline to improve its performance during combustion. The acute and chronic health effects from exposure to gasoline and its additives have been recognized and include cancer, damage to the central nervous system, and intoxication. These impacts especially predominate among lower-income populations that live closer to service stations, refineries, and transport or storage facilities (O'Rourke and Connolly 2003, Paul R. Epstein and Selber 2002). Petroleum hydrocarbon facilities are potential sources of site contamination. These facilities range from refineries to retail service stations (MENZ 1999).
2.3 General physical and chemical properties Understanding the behavior of individual PHC compounds and the mixtures is very important, because the reason that the composition and properties of individual PHC substances and mixtures have direct effects during the phase state, and influence the migration behavior and receptors (MENZ 1999). There are direct links between the properties and composition of single PHC compounds. Changes in the migration behavior are directly
6 affected by them, such as variations in the phase states (volatilization, solubilisation, photochemical and microbial oxidation), the migration behavior (sorption, dispersion, dilution, etc.), and release impact on receptors (biological toxicities) (MENZ 1999, Chen 1992a) see appendix A for more detailed information.
In each hydrocarbon structural group and subgroup, there are homologous series, but every member of the series differs from adjacent members by a repeating unit such as a CH2 group. With such homologous series of PHC, variations of the physical properties of compounds follow the number of carbon atoms. The polarity of PHC structures governs the degree to which molecules interact with each other and with water. Aromatic hydrocarbons tend to be more soluble in water and less volatile than aliphatic hydrocarbons with a corresponding number of carbon atoms. In general aromatic hydrocarbons are more polar than aliphatic hydrocarbons. It is important to mention that a number of the more soluble aromatic components such as benzene, toluene, ethylbenzene, and xylene, especially the alkylbenzenes, have extremely low taste and odor thresholds in water and can render drinking water unacceptable to consumers at relatively low levels of contamination. Other PHC components can be detected by odor and/or taste in drinking-water at concentrations of a few micrograms per liter (WHO 2008).
PHC are oftentimes characterized by the number of carbon atoms in their molecules. PHC are classified as aromatic and aliphatic, depending on the arrangement of the hydrocarbon molecules. Aliphatic hydrocarbons are arranged in a straight chain and aromatic hydrocarbons are arranged in a ring with six sides. Moreover, aromatic hydrocarbons are classified according to the number of their rings. Monocyclic Aromatic Hydrocarbons (MAHs) consist of one ring. The MAH constituents of petroleum contain benzene, toluene, ethylbenzene, and xylenes (BTEX). Dicyclic hydrocarbons have two rings and polycyclic aromatic hydrocarbons (PAHs) have more than two.
2.3.1 Physical and chemical properties of PHC The main physical and chemical features of PHC that affect their transport and fate in the environment are solubilities in water, volatility and vapor pressure, density and molecular weight, viscosity, boiling point, pour point and paraffin content (MENZ 1999, Sara J. McMillen et al. 2001) (see Table A-3). The composition of crude oil differs greatly and the differences in composition are reflected in the API gravity (density) values. The pour point is the temperature point below which crude oil will not flow in a horizontal tube. The significant physical and chemical processes which will have an effect on the fate and transport of PHC (MENZ 1999) are (i) adsorption (comprising surface to surface chemical bonding with organic compounds and inorganic compounds), (ii) diffusion (due to density or concentration gradients), (iii) advection (the transport of chemical constituents by groundwater movement), (iv) dispersion, (v) chemical degradation (through abiotic transformations due to naturally occurring chemical reactions) and (vi) volatility, (which controls the movement of PHC with air or other gasses).
2.3.2 Biological processes Biological processes are significant processes which have major influence on contaminant fate and transport as well as degradation of PHC components. Microorganisms in the subsurface environment are located on the surface of the geologic material, and use carbon and energy in PHC contaminants as a source of energy for biotransformation processes. (MENZ 1999). The most important influencing factors on the type and rate of biodegradation are:
1. The composition and size of the soil microbial population 2. The presence of a suitable and bioavailable source of energy (carbon) 3. the presence of oxygen 4. The conducive soil conditions: i.e. a pH between 6 and 9, warm temperatures, and high moisture content 5. The presence of essential elements including N, P, K, Ca, Mg, S, Fe, Mn, Cu, and Zn 6. The toxicity of the compounds and the concentrations to which micro-organisms are exposed
2.3.3 Fate, transport and attenuation processes of PHCs The fate and transport of a PHC mixture is a key approach in the assessment of health risks to humans from PHC, because it recognizes the exposure pathways and, in conjunction with receptor properties, concentrations at
7 receptors. Without considering fate and transport, the health hazards could not be included in the calculation and as a result misinformed decisions regarding site clean-up, regulatory guidance, and site characterization would be made (Sara J. McMillen et al. 2001, John B. Gustafson et al. 1997) (see appendix A).
Groups of PHC that have similar transport and fate properties, such as vapor pressure and solubility are classified by the EC fractions. This is done because of the important role which transport and fate play in determining the exposure of a receptor to a site contaminant (Chen 1992b).
PHC compounds with high solubility tend to migrate to groundwater and represent a possible risk to humans and the ecological system when this groundwater is used (Appendix A explains PHC compounds). THPCWG guarantees that the method of risk assessment by selecting fate and transport criteria of the fractions will correctly identify the PHC fraction responsible for that risk in the place of exposure even if there are several exposure pathways to the receptor (Sara J. McMillen et al. 2001).
The main differences between aliphatic and aromatic PHC fractions are related to their solubility and other fate and transport properties and in the fate and transport characteristics linked to the EC numbers of the combinations (see appendix A: Fig. A-1).
By dividing PHC into these transport fractions, experts are able to model their movement through environmental media. This information helps to estimate the potential for human exposure to complex PHC mixtures figure 2-2.
Figure 2-2 The role of fate and transport in risk assessment of contaminated sites (Ferguson et al. 1998)
2.4 Impacts of PHC on human life and the environment PHC contamination is considered a critical environmental issue; PHC accumulation surely affects human health and ecosystems (ZHOU Qixing et al. 2011). PHC contaminated land varies widely in complexity, physical and chemical characteristics, and the possible risk it poses to human health and the environment (MENZ 1999).Many types of health problems may result from the exposure of humans to PHC-contaminated sites. These health issues range from simple symptoms, such as nausea to serious ailments, such as cancer. Some contact is even potentially lethal. (Istrate et al. 2018, Swartjes 2011a). For classification purposes, toxicity criteria methodologies were developed by e.g. USEPA and the TPHCWG for fractions of PHC (screening criteria) as will be shown for on several examples in the subsequent sub-chapters. In contrast to human well-being, the ecological system considers a group of potential ecological receptors or habitats that may involve various types of different vulnerabilities to chemicals contaminants such as PHC. These receptors and habitats include areas protected by a regulatory authority or habitats valued by society, or major components of the ecological system. Especially aquatic habitats such as streams, lakes, and estuaries, wetlands, and ecologically important areas that serve as feeding areas, breeding grounds, or refuge for endangered species are considered valued habitats (Chintan Pathak and Mandalia 2012, CONCAWE 2003)
2.4.1 The Total Petroleum Hydrocarbon Criteria Working Group (TPHCWG) approach The Total Petroleum Hydrocarbon Criteria Working Group approach provides a solution to sites containing large numbers of individual compounds such as petroleum hydrocarbon distillates and crude oils. There are many analytical models to describe the pathway of the chemical from the source to a receptor. However, these methods describe the transport of chemicals in the environment individually. Therefore, such an approach is convenient
8 for sites with a relatively small number of chemicals. The TPHCWG classified petroleum hydrocarbons into a relatively small number of fractions with similar physical-chemical properties, simplifying the modeling of their movement in the environment. Fraction-specific properties can then be used to estimate the partitioning of the specific fraction in the soil-water-air systems. Fate and transport models can then be applied as well (Brassington et al. 2007, D.A. Edwards et al. 1997). Accordingly, the method describes the reference doses (RfDs) and reference concentrations (RfCs) related to the EC numbers as shown in Table 2-1 (D.A. Edwards et al. 1997) (see Table: A-4,5,6,7,8,9).
Table 2-1 Preliminary TPHCWG toxicology (D.A. Edwards et al. 1997)
2.4.2 Massachusetts Department of Environmental Protection (MADEP) approach MADEP developed six carbon ranges based on differences in toxicity (Aliphatic: C5-C8, C9-C12, C9-C18, C19- C36 & Aromatic: C9-C10, C11-C22) (MADEP 2012) (see Table A-1& A-2). MADEP was the first state regulatory agency who used a petroleum fraction method for characterizing and assessing the potential risk to human health. The MADEP approach is based on a surrogate compound toxicity, risks connected to BTEX, and MTBE and carcinogenic PAHs. MADEP recommends the use of an alternative analytical technique for characterizing the Volatile Petroleum Hydrocarbon (VPH) fractions and the extractable petroleum hydrocarbon (EPH) fractions. The Massachusetts Contingency Plan (MCP) cleanup standards have been promulgated for these EPH/ VPH fractions. MADEP recommends using a compound-specific approach to assess non-cancer risks from xylene, ethylbenzene, and toluene and cancer risks from benzene and the carcinogenic PAHs (Brassington et al. 2007).
2.5 Total petroleum hydrocarbon (TPH) Analysis of Total Petroleum Hydrocarbon (TPH) is largely used as a measurement for proving the existence of PHC in soil materials. TPH is known as the commensurable magnitude of petroleum-based hydrocarbons in an environmental medium such as soil, water, and sediments. It clarifies the overall concentration of petroleum hydrocarbons in a sample. TPH is a method for detecting various compounds by dissolving them in several solvent types, then using different techniques such as infrared, gravimetric and gas chromatography to measure them (Sara J. McMillen et al. 2001, CONCAWE 2003). The American Petroleum Institute (API) introduced 1% TPH as a technical management base level for the exploration and production (E&P) management of contaminated sites. TPH with a 1% management level used by some states in the USA with regard to the protection of groundwater resources and plant life, was shown to be achievable, particularly through bioremediation (Sara J. McMillen et al. 2001). TPH is not an explicit index of the risk demonstrated by PHC contaminations with known concentrations. The risk is determined by mobility, toxicity, and exposure to human and environmental receptors. The main indicators are the relative amounts of the individual, groups or families of PHC mixture’s constituents (CONCAWE 2003). TPH characterizes a mixture of hundred chemical compounds produced originally from crude oil. Some products are light and therefore evaporate easily, and others are dense, semi-solids which are non-volatile. It is assumed that many such PHC-contaminated sites exist, because of the wide use of such products as fuel. Therefore, contaminations from PHC products include several of these hydrocarbons. The large number of hydrocarbons led
9 to the development of measurements to verify the total amount of all hydrocarbons in a specified sample of environmental media (air, soil, water). This TPH amount is helpful as a general indicator of PHC contaminations at a specific site. The measured TPH value indicates the specific PHC in the sample which might affect people or the environment. The TPH is grouped into families or groups of PHC, called PHC fractions according to their influence on the environmental media. As a result, each fraction consists of many individual compounds which are indicators (ATSDR 1999).
2.6 Sampling and analytical methods to delineate PHC The selection of an appropriate analytical method is a substantial process for quantifying the 13 transport fractions. There are three main types of PHC analytical methods: a. TPH concentration analysis b. PHC group type concentration analysis c. Individual petroleum constituent concentration analysis. TPH concentrations are a measurable value calculated by a particular method, the output of which is a single number that represents the combined concentration of all petroleum hydrocarbons in a sample. PHC group type methods separate and quantify different categories of hydrocarbons (e.g., aliphatic, aromatic, and polar/resins). This way they can identify the product. However, individual constituent methods quantify concentrations of specific compounds such as benzene, ethylbenzene, toluene, and xylenes (BTEX), and polycyclic aromatic hydrocarbons (PAHs). Resulting concentration data for individual PHC constituents can be used to provide the necessary toxicity data required for risk assessment. TPH measurement methods for determining the total amount of hydrocarbons in the environment differ greatly. These different methods often return different findings, because they are designed to analyse different subsets of PHC. TPH is defined by the method used to analyze it as already mentioned in the previous section. There are four commonly used TPH testing methods (gas chromatography (GC), infrared spectrometry (IR), gravimetric analysis, and immunoassay (MENZ 1999). Final results will also be influenced by aspects such as the collection and preservation of samples, extraction procedures in the lab as well as measurement uncertainties and detection limits. Today, sampling, collection, and conservation recommendations are provided by many international guidelines (DIN, U.S.EPA, BS). (MENZ 1999, Environment-Canada 2008)
2.7 Subsurface characteristics and forms of PHC contamination Understanding the features and interactions between the different subsurface materials and structures is required to assess the allocation of contamination and to define appropriate management options. The subsurface is a multi-material with the mobile environment and contains living organisms and human structures. The main subterranean materials are geological material and subsurface water (MENZ 1999).
2.7.1 Geological material properties Soil and bedrock materials are the geological material which can be exposed to PHC contamination by subsurface release. Soil properties are a key factor influencing the release of petroleum PHC into the subsurface environment. Soil physical and chemical properties vary in response to climates, precipitations, vegetation, microbial activities, chemical transformation, etc. The significant physical and chemical properties of soil that specify its characteristics and, therefore, influence the fate of PHC (Chen 1992b) are (i) soil classification and grain size distribution, (ii) porosity (see Table A-10 & A-11), (iii) permeability, (iv) organic matter content and (v) cation exchange capacity. Soils include unconsolidated sediments, fill and subsoil and have different particle sizes. However, rock is consolidated naturally occurring material and includes sedimentary, igneous or metamorphic rocks. The main physical characteristics of geological materials which influence the migration of liquids due to that media are effective porosity, permeability.
2.7.2 Subsurface water properties The pore spaces in the subsurface are filled with air, water and other minor liquid and gaseous components. Liquids in the subsurface exist in two forms (i.e. within pore spaces (interstitial water) and in chemical combination with rock). Figure 2-3 shows the vertical allocation of subsurface water and air with the division of the subsurface into an unsaturated zone (also vadose zone, zone of aeration, i.e. less than 100% of the pores are filled with water) extending from the ground surface to the water table as well as the saturated zone (the phreatic
10 zone) where in general the pores are full of water. The saturated zone expands from the water table down to the bedrock (MENZ 1999).
2.7.3 Groundwater flow and aquifers Groundwater is the water located in the saturated zone which is capable to flow. Aquifers are a notion of groundwater storage reservoirs that receive recharge from sources such as rainfall and discharge by pumping from wells or by gravity. Groundwater flow is in most cases the main reason for the migration of PHC contaminants in the subsurface. It depends on the characteristics of the geologic material such as porosity and hydraulic conductivity (see Table A-12), and the hydraulic gradient. Groundwater aquifers expand over broad fields and regions, and are classified by the following features: a. The permeability of geologic formations b. The effective porosity of the aquifer geologic materials c. The presence of unconsolidated or consolidated materials (MENZ 1999).
Figure 2 -3 The subsurface water profile (MENZ 1999)
2.7.4 Forms of PHC contamination After releasing PHC to the subsurface, new phases of PHC are formed, such as solid, liquid, dissolved, and vapor phases. The liquid phases occur in mobile or free, immobile residual liquids, or free products. The dissolved phase ensues in places of water infiltration, residual films of water or groundwater. The vapor phase is found in the subsurface where pore spaces are free of water in the unsaturated zone(MENZ 1999).
2.8 Examples of selected important PHC Petroleum Hydrocarbon (PHC) includes foremost hydrocarbons, heteroatom compounds and comparatively low concentrations of metallic constituents. In general PHC compounds can be classified into two main categories: hydrocarbons and nonhydrocarbons. Most PHC products are hydrocarbons which cover the majority of their components (saturated hydrocarbons: aliphatic, unsaturated hydrocarbons: aromatics), and mostly they are measured as TPH. The organic nonhydrocarbon compounds are present in crude oils in significant amounts and contain mainly sulfur, nitrogen and oxygen heteroatoms. However, organometallic compounds and inorganic salts occupy small amounts. These components of substances are mostly concentrated in the denser distillation fractions (asphalt) and residues during crude oil refinement (Weisman 1998a). See Appendix A for classification of TPH compounds.
2.8.1 Crude oil Crude oil is a liquid mixture of hydrocarbons in underground reservoirs and remains in the liquid phase under atmospheric pressure. Additionally, vapor known as condensates are attached to crude oil which are hydrocarbon mixtures in the gas phase which change to liquid in atmospheric situations under reservoir pressures and temperatures (Sara J. McMillen et al. 2001). Crude oil has various compositions and these differences are reflected in the API gravity values for crude oils, which have the following characteristics: a. Crude oil is less dense than water with a specific gravity ranging from 0.85 to 0.98 (as compared to 1.0 for water) b. Crude oil is a viscous liquid at surface temperatures and pressures
11 c. Crude oil is moderately soluble in water, with the solubility increasing with API gravity. The composition of crude oil may affect transport and fate in the environment. Therefore, it can influence risk- based decision making. Knowledge and understanding of the specific composition of PHC is required before nrisk-based decision-making at suspected PHC contaminated sites is undertaken. Therefore, it is highly recommended to specify the risk characterization on a site (Sara J. McMillen et al. 2001).
2.8.2 Petroleum fuel mixture production PHC fractions are either from the refining of crude oil or blends of refining fractions with reprocessed refinery streams. PHC products are produced to meet set specifications for refinery operations. Specifications guide the efficiency of PHC products, which are tested to ensure the appropriate physical and chemical properties for the intended usage. PHC products are used throughout our life in numerous consumer products. The wide range of commercial PHC products needs varied specifications. Important specifications are: boiling range distribution, elemental composition, viscosity, flash point, pour point, viscosity index, API gravity, specific gravity, color, ash content, and water content. There are many other factors which are part of the specifications of a particular product for a specific use or application (Weisman 1998a).
Petroleum fuel mixture is known as follow: • Gasoline: C4-C12 boiling range; • Naphthas / Solvents: C6-C12 range; • Aviation Gasoline; • Jet Fuels: C6-C14-16; • Kerosene: C6-C14-16; • Diesel Fuel: C8-C26 range; • Fuel Oils: C8-C>40; • Lubricating Oils: C20-C45+ (Potter and Simmons 1998) explains the general characterization of individual petroleum fuel mixtures.
2.8.3 Metals The concentrations of metals in crude oils are not sufficiently high to pose a significant health risk at residential sites even at an overall oil concentration in excess of 650,000 mg/kg (65 wt %). Therefore, metals are unlikely to be a major risk management consideration at crude oil spill sites, and routine analyses for metals in soils at crude oil spill sites is not recommended. However, it may be necessary to evaluate metals at those sites where multiple spills may have occurred or at land farms which have received multiple applications of oily wastes (Sara J. McMillen et al. 2001). EPA focuses on seven inorganic (involving 7 metals) and 12 radioactive hazardous substances. Table 2-2 shows these contaminants (ITRC 2010).
Table 2 -2 Important metals and radioactive hazardous substances found in groundwater
Hazardous substance description Specific metals Arsenic, Cadmium, Chromium, Copper, Lead, Nickel, Selenium Radioactive hazardous Americium, Cesium, Iodine, Neptunium, Plutonium, Radium, Radon, Strontium, Technetium, Thorium, Tritium, Uranium
3 Management of PHC contaminated sites The contamination of soil and water resources by petroleum hydrocarbon (PHC) is a widespread environmental problem (Dominguez et al. 2012). Sites contaminated with PHC can be found in many countries. As already mentioned, these sites are found at oil fields as well as refineries, fuel stations or other facilities. Site-specific information needs to be gathered regarding about the geological, environmental, economic and social aspects of a contaminated site, such as surface, subsurface, atmospheric, and biotic migration pathways, geology, hydrogeology, hydrology, meteorology, and ecology. Information on human and environmental receptors in the area surrounding the contaminated site needs to be collected. Residential, agricultural, municipal, or industrial lands and wells should be located, and surface water uses in the surrounding areas and areas downstream of the contaminated site should be identified. Regional information will help to identify background soil, water, and air
12 quality characteristics (USEPA 1988a). Demographic and land use information will help to identify potential human receptors (USEPA 1988a, Environment 2010).
3.1 Land use A key factor in a risk-based management approach is that the risk evaluation is linked to the usage or function of land. Land use is categorized into several zones or area such as children’s playgrounds, residential areas, commercial and industrial areas, recreational areas, agricultural areas or nature reserves areas. Land use classifications only provide a general view of the activities and their intensity taking place at the site. For more concrete data, land usage is additionally subdivided resulting in more detail on the various activities which happen at the site (Swartjes 2011b). Some management systems use soil and groundwater criteria, so-called “Screening Values (SVs)” to determine remediation targets. Measured concentrations of contaminants in soil and groundwater are compared to predetermined SVs related to the actual or intended land use of a site (Ferguson et al. 1998). What is the relation between risk and land use? People’s activities and behavior determine the risk they are exposed to on a site (intensity). If governments value their citizens’ wellbeing and put greater weight on the protection of human health, this policy will demand that risk assessment is carried out for a specific site (Swartjes 2011a). Identifying the receptors that might be exposed to the chemicals (PHC) at potential sites is done by characterizing the site environment. The main factor in identifying these receptors is the current and expected future land use for the site. In the past, authorities required site managers to take into consideration all possible future land uses, including residential use, in all risk analyses. An assumption especially for most exploration and production (E&P) sites is that future land uses include farm-land or park-land. In the USA authorities are currently focusing on protecting current land uses and have allowed more flexibility in the selection of appropriate future land use scenarios. Therefore, more flexibility resulted in developing regulatory criteria for site cleanup (Sara J. McMillen et al. 2001).
3.2 Risk assessment and management approaches In different countries, the risk-based approach has been adopted as the main method for the management of contaminated sites (API 2001). The assessment and management of risks are established and connected to pollutant linkage. Assessment of the risk for contaminated sites is usually based on a source-pathway-receptor concept (Thomsen et al. 2015, Latawiec et al. 2010) as shown in Figure 3-1. It shows that the pollutant linkages consist of a source of contamination, pathway, and receptor. As a result risk control is based on breaking the pollutant linkage (API 2001, E.A. Vik et al. 2001, Cundy et al. 2013). Understanding the risks connected to contaminated sites and model procedures for managing these risks have contributed to the development of contaminated site assessment and the respective management approaches. Practical approaches have become necessary, due to the dramatic increase in the number of contaminated sites. In many advanced countries the need for the integration of an appropriate site management during the spatial planning of sites is an important development. Currently, the sustainability concept is supported in many countries all over the world (Swartjes 2011b, Slenders et al. 2017).
Figure 3-1 The pollutant linkage (source, pathway, receptor) (E.A. Vik et al. 2001)
There are many approaches and concepts, such as: a. Multifunctional approach
13 b. Fitness-for-use concept: (fit-for-purpose or suitable for use), a more cost-efficient alternative for management of contaminated sites c. A more pragmatic approach: (mentality change, natural attenuation) d. Market-oriented approach to site development e. Integrated approaches: (Interdepartmental, spatial planning, (chemical, physical and biological soil quality assessment), (environmental, socio-cultural and economic assessment), life cycle assessment) f. Technical approaches: (Risk assessment methodologies, conceptual model, tiered approach, the weight of evidence, decision support systems) (Swartjes 2011b). Risk-based decision-making is the procedure of making decisions to manage environmental issues based upon an assessment of the potential risks that chemicals, such as PHC at a site may pose to human health and the ecosystem. The general framework for risk-based decision-making was originally developed by the USEPA in response hugely to the requirements of the Comprehensive Environmental Response and Contingency Liability Act of 1980 (CERCLA). This framework has been purified over time and multi- tiered approaches to risk-based decision-making have subsequently been developed. A major goal of the framework is to stipulate that management decisions for contaminated sites provide an adequate level of protection for human health and the ecosystem. Therefore, a health risk evaluation process was developed and the overall risk characterization is used to drive site management decisions (Sara J. McMillen et al. 2001). There are many contaminated site management frameworks which are based on risks. The graph in Figure 3-2 explains the framework accepted by the US national research council (Swartjes 2011a). The increase in the understanding of the risks related to contaminated sites and of methods for risk management have contributed to the development of a soil contamination approach (Swartjes 2011a). The framework recommended by NRC 2009 uses the concept of “maximizes the utility of risk assessment,” with emphasis on confirming that risk assessments are well-attuned to the problems and decisions, and can therefore describe the decision-making process. Accordingly, the 2009 NRC report recommends the development of a framework to improve the efficacy of risk assessments (USEPA 2014, Fitzpatrick et al. 2017).
Figure 3-2 Risk assessment and risk management framework of NRC 1983 (NRC 1983)
Risk-based land management (RBLM) is the setting for a combination of risk assessment and solution options. The comprehensive process of decision making within a RBLM framework should encompass the following aspects: fitness for use, environmental protection, and long-term care. These three concepts are the key components of the of RBLM conception (Bardos 2003). The Fitness-for-Use concept implies that the assessment
14 and management of the contaminated site are related to a specific type of land use (Swartjes 2011b, Bardos 2003). Environmental protection aims to prevent unfavorable effects on the surrounding environment and also to conserve qualitatively and quantitatively the resources. Long-term care monitors and controls the contamination (Bardos 2003). The RBLM conception aims to protect peoples’ health and the environment with the optimized use of novel technical solutions in a sustainable manner by integrating different approaches (Bardos et al. 2016). Figure 3-3 describes the key elements of the framework accepted by USEPA for human health risk assessment in order to inform the decision making in a way that includes a wide range of the risk assessment processes. The main elements (Fitzpatrick et al. 2017)of the framework are as follow:
• Planning, scoping, and problem formulation • Public, stakeholder, and community involvement • Exposure and effects assessment, and risk characterization • Informed decision making
Figure 3-3 U.S. EPA framework for human health risk assessment to inform decision making
Benefits of the RBDM process are: a. Each site is treated individually b. The remedial measures result in cleanup levels that are environmentally acceptable for the given site characteristics and anticipated land use for situations where there are groups of sites, the RBDM process allows resources to be focused on sites or areas that have greater environmental concerns c. The RBDM process also allows reasonable but conservative regulations to be incorporated.
Utilization of the RBDM process: a. Realizes the differences of each contaminated site b. Supports and encourages owner rather than regulatory-guided activities uses and integrates human and ecological risk-based knowledge c. Provides a focus on the fulfillment of site-specific environmental protection. Risk assessment is a process that combines science, policy, and professional rules. Risk-based decisions are sometimes met with intense and divisive criticism by industry and environmental stakeholders, as well as the public, in part because data gaps and uncertainties in the risk assessment process require the use of professional
15 rules and judgment. Thus, it is essential that the rationale for each decision in the risk assessment process is clearly stated and justified, and that the decision-making process is transparent. This will facilitate the development of supportable, reproducible risk assessments and aid regulatory agencies in addressing the challenges posed by risk-based decisions (ITRC 2005a). According to the U.S. EPA, risk assessments are implemented in order to convey risk management decisions (USEPA 2014). Throughout the process of planning and analyses, it is important to confirm that the assessment will address the information needs of the decision makers, as shown in Figure 3-4 (Suter and Cormier 2011).
Figure 3-4 The collective process for implementing environmental evaluation (Suter and Cormier 2011)
Risk assessments consist of the following steps (Ferguson et al. 1998, NAP 1983, USEPA 1989, NRC 2009): 1. Hazard identification: Defines whether a specific chemical is or is not causally connected to specific (adverse) health effects 2. Dose-response assessment: Describes qualitative or quantitative (screen/guideline values)(S/G Values) relation between the magnitude of exposure and the probability of adverse the health effects occurring (critical effects) 3. Exposure assessment: Determines the extent of human exposure, assesses the concentration, magnitude, frequency, duration, and route of a specific agent (Dennis et al. 2016) extending to the target population, 4. Risk characterization: Informs and advises decision-making on the size and magnitude of human and environmental risks, including the probability of occurrence, severity for a given population and associated uncertainties. Risk assessment is a scientific method to evaluate potentially undesirable effects. In Europe, for example, it is used to set priorities and is an indicator for qualified aims (Thomsen et al. 2015). Initially, the risk assessment of contaminated sites is based on suspicion of soil or groundwater pollution. At first sight this qualitative data may lead to a subjective evaluation of risks to the humans and ecosystem (Ferguson et al. 1998). Evaluating the importance of risks by using socially accepted standard procedures is considered a significant target of risk assessment (Defra 2011). Finally, the risk assessment process describes and communicates the dangers, thus influencing decision making. Hence the risk assessment methodology is powerful enough to keep decision making as objective and transparent as possible (Ferguson et al. 1998).
3.3 Priority and ranking approach In the EU soil plan, every country should recognize the contaminated sites in their national province and establish a national remediation strategy identify the contaminated sites. Those sites should be prioritized and ranked in a specific manner to reach the target of risk reduction. Risk assessment has a major function to set
16 priorities; the risk is used as an indicator to describe contamination of soil and groundwater, accordingly, it is used for comparative analysis as risk-based priority setting (Ferguson et al. 1998). In order to find proof of the soil and groundwater contamination, the situation of the sites suspected of being contaminated needs to be investigated. Such studies for all locations with limited sources and in short time is not feasible, but attention should be paid to some lands with high potential risks (contamination). Suspected contaminated land must be identified. A list of potential or alleged contaminated sites is available and can be used to prioritize these sites by using risk assessment methods. These methods use spatial analyses as the contamination problems are classified as inherently spatial. Every area displays specific characteristics, diverse receptors, and different habitat preferences. Chemicals are transported in the environmental media in properties with irregular concentrations Remediation plans might be restricted due to limited financial resources. Therefore, it is not possible to reduce the identified regional risks at the specified location. This explains the importance of ranking risks in term of value, in order to select those to be investigated further or to rank the possible remediation technologies (Pizzol et al. 2011). Remediation is a risk reduction process for contaminated sites. The remediation of contaminated sites is ranked differently from country to country. Some countries, rank the health hazards as top priority while the cost factor of remedial options is given lower priority. For other countries the targets of remediation are realized based on human health or ecological risks from the contaminants, but the remediation options are chosen based on engineering criteria such as the capability to meet the targets and their cost-effectiveness. Therefore, such criteria lead to the restriction of the range of deemed options (Efroymson et al. 2004).
3.4 Risk management options and Remediation Technologies Risk management or risk reduction or remediation process denotes processes for assessing the various systematic options and selecting the appropriate ones. Risk assessment is controlled by social, economic and political concerns (NAP 1983). Risk management can be summarized as a framework consisting of problem context, risk assessment, options, decisions, actions, evaluation, and risk communication (ITRC 2015a). Risk management concentrates on breaking the contact between pollutant linkage, by monitoring the contaminant source, managing the pathways, saving the receptors or a combination of these elements (Cundy et al. 2013). Risk management begins with a remedial investigation in which suitable treatment actions at the contaminated site are defined. The remedial investigations characterize the contamination at the site and obtain information needed to identify, assess, and choose cleanup options. Remediation plans or studies include assessment, analyses, and the development of remediation options and are always conducted concurrently to remediation investigations (USEPA 1989). (USEPA 1989) A significant criteria to evaluate, assess and develop a reasonable range of remediation options as follow: (i) comprehensive protection of human health and the environment on a long and short term basis, (ii) cost-effective and implementable technology which is accepted by the community. The remedial investigation and feasibility study (or options appraisal) process are a flexible stage in order to realize a high-quality outcome within the time frame and cost-effective technique. According to (USEPA 1988a, 1989), remedial investigations are performed to characterize the contamination at the site and to obtain information required to identify, assess, and select remedial action alternatives. The feasibility study also involves an analysis of alternatives based on the nine NCP evaluation criteria.
Risk management is broadly defined as the whole risk-based procedure for contaminated site management. Therefore, risk assessment is considered the main component of risk management. Risk management is appropriate when the outcome of the risk assessment is that a specific risk is unacceptable and undesirable. It contains avoiding the risks, mitigating or removing risks and communication about the risks with the parties involved (stakeholders). The keyword in risk management is risk reduction. The procedure of achieving risk reduction is explained as follows: risk management relates to the removal or control of the source of contamination (oil spill, oil storage tank, leaking pipeline); this is source control treatment (contamination of the upper soil layer), or to blocking the pathway from source to receptor (USEPA 1988a, 1989). The challenge is to find the optimum balance between the most effective and most cost-effective method by weighing the short-term advantages against the costs of rehabilitation. The most direct way of risk reduction is remediation (cleanup, restoration) which is defined by the elimination of the source and the resulting soil contamination. The objective of remediation in the current years has often been to achieve a concentration where the risks for human health, the ecosystem (soil, plant, organisms), the groundwater and/or safety of food is
17 curbed to acceptable risk levels. A simple solution for contaminated site problems is changing land use and closing the major exposure pathways (USEPA 1988a, 1989). The selected remediation technology for restoring contaminated sites is determined by many important aspects, such as site characterization, time frame, costs, and regulatory considerations. The effective remedial action also relies on appropriate design, planning, selection, and organization of the remediation technology which is related to soils, contaminants and the system implementation (Khan et al. 2004b). Remediation procedures are generally classified into two classes: a. In-situ remediation technology methods manage soil and/or groundwater on-location, so that the contaminated soil does not need to be excavated or groundwater extricated. The methods offer economic benefits, can be easily implemented at sites and raise safety to the general public and workers. The effective implementation of these methods needs the investigation of subsurface conditions (Krishna R. Reddy et al. 1999). b. Ex-situ remediation technology methods require the extraction of soil and/or groundwater. The remediation process depends on site-specific conditions. Therefore, surface remedy must be implemented on location or off-site. There are many constraints that limit the use of these methods, for example, the impact on neighboring streets and properties. As a consequence, transport of contaminated substances to urban landfill sites present a problem. Remediation processes must be managed and monitored through remediation activities. Ex- situ remediation methods do not require attention to subsurface conditions and is therefore preferable. (Krishna R. Reddy et al. 1999). Classification of remediation technologies are divided into two categories and depend on their scope of application:
1- Technologies for the vadose zone, where the vadose is the ground geological layer extending to surface above the water table level. In many cases, remediation techniques appropriate for vadose zone (figure 6-1) are not able to treat contaminated groundwater 2- Technologies for saturated zone, another technique
Figure 3 -5 Remediation technologies for vadose zone (Krishna R. Reddy et al. 1999)
Different remediation technologies are adequate for both in-situ and ex-situ remediation and are suited for the remediation of a wide range of contaminants. Ex-situ technologies offer a high standard of remedial efficiency. Examples of ex-situ are dig-and-dump (landfills and engineered landfills), pump-and-treat, adsorption, bioslurries, incineration, advanced oxidation processes, dehalogenation, ion-exchange, sorption by natural
18 materials, solid-phase bioremediation, slurry-phase bioremediation (Bioreactors), constructed wetlands and solidification /stabilization (Kuppusamy et al. 2016) Classification of remediation technologies used for contaminated soil and water relies on being distinguished by physical/chemical and biological processes. The selected and applied remediation technology relies heavily on the source (contaminant), the media (soil, water), their economic viability, the estimated time to effective results, and the required effectiveness of each method (Kim et al. 2014).
The two major types of remediation technologies are in-situ and ex-situ. In-situ remediation includes treating contaminants on-site whereas ex-situ includes physically extracting media from a contaminated site and transporting it in order to dispose at another site (landfill) for treatment. If the pollutant exists only in soil in an ex-situ site, the soil is excavated. If pollution has extended to the groundwater, it is pumped up and both the contaminated soil and water are removed. In-situ and ex-situ technologies each have specific benefits and costs. The main advantage of in-situ technologies is that contaminated soil does not need to be removed or transported. The disadvantage of in-situ technologies is that they are inoperative when contaminants are removed in contrast to ex-situ remedial options. However, the necessary excavations for ex-situ remediation technologies not only lead to higher costs but also to adverse health risks to the workers by exposing them to contaminants. Nevertheless, ex-situ treatment generally requires less time to achieve an efficient contaminant treatment, can be easily monitored and standardized. Treated soil may be used for different purposes after ex-situ treatment, for example, for landscaping purposes. (Kuppusamy et al. 2016). (See the description of the remediation technologies options in appendix E).
3.5 Natural attenuation (NA) Natural attenuation processes are chemical, physical and biological processes which occur without the interference of humans, as a result a lowering the body, capacity, toxicity, mass, load, mobility and the concentration of contaminants in groundwater or soil. These processes include chemical transformation, sorption, dispersion, diffusion, and evaporation of contaminants and biological disintegration. The monitoring process of Natural Attenuation is an important step where monitoring measures for the effectiveness of natural attenuation processes are controlled. Another important supporting and stimulating process to natural attenuation is known as enhanced natural attenuation, and done by input substances to the process (Barbara Kabardin and Frauenstein 2011, C.M. Kaoa and Prosser 2000, UBA 2009). Figure 6-2 shows the reduction in concentration with distance.
Figure 3 -6 Process of natural attenuation of contaminants dissolved in groundwater (CONCAWE 2003)
Natural attenuation of PHC takes place in soil and, in certain circumstances is considered an effective management option for residual PHC. PHC contaminants on the surfaces of soil particles, are rapidly adsorbed by the soil, but transported more slowly in groundwater. However, in groundwater, the main physio-chemical processes are adsorption, dispersion, diffusion, and volatilization. In groundwater, the reduction of PHC contaminants results from spreading and mixing through pores, and the process of adsorption, dispersion, and diffusion reduce the concentrations before reaching the specified receptor. Therefore, they contribute to the reduction of risk. (CONCAWE 2003, Mulligan and Yong 2004).
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The main natural attenuation technique is biodegradation, which is a biological or microbial process. The driving forces behind NA are naturally occurring micro-organisms, which utilize the PHC contaminants as a source of food. Natural attenuation processes are widely used as a remedial option (CONCAWE 2003). It is a contaminant remediation strategy uses to rule the transportation of the contaminant by contaminant mass reduction and plume containment (Mulligan and Yong 2004, Jong Soo Cho et al. 1997, Scow and Hicks 2005). (NRC 2000) and (Barbara A. Bekins et al. 2001) concluded the next significant comments which should be considered when implementing NA: 1. Natural attenuation is established as a remediation approach for a few exclusive types of contaminants, mostly BTEX 2. Natural attenuation should never be considered a neglect or presumptive remedy 3. To achieve remediation objectives, natural attenuation may have to continue for a long period (years or even decades) 4. Natural attenuation of some compounds can form hazardous byproducts that in some cases remain in the environment 5. Natural attenuation processes cannot destroy metals but in some cases can debilitate them 6. If natural attenuation is shown to be effective at sites, long-term monitoring will be necessary to ensure that key attenuation processes continue to control contamination 7. Natural attenuation of some compounds can form hazardous byproducts that in some cases remain in the environment 8. Eliminated contaminant sources can speed natural attenuation in some cases, but in other cases, it can interfere with natural attenuation Another term is known as Monitored Natural Attenuation (MNA) (Farhad Analoui et al.), which indicates a dependence on NA processes for treatment by the precise monitoring of addressing the stressor source in spatial and time factors (Faisal I. Khan and Husain 2001, Declercq et al. 2012). MNA can play a significant role with improved soil types and properties (composition, texture, and microbial content). Therefore, MNA can be influenced by different soil zones (Sarkar et al. 2005).
3.6 Ecological assessment of petroleum hazards Ecological risk assessment is defined in the framework of USEPA as “a process that evaluates the likelihood that adverse ecological effects are occurring or may occur as a result of exposure to one or more stressors” (USEPA 1992a). The framework defines a stressor as any physical, chemical, or biological object that can generate an adverse ecological response. Adverse responses can range from sublethal chronic impacts in individual organisms to a loss of ecosystem function (USEPA 1997a). The ecological risk assessment framework is shown in Figure 3-5. The risk assessment process is based on two main components: (i) characterization of exposure and (ii) characterization of ecological impacts. The human health risk assessment process is better defined and more forthright, while ecological risk assessments, which can include multiple receptors and contaminants, depend basically on a less specified weight-of-evidence approach. Ecological managers must explain goals into specified objectives guiding to an ecological aspect which can be quantified in the ecosystem under evaluation (Poucher et al. 2012).
The purification of the process and outputs describe how to connect management goals with assessment endpoints and measures of effects. They support a tiered approach wherein the projects conducted for each tier are designed to reduce the uncertainty identified in the previous tier (Poucher et al. 2012). The tiered approach can be explained as problem formulation. Initial work in problem formulation includes the integration of available information on sources, stressors, effects, and ecosystem and receptor characteristics. The first step in the analysis is to determine the strengths and limitations of data on exposure, effects, and ecosystem and receptor characteristics. Risk characterization includes a summary of assumptions, scientific uncertainties, and strengths and limitations of the analyses. The final output is a risk description in which the findings of the integration are presented, including an interpretation of ecological adversity and descriptions of uncertainty and lines of evidence (USEPA 1998).
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Figure 3-7 Ecological risk assessment framework (USEPA 1997a)
Figure 3-6 shows the eight steps of the ecological risk assessment guidance for a contaminated site with many Scientific/Management decision Points (SMDPs) which seeks team-work from risk assessors and risk managers. The steps are explained in the guidance as:
1st step: Screening-Level, problem formulation and ecological impact evaluations
2nd step: Screening-Level, an estimate of preliminary exposure and risk calculation, (SMDP: the decision about if a full ecological risk assessment is necessary)
3rd step: Baseline risk assessment, problem formulation, (SMDP: Agreement among the risk assessors, risk manager, and other involved parties on the conceptual model, including assessment endpoints, exposure pathways, and questions or risk hypotheses)
4th step: Study design and data quality objectives, (SMDP: Agreement among the risk assessors and risk manager on the measurement endpoints, study design, and data interpretation and analysis)
5th step: Field verification of sampling design, (SMDP: Signing approval of the work plan and sampling and analysis plan for the ecological risk assessment)
6th step: Site investigation and analysis of exposure and impacts, (SMDP: Signing the Record of Decision (RoD))
7th step: Risk characterization
8th step: Risk management, (SMDP: only if a change to the sampling and analysis plan is necessary)
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Figure 3-8 The main steps of the ecological risk assessment process for contaminated sites (USEPA 1997a)
Decision making in ecological risk assessment and management should consider risk assessment findings with social, economic, political and legal information as a basis for risk communication with stakeholders. The findings from the risk assessment process should be supported by sufficient resources and any obstacles and correctable deficiencies should be indicated so as to facilitate decision-making processes (USEPA 1998). A risk assessment process faces challenges which largely influence environmental management decisions, the risk assessments often do not connect directly or transparently to protection goals and the requirement to reduce the use of vertebrate animals in toxicity tests and – at the same time – to examine further and new chemicals (Forbes and Galic 2016).
3.7 Sustainable remediation approach In recent years there has been a growing concern about including a sustainability concept as a decision-making criterion in remediation projects. Achieving sustainability is an integral part of an effective remediation (NICOLE 2010). An example definition of ”sustainable remediation” is “the wise and ideal utilization of resources during risk management process with respect to human life, costs, ecology and near society” (Dunmade 2013). RBLM conception aims to achieve the protection of health and the environment with the optimized use of developed technical solutions in a sustainable manner by integrating different approaches (Bardos et al. 2016). The famous international frameworks (see appendix B: B.1) and the overall method of sustainable risk-based land management is included: (a) risk-based land management, (b) stakeholder engagement, and (c) risk communication (The whole method is described in (appendix B: B.2, B.5, B.6)).
3.7.1 Managing sustainable remediation method In the management of contaminated sites the remediation process is currently determined largely by time and cost factors, thus impacting the environment and how efficient the process is. Several remediation options are compared with special focus on environmental benefits, socio-economic and economic benefits (Onwubuya 2013). The Clarinet European platform believes that sustainable contaminated site management should involve the necessity for sustainable development in addition to the choice of a convenient remediation technique. U.S. EPA stipulates that green remediation factors might be involved in the assessment of the economic effectiveness of remediation projects (Witters et al. 2012a). (Selected management approaches from USA and UK are described in appendix B: B.7, B.8).
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3.7.2 Assessment of the sustainable remediation method Sustainability development is becoming a new imperative in the contamination remediation projects. A key issue is an implication for stakeholders such as regulators, responsibility owners, consultants, contractors, and technology dealers (Hou and Al-Tabbaa 2014). Sustainability assessment (SA) and sustainability indicators (SI) are tools to support decision-making for SD in various fields. There are different broad definitions of SA such as a process which directs decision making towards sustainability. Therefore, it is considered as a strategy for decision making. SA, in reality, plays a key role in the decision-making for SD. It contributes to understanding the challenges which sustainability decision-making faces represented by interpretation, information-structuring, and influence. Therefore, they are managed by generating information, activating dialogue among stakeholders, teaching societies and framing complexity (Waas et al. 2014). However there is an engineering dispute about the major difficulty between the interpretation of a problem needing to be defined by complex science to a solution that must be delivered by Newtonian science (Hou and Al-Tabbaa 2014, Fenner et al. 2006). The difficulty probably resulted from implementing the project stages in an engineering context, problem definition, solution selection, and implementing the solution among plan, construction, and operation. The project processes are shaped by the environmental-socio-economic frame. Although such a complex framework is widely adopted it is difficult to measure. Conventional and analytical methods in design, plan, and construction processes are an additional contribution to it (Fenner et al. 2006). The sustainability assessment concepts requires tools to outline the sustainability complexity either in the presently or the past (Hou and Al-Tabbaa 2014). The evaluation of selected technology by using the sustainability assessment approach to treat a contaminated site is an important step in the decision-making process and management method of remediation procedures (Rizzo et al. 2016). (Selected assessment approaches from USA and UK are described in appendix B: B.9, B.10, B.11).
3.8 Decision-making process in management and assessing sustainable remediation The decision-making for remediation projects must be aware of undesirable levels of risks to human health, and the environment. The elimination of these risks remains the main purpose of a remediation project and should not be offset against other criteria such as cost, resource usage etc. Sustainable remediation must find the optimal method to reach the appropriate risk management method which minimizes damages and maximizes wider benefits (Rizzo et al. 2016). Decision-making processes in sustainable risk-based management of contaminated sites needs to be boosted by sustainability assessment methods. Sustainability assessment is considered a sub- process of a comprehensive sustainability management process where it is required to balance all the three components (environmental, social and economic) of sustainable development. Sustainability management is a complicated process so the development of a framework to include the balancing of the three sustainability components is an important target (Bardos et al. 2011). Therefore, countries have developed various approaches to measure sustainability at remediation sites. Such approaches are life cycle assessment, cost-benefit analysis and Multi-criteria decision making as described in (appendix B: B.12, B.13, B.14).
3.8.1 Use of Fuzzy Logic in decision making Professor Zadeh’s principle of incompatibility suggests complexity and ambiguity (imprecision) are correlated: ‘‘the closer one looks at a real-world problem, the fuzzier becomes its solution’’ (Dernoncourt 2011). The fuzzy logic approach has been used in many different areas of scientific research and was found to be a strong tool in different fields of sustainability studies including sustainability indicator analyses, multi-criteria decision making, system dynamics, fuzzy logic, and environmental or extended cost-benefit analysis (Flour et al. 2014). Fuzzy logic is used to simulate human reasoning and predicting unexpected outcomes and can handle uncertainties and partial truths, which is used extensively in many types of research. It manages complicated systems where mathematical representations are not advisable (Flour et al. 2014). Fuzzy methods are helpful in the following two general situations: 1. Cases including highly complicated systems whose attitudes are not well sensed 2. Cases where an approximate, but fast, solution must be secured. A fuzzy system can aggregate models of orders or uncertainty because it tries to realize a system for which no model exists. Thus it understands uncertain information that can be in a sense of being vague, or fuzzy, or imprecise, or altogether lacking (Ross 2004).
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3.8.2 Fuzzy sets and membership: There are different elements of uncertainty. Making decisions about processes which include nonrandom uncertainty, like the uncertainty in natural language, has been displayed to be less than perfect. The idea suggested by the scientist Lotfi Zadeh suggested that set membership is the key to decision making when faced with uncertainty. In fact, Zadeh made the following statement in his seminar paper of 1965: “Fuzzy logic and fuzzy set theory have been strongly applied in ambiguity and uncertainty modeling in decision making because in such systems, uncertainties obtained in both inputs and outputs of the system which has been designed to formulate the uncertainties” (Polat et al. 2015).
Figure 3 -9 Example of linguistic values of Figure 3 -10 Example of linguistic values and a basic indicator fuzzification of input variable
The essential objective of such systems is as the name implies to assist in decision making. Fuzzy logic can be very helpful for decision making, either to discover principles or fuzzy inferences to better understand the data and thus report decisions or to perform fuzzy queries on expert knowledge.
Figure 3-11 General overview of a fuzzy system (Dernoncourt 2011):
1. the input 2. the fuzzier corresponding to the linguistic variables is called fuzzification method 3. the inference engine is determined by the choice of fuzzy operators 4. the fuzzy knowledge base is the set of fuzzy rules “IF…THEN…” 5. the defuzzier is the part where the method of defuzzification must be chosen 6. the output is the final decision. Fuzzy logic methods base their decisions on inputs in the form of linguistic variables derived from membership’s functions (Chin-Teng Lin and Lee 1991).
3.9 Uncertainty and variability associated with a risk-based management of contaminated sites Dealing with the real and complete truth is not always a practical option in the real world. A carefully applied risk analysis with all hypothesizes and clarified uncertainties (lack of knowledge), offers the best available interpretation of the existing data. There are many types of uncertainties in risk analyses. They are produced by a lack of credible data, applied models, applied hypothesizes about exposures and hazards and may consider the probability of an adverse effect from a specific hazard (Molak 1997). Different uncertainties related to risk assessment of contaminated sites have many classes. Such classes as the primary selection of chemicals used to assess exposures and risks on the basis of the sampling data and available toxicity information. Other sources of uncertainty are inherent in the toxicity values for each chemical used to characterize risks. Additional
24 uncertainties are inherent in the exposure assessment for individual chemicals and individual exposures which reflect a basic uncertainty factor (Öberg and Bergbäck 2005). These uncertainties are usually driven by uncertainty in the chemical monitoring data and the models used to evaluate exposure concentrations when lacking monitoring data, but can also be driven by population intake parameters. Finally, additional uncertainties are incorporated in the risk assessment when exposures to several chemicals over multiple pathways are summed.
Sources of uncertainty related to exposure assessment are the monitoring data, the exposure models, the used assumptions and input variables of assessment of exposure assessment and the values of the intake variables used in intake calculations. There are different classes of uncertainty linked to the calculated toxicity values, which is the reason that the toxicity information of the contaminants at contaminated sites is limited. Sources of uncertainty related to toxicity values may involve the application of dose-response information whether from effects observed at high doses to predict adverse health effects, short-term exposure studies to predict the effects of long-term exposures, and vice-versa, animal studies to predict effects in humans, and homogeneous animal populations or healthy human populations to predict the effects likely to be observed in the general population consisting of individuals with a wide range of sensitivities (USEPA 1989, Ibrahim M. Khadam and Kaluarachchi 2003).
Specifying the hypothesizes and uncertainties inherent in the risk evaluation is a significant step to set the risk estimates in appropriate perspective and to identify areas where a conservative amount of additional data might significantly improve the basis for selection of a remedial scenario. It is also significant to distinguish the main site-linked variables and hypothesizes which contribute more to the uncertainty, than to quantify the degree of uncertainty in the risk assessment. Different sources of ties must be evaluated, such as the definition of physical setting (land use, exposure pathways, chemicals of concern), the applied model and hypothesizes, fate, transport and exposure parameter values, and uncertainty assessment methods (USEPA 1989). The uncertainty assessment can provide an important basis for motivating further modifications to the project prior to setting final remediation goals. It can be used during the post-remedy assessment to identify areas requiring specific attention (USEPA 1991a).
3.10 Uncertainty in decision-making process Random quantities or ambiguous data are frequently uncertain or incomplete information included in real-world contamination in order to reduce problems (Lu, Feng, He, & Ren, 2015). Uncertainty associated with data is frequent (Balasubramaniam et al. 2007), and predictions by experts about environmental impacts are based on understanding the project study. This understanding bases on subjective judgments and scarce data about complex and uncertain processes, resulting uncertain calculations (Bojorquez-Tapia et al. 2005). The source of uncertainty stems from the judgments between experts and stakeholders in the decision criteria measurements, the ranking or the hierarchy of uncertainties, decision criteria weights, and decision criteria performances (Bojorquez-Tapia et al. 2005, Huang et al. 2016). Uncertainties in the decision making process for contamination reduction include solutions for the recognition of ecological and social systems (Armitage et al. 2009), uncertainty due to risk assessment components (Algreen et al. 2015, Igor Linkov and Burmistrov 2003), objectives of several diverse stakeholders, and must be dealt with under politically and emotionally charged conditions (Enrico Zio and Apostolakis 1999). Uncertainties in weightings and scores were dealt with by preparing a number of different weighting and score sets based on the expected views of different stakeholders (Harbottle et al. 2008). Uncertainties exist in field collected data and modeling results (I Linkov et al. 2006). A decision-making process for the management of contaminated sites must take into account social, environmental, and technological factors. Such factors involve multiple sub-criteria, which makes the process inherently multi- objective. Therefore, decisions are not well documented and not justified, which makes it difficult to assess uncertainty ranges in the resulting magnitude of risk estimates (Linkov et al. 2005)
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4 Development of sustainable risk-based management of PHC contamination framework for “Libya” The management of contaminated sites generates high costs, and requires the spending of a huge amount of money annually. Hence, solving contaminated sites problems makes achieving sustainable risk-based management (Sustainable Remediation (SR)) an important target (Bardos et al. 2016, Bardos et al. 2011). Sustainable remediation is the application of the principles of sustainable development for a remediation project, as described by the Brundtland Report, which defines the sustainable development as a “development that meets the needs of the present without compromising the ability of future generations to meet their own needs” (Singh et al. 2009, 2012, WCED 1987) to a risk-based contaminated land management (Bardos et al. 2011). The basic rule of management of contaminated sites in the past decade was based on the protection of human health and the environment against unacceptable risks, in order to assure a location fit for use again. Recently the concept of sustainability has become a criterion for the decision-making process. Sustainability interests involve environmental, economic and social outcomes of risk-management operations (Hou and Al-Tabbaa 2014, Rizzo et al. 2016, Bardos 2014). (Witters et al. 2012a, Witters et al. 2012b) mentioned that remediation activities should be implemented parallel to a sustainability development because otherwise there is no value of remediation.
Proposed sustainable remediation framework for Libya The World Bank (WB 2014) drew key conclusions and made important recommendations to improve the situation of low and middle-income countries in Latin America & the Caribbean Region with regards to developing a program for contaminated land management. The recommended plan includes two main subjects:
1. Policy and strategy: A policy which is aware of the sustainability and quality of the soil. Environmental problems arise if environmental releases in urban areas continue. No action means more severe impacts on human health, the ecosystem, and costs. A management of contaminated sites method must be established efficiently and effectively including a priority system. The environmental protection principle is the basic role. Additionally, the management method should also include a prevention, treatment, and emergency plan. Stakeholders for the management of site contamination, such as landowners, investors, environmental contractors and etc. should be involved from the start. The comprehensive management method should be accomplished with adequate public transparency. A sustainable-risk based management approach is highly recommended as a rehabilitation concept. Financial support from governments is needed to boost and fund such large rehabilitation projects. 2. Implementation: The management of contaminated sites should be completed swiftly. Therefore, the creation of a national management method is a key document for implementing to get valuable findings. The public should be involved in implementing the management method sharing remediation technology suppliers, partnering with special stakeholders (such as consultants, universities, private and public laboratories) and in particular communicating with consulting firms. Technology and know-how transfer is important to support decision-making and to support short and long-term policies.
The appropriate policy and legislative framework is a basic element of the effective and practical management of contaminated land. A framework should be developed in order to establish important common national principles, design options and environmental protection against any new contamination (WB 2014).
The proposed sustainability framework should enhance the next aims of sustainability (Bardos et al. 2011, Frederic Coulon et al. 2016) in the management of contaminated sites: a. Risk-based management of contaminated sites b. The broad effects of the management options should be accepted c. Stakeholder engagement and transparency of decision-making processes d. The pillars of sustainability (environment, social, economic) should support the decision making as a balancing criterion.
Libya needs a sustainable remediation approach to improve its preliminary actions on the management of PHC contaminated sites.
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4.1 Libya Libya, a country located in North Africa, lies approximately between 10 and 25 East and 20 and 34 North, along with the southern coast of the Mediterranean (Mohammed Al-Idrissi et al. 1996, Ben-Mahmoud 2001).
Figure 4-1 Map of Libya (GSDRC 2014)
Libya is one of the three largest countries in Africa with an area of about 1.75million Km2 and a population of about 6 million inhabitants which is considered small compared to the area. (EEA 2015). The Sahara Desert and Mediterranean coast are the main natural features of the country, which is covered by sand to 95 %. The arable land is just 4%, with the remainder involving rocky outcrops and loose surface materials (JRC 2013).
4.1.1 The climate of Libya Libya is located in the Mediterranean to the north and Niger and Chad on their southern borders. The climate in Libya is determined by the interaction between the Mediterranean Sea and the Saharan desert (Martina Zeleňáková et al. 2014a). According to the geographical location of Libya, the north is affected by a Mediterranean climate during the winter season (Martina Zeleňáková et al. 2014b, LNMC 2009). The greatest
27 part of the country is desert, in which nearly 90.8% of the area is hyper-arid, 7.4% arid, 1.5% semi-arid and 0.3% is classified as sub-humid. The topography of Libya is generally free of hilly mountains, with the exception of two regions in the north-east and north-west (Ageena 2013).
4.1.1.1 Climatic components (temperature, precipitation, relative humidity, cloud amount) The annual temperatures in Libya during winter and summer depend mainly on latitude and elevation. In southern Libya the annual temperature reaches 23.4 °C at Sabha and 23.4 °C at El-Kufra, in mid-Libya at Jalo (22.4 °C) and at Ghadames (21.9 °C), while in northern Libya temperatures range between 16.5 °C at Shahat on the Jebal El- Akhdar, 19.8 °C at Zwara in the west of the coast and 20.5 °C at Sirt and Ijdabia on the Gulf of Sirt. Rainfall is the key precipitation in Libya. The mean annual precipitation changes from 0 mm in the south of Libya to 600 mm on the coast. Relative humidity is generally low during the year due to minimizing evaporation and scarceness of water vapor. The mean annual relative humidity drops from 65-75 % in the coastal zone to less than 35 % in the desert. Cloudiness is highest in the coastal zone and decreases to the south and from the east to the west (El-Tantawi 2005).
4.1.1.2 Characteristics of the Libyan climate The climate at a certain location is created over space and time by the interaction of multiple elements in the atmosphere. The two main determining climatic components are temperature and precipitation which are therefore used to identify the characteristics of the climate in a country. With regard to these characteristics, Libya is an arid country with only traces of precipitation from the southern border to just south of Jabal Naffusah in northwestern Libya and Jabal El- Akhdar in northeastern Libya. Based on Köppen’s climatic classification, Libya is mostly dominated by a hot desert climate type (BWh) which covers a large percentage of central and southern Libya and to a lesser extent by a hot steppe climate type (BSh) in northern zones, and a Mediterranean zone (CSa) in northeastern Libya on Jebal El-Akhdar (El-Tantawi 2005). Figure 4-16 shows the climatic types in Libya.
Figure 4-2 Types of climate in Libya (El-Tantawi 2005)
4.1.2 The Libya’s oil and gas industry Libya became an oil exporting country in 1961. The Libyan government established the Libyan Petroleum Company (Lipetco) to manage the oil business, which was later replaced by the Libyan National Oil Corporation (Viscarra Rossel et al.) in 1970, Since then only the NOC has the right to control the oil industry throughout Libya so that the NOC is the ultimate stakeholder with comprehensive power over the rules and legality of the oil industry (AHMED 2016, AOORG 2012).
4.1.3 Environmental problems of the Libyan oil & gas sector Land contamination management is regulated by various laws and regulations in Libyan legislation and includes many important subjects. The laws deal with the protection of human health and the environment and the prevention of contamination. Nevertheless, there are no specific standards and guidelines for the oil & gas industry in Libya for managing Libya’s soil and environment. The overall environmental problems of the oil and
28 gas industry in Libya are summarized regarding the NOC point of view (NOC: interview) and that of the Environment General Authority (Meyer et al.):
• Insufficienct local regulations: Shortage in the oil sector and no definitions (stakeholders) • Environment General Authority (Meyer et al.): A badly organized body which needs more specialized staff and is not independent • Towards a culture of environmental protection • National Oil Corporation (Viscarra Rossel et al.): Need international experts and an environmental management procedure • Government: Must pass laws and regulations with clear, penalties when breached • Libya needs support to develop comprehensive and systematic planning in soil protection and risk management. Such an approach should include monitoring, post-remediation, and human health assessment. Table 4-1 shows some legislation in Libya for protecting the environment, natural resources including agricultural, pastures, urban development, rationing water and soil use, the protection of renewable and non- renewable natural resources etc. (see appendix C: Table C.1).
Table 4-1 Some selected significant natural resources and environmental laws and legislations in Libya (Ali et al. 2011). Law and Legislation Major features Law 26- 1972 The establishment of a public board of water responsible for proposing public policies and legislation concerning water, and follow up their implementation, as well as overseeing the follow-up projects related to water abstraction, digging wells and methods of using them (Law:26 1972). Law 46 - 1972 Protection of shrub-land (Law:46 1972) Law 827 - 1980 The establishment of the General Authority for Scientific Research and its bodies specialized in various fields (Law:827 1980). Law 5 - 1982 Protection of pastures and forests (Law:5 1982) Law 7 - 1982 Protection of the environment (Law:7 1982) Law 790 - 1982 Organization of drilling operations and the preservation of water sources (Law:790 1982) Law 1 - 1983 Agricultural inspection (Law:1 1983). Law 15 - 1984 Protection of animals, trees, prohibition of hunting wild animals, and the prohibition of tree cutting for urban expansion (Law:15 1984) Law 72 - 1988 Establishment of the Arab Center for Desert Research and development of desert communities (Law:72 1988) Law 15 - 1992 Protection of agricultural lands, pastures and forests and converting them to irrigated agricultural lands (Law:15 1992)
4.1.4 Management of water resources in Libya Groundwater is the major source of water supply for the 88 % of the water needed in Libya (El-Tantawi 2005). The important objectives of the national water resources strategy for the duration of 2000-2025 prepared in 1999 are to minimize the deficit in the water budget and prohibit impairment of water quality. Law No.3-1982 covers the definition of organization and utilization of water resources, the law regulates the possession of water, drilling, control and management, and pollution control and the penalties for any violations. The water Law No. 3-1982 and the Environmental Law No. 15-2003 stipulate general awareness to the protection of water resources and especially groundwater aquifers. Various institutions, such as The General Water Authority (GWA), The Ministry of Agriculture, The Ministry of Housing and Utilities, The Ministry of Energy, The Man-Made River Project, The General Company for Water and Wastewater, The General Company for Desalination, and The Environmental General Authority (Meyer et al.) are involved in the development and management of major water resources and projects. GWA runs five water regions of Libya, which were established by Decree 791- 1982 through branches of the Western zone, Central zone, Southern zone, Eastern zone and Kufra and Sarir. (UNEP-MAP and UNESCO-IHP 2015), as shown in Figure 4-17.
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Figure 4 -3 The five water regions of Libya (Nwer 2005)
4.1.5 Soil classification in Libya The Mediterranean coast and the Sahara Desert are the country’s major natural features. There are several highlands but no true mountain ranges except in the largely empty southern desert near the Chadian border, where the Tibesti Massif rises to over 2200 meters. Only 4 percent of the country is arable land, the rest is rocky outcrops and loose surface materials. In addition, there is a shortage of land which receives sufficient rainfall for agriculture. The highest rainfall occurs towards the north, in the Tripoli region (Jabal Nafusah and Jifarah Plain) and in the northern Benghazi region (Jabal al Akhdar). These two areas are the only regions where the average yearly rainfall exceeds the minimum (250-300 mm) considered necessary to sustain rain-fed agriculture. Arable land is just 2% of the total land area of Libya, and 4% is suitable for grazing livestock. Most of the agricultural areas are located in Al-Jabal al Akhdar in the North East and Jifarah Plains near Tripoli. The primarily dry soil in Libya is determined by the natural conditions in the various parts of the country. Almost the entire soil in the country needs a comprehensive fertilization programme for acceptable rates of yield. The main characteristics of Libyan soil are low organic matter, low nutrients and high levels of calcium carbonates (JRC 2013). Table 4-2 shows that Entisols and Aridisols are the most important soil types in Libya (H.A. Zurqani et al. 2011).
Table 4-2 The most important soil types in Libya Tripoli Fezzan Benghazi Sirt Entisols Entisols Entisols Entisols Aridisols Aridisols Aridisols Aridisols Inceptosols ------Inceptosols ------Alfisols ------Mollisols ------Vertisols ------
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4.2 Proposed risk-based land management framework for Libya The proposed method for managing PHC contamination for Libya should be based on criteria which agree with the principles of a wide range of sustainable remediation approaches (Rizzo et al. 2016): a. Risk-based land management: protection of human health and ecosystem b. Management of contaminated sites c. Improvement of the benefit of remediation solutions d. Safe working practices e. Stakeholders engagement f. Transparency of decision-making processes g. Emphasis on technical environmental issues and actions h. Implication of the three pillars or elements of sustainability i. Use of sustainability indicators (metrics) j. Balanced decision-making process k. Implication of sustainability assessment method l. Emphasis on socio-economic factors/community impacts m. Long-term vision n. Response to regulations o. Wise use of limited resources p. Record keeping q. Sound science
The core element of the management of contamination approach is the risk assessment process, while the focus is the land use. Therefore, the proposed criteria consider the driving components of risk assessment processes such as Screening Values (TVs) which will be discussed in chapter 5 and the land use scenarios where some international management frameworks have similar geographical characterization.
4.3 Stakeholder engagement method for Libya The direct deals between governments and private investors in the petroleum sector leads to significant information asymmetries between the parties. However, the private operators usually have much better knowledge of geology & hydrogeology, appropriate production schedules, technology and associated costs, and the environmental impact of the project. Such experience is gained from previous works such as exploration, drilling or other operations that were conducted (Silvana Tordo et al. 2011). (Farhad Analoui et al. 2015) made recommendation to the Libyan NOC for improving practices in the strategic management process. Board effectiveness, medium-term objectives and social responsibility are important aspects of environmental scanning. (AHMED 2016) observed that there are critical effects on robust decision making: (i) personal experience, (ii) conflict of interest and (iii) leadership, and cultural background. Therefore, recommendations are introduced as the implementation of a complex model of decision-making (CMDM). Hence the other stakeholders are considered contributors to environmental factors in the decision-making process. Stakeholders are identified by (AHMED 2016, Ibrahim Eldanfour et al. 2014), who may participate in the organizational activities of Libya’s oil and gas industry as seen in table 4-3.
Table 4-3 Influence and relevance of Libyan oil industry stakeholders (AHMED 2016, Ibrahim Eldanfour et al. 2014) Stakeholder category Output Influence and significance to the oil industry National Oil Corporation Obtain optimum returns and Oversees and runs of the entire (Viscarra Rossel et al.) overall development of the industry (industry economy Management) International Oil Companies Development of upstream Drafted the Libyan petroleum (IOCs) industry law and regulations (LPL), ensuring international best practices
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Libya Petroleum Institute (LPI) Enhance field research and studies in exploration, reservoir development exploration, oil and gas processing and a range of services in environmental monitoring General People’s Committee for Financial transparency and supervision of revenues, Inspection and Control (GPCIC) accountability expenses and recovering of misappropriated funds General People’s Committee for Monitoring, evaluation, and Financial disclosure, ensuring Planning and Finance (GPCPF) investigation of irregularities conformity/ compliance systems, risk management Local community-employee Opinion and support Opinion and support (latent impact)
Stakeholder engagement and collaboration are connected to people aware of environmental contamination problems and more concerned about resulting risks, and whose living standards is determined by environmental implications. This results is increased and improved stakeholder engagement which will make risk management decisions more effective and robust (Defra 2011). It is important to analyze stakeholder engagement in order to identify who and when to involve stakeholders in which activities. An early involvement of stakeholders in the management process is encouraged to make more effective and robust risk management decisions.
(Hermans 2005) described a method for stakeholder analyses (actor analyses) that meets the demands of an analytically valid feasibility practice. It is known as a model-based approach for actor analysis. The method is generally used as a model to analyze stakeholders and generally contains the following steps:
1. Definition of purpose, questions, and conditions for stakeholder analysis 2. Preliminary scan of stakeholder network (analysis), including the identification of stakeholders 3. Adoption of a model for stakeholder analysis 4. Data collection 5. Structure and analyses data and 6. Interpretation and presentation of results, translation into conclusions and recommendations (stakeholder management strategies)
The stakeholder analysis methods include a quick scan of the main stakeholders classified into four categories: (a) knowledge, (b) regulators, (c) business, and (d) society (Norrman et al. 2016). Identification of stakeholders should be done by NOC, EGA, and GWA. Academic staff must be consulted and involved as an important stakeholder.
According to Figure 4-1 (ITRC 2015b), the proposed stakeholders in contamination projects in the oil & gas sector in Libya are:
• National Oil Corporation (Viscarra Rossel et al.) • Oil companies • Environmental consultants • Risk assessment experts • Tribal leaders • Inhabitants • Farmers Union • Agricultural associations • Environmental General Authority (Meyer et al.) • General Water Authority (GWA) • Community leaders
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• Local councils • Investors • NGO (Environment) • Affected people
Table 4-4 Proposed Libyan stakeholder categories in the oil sector according to (Norrman et al. 2016) category Example description Comments for Libya (a) LPI, oil companies, Universities, Experts, consultants knowledge environmental consultants, risk assessors (b) Water & environmental authorities GWA, EGA, GPCPF regulators (c) Environmental contractors Investors, environmental contractors business (d) Tribal leaders, farmers union, Agricultural society People (Inhabitants) associations, Community leaders, Local councils, NGO
By using the actor analysis (stakeholder analysis) method, environmental experts are assisted in finding a multi- actor environment and to give stakeholders significance, influence, and arguments in the analysis. These methods provide knowledge about interests, relations, influence, problem perceptions, and the concerns of the stakeholders are included in the study (Hermans 2005).
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4.4 Management and assessment of sustainable remediation method for Libya Table 4-5 The Main objectives of sustainable remediation & proposed procedures and guidelines
1
Ge
-
MH
1- MP-UK/MH-GE: Model Procedures-UK or Management Handling,Germany; 2- ITRC: Interstate Technology and & Regulatory Council; 3- US EPA: United States Environment Protection Agency; 4- NICOLE: Network for Industrially Contaminated Land in Europe; 5- SURF-UK: Sustainable Remediation Forum-UK 6- ISO: International Organization for Standardization; and 7- ASTM: American Society for Testing and Materials
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Table 4 -6 The proposed frameworks & guidelines & roadmaps to achieve sustainable remediation aims The objective Procedure/Guideline Description Risk-based land MP-UK/GE Comprehensive Risk-based land management procedure: management http://www.claire.co.uk/index.php?option=com_content&view=article&id=187&catid=45&Itemid=256 MH-Ge Manual for Management and Handling of contaminated sites: http://www.umweltbundesamt.de/ ITRC Guidelines: (http://www.itrcweb.org/Guidance), ITRC issues technical documents and regulatory guidance documents that extended and deepen technical knowledge and facilitate the quality of the decision-making process. They are varied in different aspects such as risk management, remediation etc. some selected documents: - Risk assessment: (ITRC 2015b, 2008b, 2005b) - Risk management: (ITRC 2011a, 2012a) There are various ITRC documents which demonstrate Technical and Regulatory Guidance such as sampling (ITRC 2012b) US EPA Guidelines: USEPA provides regulations, standards, guidelines and other technical information about chemicals to protect human health and environment by using science (https://www.epa.gov/) Accept of wider MP-UK/MH-GE Comprehensive risk-based land management procedure impacts of risk ITRC Guidelines: (http://www.itrcweb.org/Guidance), The ITRC Remediation Risk Management documents address the management process for managing uncontrollable project activities or circumstances that may result in negative consequences to remediation system performance. Some selected guidance: - (ITRC 2011b, c) US EPA Guidelines: https://www.epa.gov/environmental-topics/chemicals-and-toxics-topics Transparency & SURF-UK Framework: http://www.claire.co.uk/projects-and-initiatives/surf-uk engagement of Principles: SURF-UK principles (Slenders et al. 2017, Bardos et al. 2011) stakeholders ITRC Guidelines: Stakeholders, definition & engagement (ITRC 2015b, 2011b, c) NICOLE Roadmap: A sustainable remediation project is one that represents the best solution when considering environmental, social and economic factors – as agreed by the stakeholders (NICOLE 2010). Balanced outcomes of SURF-UK Framework: http://www.claire.co.uk/projects-and-initiatives/surf-uk sustainability pillar Principles: SURF-UK principles (Slenders et al. 2017, Bardos et al. 2011) ISO Guidance: ISO/CD 18504, Soil Quality—Guidance on Sustainable Remediation, it is expected to be “significantly future methodology (Slenders et al. 2017). It provides a standard methodology, the key components, and assessment of sustainable remediation (ISO 2016). ASTM Standard guide: This guide is intended to provide incremental steps to incorporate sustainable elements into cleanup projects (Rizzo et al. 2016, ASTM 2013)
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The proposed sustainable risk-based land management method: a. Adopting soil pollution prevention laws and regulations international environmental experts b. Adopting a management procedure (Examples: UK or Germany) c. Adopting the roadmap for the SuR project SURF-UK or NICOLE d. Identification of stakeholders (NOC, LPI, Landowners, Risk assessors.etc.) ITRC e. Stakeholder engagement process how should it be managed DM experts f. Risk communication process how should it be managed DM experts
Table 4-7 The overall process of sustainability approach in risk management of land contamination
Table 4-8 The decision-making process in management of land contamination
The proposed method for management of contaminated sites in Libya
Steps Action Decision on further action & output Stakeholder engagement Collection of suspected sites / Identification Registration all of the suspected sites Identification S0 preliminary assessment Go to the next level Be eliminated & Classification Historical exploration / Preliminary Risk Assessment Identification of the Conceptual Site Model & pollution linkage: S1 (RA) (CSM) opinions Assessment S1 Go to the next level Be eliminated Fast Action Orientating investigation / Generic Quantitative RA Evaluation of pollutant linkages By using screening values or S2 guidelines values opinions Assessment S2 Go to the next level Be eliminated Fast Action Control Detailed investigation / Detailed Quantitative RA Evaluation the risk by using criteria & tools opinions S3 Assessment S3 Go to the next level supervision Fast Action Control
Risk prioritisation S4 Remedial investigation / options appraisal opinions Remedial decision Go to the next level supervision Control Remediation / Implementation of Remediation strategy opinions S5 Remediation monitoring supervision Be eliminated Fast Action Control
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4.5 International methods of contaminated sites management Description some selected international procedures of contaminated sites management Risk-based management of contaminated sites and systems for pollution protection are of great importance in Europe and North America. In the UK, particularly ingenious and cost-effective methods have been developed. Therefore, the UK experiences and practices in the application of risk-based management of contaminated sites should be utilized globally (Sam et al. 2016). Germany is also one of the European countries that has developed approaches, planning, and strategies for the rehabilitation of contaminated sites. Germany has a long tradition in the restoration of sites especially in the field of the rehabilitation of brownfields. Over the decades many changes have occurred in various industries influencing the different land use at different points in time. As a result, a rehabilitation approach, management policies, sustainability, and land use planning becomes a necessary action (Ana Luiza Silva Spı´nola et al. 2010).
4.5.1 Management of contaminated sites in the Germany In Germany the legal basis for soil protection is The Action Protection against Harmful Changes to Soil and on Rehabilitation of Contaminated Sites (Federal Soil Protection Act) (Bundes-Bodenschutzgesetz - BBodSchG) of 1998 and The Federal Soil Protection and Contaminated Sites Ordinance (BBodSchV) of 1999 (Frauenstein 2009, UBA 2007, Ferguson 1999). The importance of the act is to allow the beneficial use and the development of contaminated sites for sustainable utility (Ferguson 1999). Remedial soil protection includes a tiered system in which a suspicion is verified successively and with minimum potential effort and in which the decision about the circumstances of the individual matter at hand is taken if or not a need for remediation exists. (See appendix B: B.3)
4.5.2 Model procedures in The United Kingdom (UK) The model procedures in the UK follow risk-based land management approaches in a technical framework (Luo et al. 2009). The framework concentrates more on individual sites but can also be used for a portfolio of sites (EA-GOV-UK 2004a). There are two significant legal regimes relating to land contamination: Part 2A of the Environmental Protection Act (EPA) 1990 (the Part 2A regime) and the planning regime under the Town and Country Planning system. Part 2A classified the historical tradition of contaminated land by concentrating on identification and rehabilitation of such land. In this case, contamination leads to significant damage or the likelihood of significant damage to known receptors, controlled water, or to undesirable risks assessed on the current use and not on the future use (GOV.UK 2004, EA-GOV-UK 2002a). Part 2A specifically deals with the definition of “contaminated land” and “not-contaminated land”, and the planning regime, in an overarching context of sustainable development, requires development to be safe and suitable for use (EA-GOV-UK 2004a, 2002a, C. P. Nathanail et al. 2013). The act extends a completely new regime for the control of specific threats to human health or the environment from contaminated land. Local authorities are obliged to inspect their territories in order to distinguish land that may be contaminated (EEA 2000). (See appendix B: B.4)
4.6 Discussion & conclusion The proposed framework for sustainable risk-based management of contaminated sites provides guidelines for Libya to achieve sustainable remediation. Risk-based management of contaminated sites and systems for pollution protection are of great importance in Europe and North America. In the UK, particularly ingenious and cost-effective methods have been developed. Therefore, the UK experiences and practices in the application of risk-based management of contaminated sites should be utilized globally (Frederic Coulon et al. 2016, Sam et al. 2016). Libya can benefit greatly by adopting best practices as currently established in the world. This will expand the existing data and know-how, and support the timeline for effective policies and regulatory developments, and reduce the cost of these efforts (Frederic Coulon et al. 2016). A risk-based technical approach containing clear policies , integrated legislation, and professional administrators, should be designed to prioritize problem sites for rehabilitation (Luo et al. 2009). Consequently, risk prioritization steps should follow the risk characterization process. (Brombal et al. 2015) recommended for China a soil data center such as the EU soil data center (ESDAC) and the establishment of a national priority list of contaminated sites. Additionally the introduction of
37 suitable avenues should be undertaken to increase information accessibility for stakeholders, including the public. A similar policy should be initiated for Libya.
Stakeholder engagement and collaboration is enhanced when people become aware of environmental contamination problems and the resulting risks to their quality of living. This leads to more and better stakeholder engagement and will make risk management decisions more effective and robust (Defra 2011). Stakeholder analyses is a key issue of stakeholders’ engagement and determines who to involve when in different activities. The stakeholder analysis methods may include a quick scan of main stakeholders classified into four categories: (a) knowledge, (b) regulators, (c) business, and (d) society (Norrman et al. 2016). The identification of stakeholder should be done by NOC, EGA, and GWA. Academic staff must be consulted and involved as important stakeholders. Involvement of stakeholder early in the management process is encouraged to make more effective and robust risk management decisions. The Libyan government with EGA should adopt laws and regulations for the protection of soil against pollution as is done in most developed countries. An environmental management method to handle contamination should be developed. Recently, China developed a management method in collaboration with environmental experts from the UK. This could be a model for Libya. NOC and its subsidiaries should help the country through its relations with the international oil and gas companies to adopt new technologies for environmental protection and remediation. Moreover workers should be given special training in order to raise their environmental awareness. The collaboration between NOC and other international oil companies can help to introduce the sustainability approach to Libyan management systems. It is essential to familiarize the management level in the NOC and its subsidiaries with the sustainability principles, such as transparency and stakeholder engagement. Some African countries, such as South Africa and Nigeria could aid the Libyan government, EGA, and NOC, because these countries have conducted extensive studies and projects in mining and oil industries. The sustainable remediation approach is not so difficult to implement correctly as long as the right awareness, training, tools, and expert collaboration are on hand. Over the years, Libya has experienced a lot of land contamination that poses a risk to human health and the environment. The rehabilitation and management of these contaminated sites involves high costs, time delays, and multidisciplinary, complex and uncertain processes. Therefore, a management approach for the remediation of land contamination needs to be adopted. Over the past years, a lot of approaches, methods, process, and tools for the rehabilitation of petrochemicals contamination have been developed in many countries. A sustainable remediation approach is highly recommended, as an up-to-date method for Libya. The important key steps for Libya to adopt a more coherent and effective contaminated land management framework should be designed to comprise: 1. Establishing effective regulatory framework for soil pollution prevention and control 2. Strengthening capacities of environmental administrations and developing an integrated risk management system 3. Improving the soil environmental standards system 4. Developing and demonstrating integrated remedial approaches 5. Promoting public participation and joint stakeholders action 6. Developing effective funding sources for soil remediation 7. Understanding the sustainable remediation approach in order to implement it.
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5 Determining Screening Values (SVs) for Libya Screening Values (SVs) or Soil Screening Levels (SSLs) are generic quality standards accepted in many countries to adjust the management of contaminated land. They are commonly concentration thresholds (mg/kg.soil-dry weight) of contaminants in soil above which certain actions are strongly recommended and completed. National regulatory frameworks determine whether to include the exceeding of soil SVs. They extend from the need for further investigations to the need for remedial actions. Along with their different functions in the national regulatory framework (Carlon 2007), screening values are utilized as generic quality standards to evaluate contaminated sites. The application of SVs varies from adjusting long-term quality objectives, through making further investigations, to applying remedial actions. Derivation methods of SVs have scientific and political rules. They also differ from country to country, and SVs numerical values change consequently (Sara J. McMillen et al. 2001). Screening values of a site are potentially very helpful where it is problematic to determine whether land contamination exceeds a limit which warrants further investigation or reaction (USEPA 1996a). Screening values identify the lower threshold below which there are no affects, provided terms connected with the SVs are met (USEPA 2002).
5.1 Screening (threshold) approach Screening values have been developed in the USA by assuming future residential land use assumptions and related exposure scenarios (USEPA 1996a). The Soil Screening Guidance (SSG) enhances the introduction of a framework for screening contaminated soils. These guidelines cover both easy and more detailed approaches for calculating site-specific SSLs, and generic SSLs where site-specific data is limited. The Soil Screening Guidance: User's Guide (U.S. EPA, 1996) focuses on the application of the simple site-specific approach by providing a step-by-step methodology for calculating site-specific SSLs and planning the sampling necessary to apply them exclusively for future residential use (USEPA 1996a, 2002). A series of contaminant concentrations are considered by EPA. The importance of such concentrations is connected to the likelihood of exposure to levels of contaminated soil that has the potential to harm human health or the ecological system. Figure 5-1 shows the scope of the risk management concept at a contaminated land with a spectrum of soil contamination concentrations. At one end there are levels below the attention of regulators; at the other end, are levels of very high contamination concentrations that obviously justify remedial reaction (USEPA 1996a, b). Such SVs are used for applying generic SVs, in order to develop easy site-specific SVs and to develop site-specific SSLs based on more detailed modeling (USEPA 2002, 1996c). The potential pathways of exposure to pollutants in the soil are direct ingestion, inhalation of volatiles and fugitive dust, ingestion of contaminated groundwater caused by migration of chemicals through the soil to an underlying potable aquifer, dermal absorption, and ingestion of homegrown produce that has been contaminated via plant uptake and migration of volatiles into basements. SSG treats the human exposure pathways and also deals with the assessment of ecology systems (USEPA 1996b).
Figure 5 -1 Conceptual risk management spectrum for contaminated soil (USEPA 1996a)
5.2 Toxicity assessment (effect assessment) Toxicity assessment or effects assessment for contaminants are established at contaminated sites. It generally encompasses two stages: hazard identification and dose-response assessment. Effects assessment is a process to characterize the effects (USEPA 2014, Fitzpatrick et al. 2017), to weigh available evidence regarding the potential for specific contaminants to cause adverse effects in exposed individuals, and to provide, where possible, an evaluation of the relationship between the extent of exposure to a contaminant and the increased likelihood and/or severity of adverse effects (USEPA 1989). In the hazard identification stage, the type, the nature and the strength of the evidence of causation are characterized, while in the second stage quantitative
39 dose-response relationship, toxicity values such as reference doses (RfD, RfC) and slope factors are derived in order to estimate the incidence or potential for adverse effects as a function of human exposure to the agent (USEPA 1989).
The steps are defined in the toxicity assessment (Effect assessment) as follow:
1. Gather toxicity information: qualitative and quantitative for substances being evaluated 2. Identify exposure periods for which toxicity values are necessary 3. Determine toxicity values for non-carcinogenic effects 4. Determine toxicity values for carcinogenic effects, and 5. Summarize toxicity information
There are different methods for determining the potential for a substance to cause adverse health effects (carcinogenic and non-carcinogenic) in humans. They may contain controlled epidemiologic investigations, experimental animal studies, and clinical studies. Additional information is also supplied by studies acquired from sources such as in vivo or in vitro laboratory animal studies (USEPA 2014), or mechanistic or kinetic studies in a variety of test systems and comparisons of structure-activity relationships (USEPA 1989). New studies were conducted to examine additional types of data during hazard identification, for example, those from computational toxicology (quantitative structure-activity relationships, high-throughput assays) and genomic response assays (USEPA 2014).
5.3 Dose-response assessment relationship Dose-response assessment is defined according to the (NRC 1983) as the determination of the relation between the magnitude of exposure and the probability of occurrence of adverse health effects. Dose-response assessment is the second step of the toxicity assessment in the risk assessment process. The first step is the hazard identification, whereas the dose-response assessment is the method of quantitatively estimating the toxicity information and characterizing the relationship between the dose of the contaminant drawn and the incidence of adverse health impacts in the exposed population (JR 2001). In the dose-response relationship, toxicity values are quantitatively derived to estimate the incidence of adverse effects ensuing in humans at different exposure levels (USEPA 1989). A dose-response evaluation should depict and justify the processes of extrapolation used to predict incidence and should describe the statistical and biologic uncertainties in these processes (NRC 1983).
5.4 Exposure assessment Exposure assessment is described as the evaluation of the type and magnitude of exposures to the hazardous materials present at or transported from a site (USEPA 1989). “Human exposure means contact with the chemical or agent”, but it is not specified whether such contact means contact with exterior or interior boundaries of the body (USEPA 1992b). (USEPA 1992b) guidelines state that exposure to the chemical is the contact of this chemical with the outer boundary. The exposure assessment process encompasses a stressor zone (source, fate/transport, concentration in the environmental media, the point of exposure) and a receptor zone (point of exposure, target dose, biological event, effect), as shown in Figure 5-2 (WILLIAMS et al. 2010). An exposure assessment evaluates contact in a quantitative and qualitative manner , and in addition encompasses the studies of disease occurrence, disease causes, and occupational exposure (USEPA 1992b). An exposure assessment evaluates the amount of actual/potential human exposure, the frequency, duration of these exposures, and the pathways where a human could be exposed to hazards with current and future exposures (Ferguson et al. 1998, USEPA 1989). The exposure assessment process is depicted by (USEPA 1989, 1988b) in the next sections:
1- analysis of contaminant releases from a source into environmental media 2- assessment of the fate and transport of the contaminants released into the environment 3- identification, listing, and characterization of potentially exposed populations 4- integrated exposure analyses , and 5- uncertainty analyses . The further steps of exposure assessment are (USEPA 1989, 1988b):
1- Characterization of exposure setting:
40 a. physical environment: climate, meteorology, geology, hydrogeology, hydrology, vegetation, soil, and location b. potentially exposed populations: location of current populations, current and future land use, subpopulations of potential concerns 2- Identification of exposure pathways: a. chemical source: sources and receiving media b. fate & transport in release media: transportation, transformation, accumulation c. exposure point & route: to potentially exposed populations, greatest concentrations d. integration information on sources, releases, fate and transport, exposure points, and exposure routes into exposure pathways e. summary of information on all complete exposure pathways 3- Quantification of exposure: a. exposure concentrations: evaluation of exposure concentrations in groundwater, soil, air, surface water, sediment, food, Summary of exposure concentration for each pathway b. exposure evaluation of chemical intake: calculation of exposure intake from groundwater and surface water, soil sediment or dust, air, food 4- integration of chemical intakes across pathways 5- evaluation of uncertainty 6- presentation of the summary and the exposure assessment results
Figure 5 -2 Exposure process and its results from source-receptor (WILLIAMS et al. 2010)
Exposure assessment of human health is a stringent step of the risk assessment process. The analysis is applied throughout source and dose effects. It is a process which has a sequence of related steps, in which contaminants are released from sources into the environment, and contaminants move through manifold environmental media and to human receptors via multiple pathways. Exposure may result in a dose of chemicals entering the body through multiple portals of entry, mostly inhalation, ingestion, and dermal absorption (JR 2001). Exposure assessment or dose assessment is an important step, in which the findings should be compared to the dose- response results and delivered to the risk characterization step. The important role of risk characterization is gathering and linking the results from the exposure assessment to the information from the dose-response assessment. This combination and interpretation will offer a meaningful characterization of the expected health risks to humans that may be caused by agents or other chemicals in the environment (JR 2001).
5.5 Selection of Screening Values (SVs) for “Libya” from international methods To select an appropriate method for adopting Screening Values (SVs) for Libya, the method, as shown in Figure 5-3 is proposed. Soil Screening Values (SSVs) are used in different ways either for determining the necessity for remediation or the need for further soil investigation (Provoost et al. 2006). Many countries have adopted generic
41 quality standards, also known as soil screening values (SSV), to regulate the management of contaminated land. SVs are concentration thresholds above which certain actions are recommended or enforced.
Selection of SVs for Libya
International SVs approaches
Factors affecting on SVs calculation
Selection the criteria & parameters
application
SVs for Libya
Figure 5 -3 Method for selecting SVs for Libya from International SV approaches
The type of actions extends, according to national regulatory frameworks, from further site investigation to site remediation (Ferguson et al. 1998, (Provoost et al. 2008). Within the national regulatory frameworks, SVs are denoted as trigger, reference, intervention, clean-up or cut-off values (Provoost et al. 2008).
The various SSVs of countries are developed from several different derivation methods for SSVs and include scientific, political, and geographical parameter values. The eligible authorities of different countries have created different options for these values. (Provoost et al. 2008). Scientific parameters are described as the model algorithm and its model parameter values. The human health risk-based SSVs are further analyzed for the predominant exposure route ‘inhalation of indoor air/outdoor’. Political parameters are clarified as the selection of toxicological reference values or the differentiation of SSVs in different land use types (e.g. residential or industrial area). Hence, toxicological reference values are the carcinogenetic considerations, receptor at risk, and lifetime excess cancer risk. Geographical parameters are values for building properties and soil properties (Provoost et al. 2008).
5.5.1 International soil screening levels approaches Soil screening values (SSVs) are used in different ways either for determining the necessity for remediation or the need for further soil investigation (Provoost et al. 2006). Many countries have adopted generic quality standards, also known as soil screening values (SSV), to regulate the management of contaminated land. SVs are concentration thresholds above which certain actions are recommended or enforced. The type of actions extends, according to national regulatory frameworks, from further site investigation to site remediation (Ferguson et al. 1998(Provoost et al. 2008). Within the national regulatory frameworks, SVs are denoted as trigger, reference, intervention, clean-up or cut-off values (Provoost et al. 2008). The various SSVs of countries are developed from several different derivation methods for SSVs and include scientific, political, and geographical parameter values. The eligible authorities of different countries have
42 created different options for these values. (Provoost et al. 2008). Scientific parameters are described as the model algorithm and its model parameter values. The human health risk-based SSVs are further analyzed for the predominant exposure route ‘inhalation of indoor air/outdoor’. Political parameters are clarified as the selection of toxicological reference values or the differentiation of SSVs in different land use types (e.g. residential or industrial area). Hence, toxicological reference values are the carcinogenetic considerations, receptor at risk, and lifetime excess cancer risk. Geographical parameters are values for building properties and soil properties (Provoost et al. 2008).
The soil screening levels in the USA are used to distinguish sites, chemicals and pathways at sites which need more monitoring. The tiered framework for developing risk-based, site-specific soil screening levels (SSLs) contains a group of conservative, generic SSLs, a simple site-specific approach for calculating SSLs, and a detailed site-specific modeling approach for more comprehensive monitoring of site conditions in establishing SSLs. The framework emphasizes the simple site-specific approach as the most useful method for finding SSLs (USEPA 2002). Generic SSLs is the simplest and least site-specific approach, as it uses tables and provides guidance on applying generic SSLs. Generic SSLs are calculated by using a conservative hypothesis, and are therefore, they more robust compared to SSLs developed by using a site-specific approach. Site-specific SSLs are calculated with the same equations used for the generic SSLs. However, the simple site-specific calculations are more flexible because data, such as hydrological, soil, and meteorological data is used. The resulting SSLs from the simple site-specific approach is less robust than the SSLs derived from the generic approach. The reason is that the site-specific method uses amendable exposure parameters to develop the SSLs. The SSLs derived with the detailed site-specific modeling approach is more stringent than the generic and simple site- specific approaches, as they are designed for SSLs that take into account more complex site conditions such as the migration of contaminants from soil to groundwater. Throughout the site screening process the investigation should be balanced between accuracy, cost and time. U.S. EPA recommends the application of the simple site- specific method as the most useful approach (USEPA 2002).
The screening approach developed by U.S. EPA (USEPA 2002, 1996b, c) should:
1. Develop a conceptual site model (CSM) 2. Compare CSM to SSL scenario 3. Define data collection needs for soils 4. Sample and analyze soils 5. Calculate site- and pathway-specific SSLs 6. Compare site soil contaminant concentrations to calculated SSLs, and 7. Address areas identified for further study
5.5.2 Factors affecting on SVs calculation The significant factors which determine the variation between soil screening values between countries can be subdivided into scientific (e.g. algorithm plus its parameter values), geographical (e.g. building and soil properties) elements or political (e.g. toxicological reference) (Provoost et al. 2008). These factors are reasons for important variations, whereas, differences in the selected software model, (standard) parameter values, selected human toxicological and ecotoxicological criteria, cause essential variations in the many SV elements. The variation of land-use scenarios is also another important reason for different SVs (Provoost et al. 2006, Provoost et al. 2008).
5.5.2.1 The scientific parameters of SVs in the USA Scientific parameters are described as the model algorithm and its model parameter values. The human health risk-based SSV are further analyzed for the predominant exposure route ‘inhalation of indoor air/outdoor’ (Provoost et al. 2006, Provoost et al. 2008)
5.5.2.2 The political parameters of SVs in the USA Political parameters are clarified as the selection of toxicological reference values or the differentiation of SSVs in different land use types (e.g. residential or industrial area) (Provoost et al. 2006, Provoost et al. 2008).
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5.5.2.3 The geographical parameters of SVs in the USA Geographical parameters include building properties, climatic conditions and soil properties (Provoost et al. 2006, Provoost et al. 2008).
5.5.3 Selecting the criteria & parameters (Provoost et al. 2006) concluded that “It is obvious that harmonization of these elements will be complicated. However, a European action programme, like the thematic strategy for soil protection, could initiate this process of harmonization. Nevertheless, soil-clean-up standards could never be uniform over the whole of Europe, because they include country-specific elements (geographical, ethnological) and political decisions”. Therefore, it is important investigate the particular Libyan geographical, ethnological elements and political decisions.
5.5.4 Application & calculation & results One of the important exposure variables is the climate. The particulate emission factor (PEF), is used to address intake from inhalation of contaminated soil-derived particulates. This value is a function both of the site and local climatic conditions. Another input parameter used to assess the soil-to-air pathway of exposure is the volatilization factor (VF). This term is used to define the relationship between the concentration of the chemical in soil and the flux of the volatilized chemical to air.
The Köppen climate classification (Chen and Chen 2013, Kottek et al. 2006a, http://koeppen-geiger.vu- wien.ac.at/shifts.htm) is employed as a comparison tool to find which country has similar climatic conditions to Libya. As a result, the climatic conditions in some regions or states in the USA are similar to Libyan climatic conditions. This means that the same climatic condition parameters and model algorithms as for the USA can be applied in Steps and results of climatic condition comparisons:
1. Using the World map climate classification (http://hanschen.org/koppen/), (See appendix D) 2. Finding out the same or similar climatic conditions to Libya 3. Finding out the climatic conditions in Libya figure 5-4 4. California, Nevada and Arizona states have similar climatic conditions, as shown in Figure 5-5 5. The main climatic factor used for deriving the particulate emission factor (PEF) and the volatilization factor (VF), is the air dispersion factor (Q/C), and is defined as inverse of the mean concentration at the center of a 0.5 acre square source (g/m2 -s per kg/m3) or as site-specific dispersion factor 6. The climatic zone is selected 7. The source city is selected based on the similarity of annual temperatures and wind speed 8. The Q/C value by source city Las Vegas in Nevada State in the climatic zone III is selected as an ideal example, Appendix D 9. Applying the Q/C value of Las Vegas city to find out the PEF and VF 10. Finding out the SVs equation by using (https://www.epa.gov/risk 2017) 11. Appling the PEF and VF calculated values in the USA model algorithms to find out all the required SVs.
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Figure 5 -4 Climatic conditions in Libya (El-Tantawi 2005)
Figure 5 -5 Climatic conditions in the USA (Köppen-Geige 2006)
5.5.5 Screening values (SVs) for Libya Site-specific dispersion Factor (Q/C): is the inverse of the ratio of the geometric mean air concentration to the volatilization flux at the center of a square source (g/m2 -s per kg/m)
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• Q/C value of Las Vegas city of a 0.5 acre = 95.51 (g/m2 -s per kg/m3); (see appendix D: Table D-1, D- 2, D-3) ⁄ 3 3600(s h) • PEF (m /kg) = Q/C ∗ 3 (5-1) 0.036∗(1−V)∗(Um⁄Ut) ∗F(x)
Table 5-1 Parameters used for calculating PEF Parameter Definition Default PEF Particulate Emission Factor (m3/kg) ----- V fraction of vegetative cover (unitless) 0.5 Q/C inverse of mean conc. at center of a 0.5-acre-square 95.51 source (g/m2-s per kg/m3)
Um mean annual windspeed (m/s) 4.07
Ut equivalent threshold value of windspeed at 7 m (m/s) 11.32 F(x) function dependent on Um/Ut, (unitless) d 0.0616
Particulate Emission Factor (PEF) (m3/kg) Equation (5-1): “This factor represents an estimate of the relationship between soil contaminant concentrations and the concentration of these contaminants in air as a consequence of particle suspension”. It relates the concentration of contaminant in soil with the concentration of dust particles in the air.
0.5 (3.14∗D ∗T) • VF = Q/C * CF* A (5-2) 2∗푏∗DA
Table 5-2 Parameters used for calculating VF Parameter Definition Default VF Volatilization factor (m3/kg) ----- DA Apparent diffusivity (cm2/s) ----- CF Conversion factor (m2/cm2) Q/C The inverse of the mean concentration (g/m2 -s per 95.51(Las Vegas parameter) kg/m3) T Exposure interval (s)
b Dry soil bulk density (g/cm3) 1.5 (between 1.3 to 1.7) (see Table A-13:default parameters for soil screening values)
Volatilization Factor (VF) (m3/kg) Equation (5-2): „The soil-to-air VF is used to define the relationship between the concentration of the contaminant in soil and the flux of the volatilized contaminant to air.” It relates the concentration of a contaminant in soil to the concentration of the contaminant in air resulting from volatilization.
Important comments on PEF & VF: (USEPA 2002) emphasize the fugitive dust pathway during identification of CSM of contaminated sites at sites with future commercial/industrial land use. Dry-land, dusty or smoothly/finely soils, high average annual speeds of wind greater than 5.3 m/s and less than 50% vegetative cover are included. Therefore, USEPA recommends using a detailed approach of site-specific modeling to improve the SVs of the fugitive dust pathway.
The Libyan climate varies considerably from the north to the south. It is estimated that roughly 90.8 % of the area is hyper-arid, 7.5 % arid, 1.5 % semi-arid, and 0.3 % is sub-humid. The precipitation is approximately less than 100 mm in the north and decreases to zero in the south. Libya is characterized by dry and hot winds with the mean annual average temperatures ranging from 14C to 23C. The mean annual wind speed across Libya ranges from 3.2 to 6.2 m/s on the coastal line, and from 3.1 to 4.7 m/s inland (Ageena 2013).
In the individual states of the USA there are many approaches for calculating soil screening levels, which all follow the EPA Soil Screening Guidance (SSG). It is a tool developed by the agency to help standardize and
46 accelerate the assessment and remediation of contaminated sites in the USA. The department of environmental protection in Florida published a technical report for developing soil and groundwater screening levels (Center for Environmental & Human Toxicology and Florida 2005). The report follows SSG. The report also describes an assessment of PHC and sites contaminated with heavy metals. By using the Regional Screening Levels (RSLs) - Equations (June 2017) (USEPA 2017) and Florida approach, SVs for Libya are determined.
Equations ((USEPA 2002, Center for Environmental & Human Toxicology and Florida 2005, USEPA 2017))
• Determination of site-specific SVs for carcinogens in groundwater:
1∗10−6∗BW∗CF GSV(g/L) = (5-3) CSF°∗WC
Table 5-3 Parameters used for calculating carcinogens GSV Parameter Definition (units) Default value GSV Groundwater SV (g/L) BW Average body weight (kg) 70 TR Target cancer risk (unitless) 1*10-6 -1 CSF Oral cancer slope factor (mg/kg.day) 20 CF Conversion factor (μg/mg) 1000 WC Average water consumption rate (L/day) 2
• Determination of site-specific SVs for non-carcinogens in groundwater:
RfD° ∗ BW∗RSC∗CF GSV((g/L) = (5-4) WC Table 5-4 Parameters used for calculating non-carcinogens GSV Parameter Definition (units) Default value GSV Groundwater SV (g/L) ----- BW Average body weight (kg) 70
RfD Oral reference dose (mg/kg.day) Chemical-specific (Toxicity) RSC Relative source contribution (%) 20 CF Conversion factor (μg/mg) 1000 WC Average water consumption rate (L/day) 2
• Determination of soil SVs for carcinogens:
TR∗BW∗AT∗RBA SSV = 1 1 (5-5) EF∗ED∗FC∗[(CSF ∗IR ∗10−6kg⁄mg)+(CSF ∗SA∗AF∗DA∗10−6kg⁄mg)+(CSF ∗IR ∗( + ))] ° ° ° i i VF PEF Table 5-5 Parameters used for calculating carcinogens SSV Parameter Definition (units) Default vlue SSV Soil screening value ----- TR Target cancer risk (unitless) 1*10-6 BW Body weight (kg) Child, aggregate, worker AT Averaging time (days) EF Exposure frequency (days/yr) ED Exposure duration (years) RBA Relative bioavailability factor (unitless) 1.0 FC The fraction from a contaminated source (unitless)
IR Ingestion rate, oral (mg/day) SA The surface area of skin exposed (cm2/day)
47
AF Adherence factor (mg/cm2) DA Dermal absorption (unitless)
IRi Inhalation rate (m3/day) VF Volatilization factor (m3/kg) calculated PEF Particulate emission factor (m3/kg) calculated CSF Cancer slope factor (mg/kg.day)
CSF Oral
CSFd Dermal
CSFi Inhalation
• Determination of soil SVs for non- carcinogens: THI∗BW∗AT∗RBA SSV = (5-6) 1 −6 1 −6 1 1 1 EF∗ED∗FC∗[( ∗IR°∗10 kg⁄mg)+( ∗SA∗AF∗DA∗10 kg⁄mg)+( ∗IRi∗( + ))] RfD° RfD° RfDi VF PEF Table 5 -6 Parameters used for calculating non-carcinogens SSV
Parameter Definition (units) Default vlue SSV Soil screening value ----- THI Target hazard index (unitless) 1.0 BW Body weight (kg) Child, aggregate, worker AT Averaging time (days) Child, aggregate, worker EF Exposure frequency (days/yr) Child, aggregate, worker ED Exposure duration (years) Child, aggregate, worker RBA Relative bioavailability factor (unitless) 1.0 FC Fraction from contaminated source (unitless) 1.0 Child, aggregate, worker IR Ingestion rate, oral (mg/day) SA The surface area of skin exposed (cm2/day) Child, aggregate, worker AF Adherence factor (mg/cm2) DA Dermal absorption (unitless) 3 IRi Inhalation rate (m /day) Child, aggregate, worker VF Volatilization factor (m3/kg) calculated PEF Particulate emission factor (m3/kg) calculated RfD Cancer slope factor (mg/kg.day) chemical-specific
RfD Oral chemical-specific
RfDd Dermal chemical-specific
RfDi Inhalation chemical-specific
• Determination of VF: 0.5 (3.14∗D ∗T) VF = Q/C * CF* A (5-7) 2∗푏∗DA 10⁄3 ′ 10⁄3 (θa DiH +θw Dw) [ ⁄ ] n2
DA = ′ (5-8) ρbKd+θw+θaH
Table 5-7 Parameters used for calculating VF Parameter Definition (units) Default value 2 DA Apparent diffusivity (cm /s) -- Total soil porosity (Lpore/Lsoil) 1-(ρb/ρs) Average soil moisture content (gwater/gsoil) 0.1 (10%) 3 b Dry soil bulk density (g/cm ) 1.5
48
3 s Soil particle density (g/cm ) 2.65
a Air-filled soil porosity (Lair/Lsoil) η - θw
w Water-filled soil porosity (Lwater/Lsoil) ωρb
Kd Soil-water partition coefficient L/kg) Koc × foc 2 Di Diffusivity in air (cm /s) Chemical-specific 2 Dw Diffusivity in water (cm /s) Chemical-specific H Henry’s Law constant (atm-m3/mol) Chemical-specific H’ Henry’s Law constant (unitless) H × 41
Koc Soil-organic carbon partition coefficient Chemical-specific foc Organic carbon content of soil (g/g) 0.006 (0.6%)‡
• Determination of SSV based on leachability: ′ θw(Lwater⁄Lsoil)+θa(Lair⁄Lsoil)∗H SSV(mg/kg) = GSV((g/L)*CF(mg/g)*DF*[Koc(L⁄kg) ∗ foc(g⁄g) + 3 ] (5-9) ρb(g⁄cm )
Table 5-8 Parameters used for calculating SSV-leachability Parameter Definition (units) Default value GSV Groundwater SV (g/L) 5000 CF Conversion factor (mg/μg) 0.001 DAF Dilution attenuation factor (unitless) 20
Koc Soil-organic carbon partition coefficient Chemical-specific foc Organic carbon content of soil (g/g) 0.002
w Water-filled soil porosity (Lwater/Lsoil) ωρb
a Air-filled soil porosity (Lair/Lsoil) η - θw H Henry’s Law constant (atm-m3/mol) Chemical-specific H’ Henry’s Law constant (unitless) H × 41 3 b Dry soil bulk density (g/cm ) 1.5 Average soil moisture content (gwater/gsoil) 0.2 (20%) Total soil porosity (Lpore/Lsoil) 1-(ρb/ρs) 3 s Soil particle density (g/cm ) 2.65
• Determination of C sat: S ′ Csat = (Kd ρb + θw + H θa) (5-10) ρb
Table 5-9 Parameters used for calculating Csat Parameter Definition (units) Default value
Csat Soil saturation concentration (mg/kg) -- S Solubility in water (mg/L) Chemical-specific Total soil porosity (Lpore/Lsoil) 1-(ρb/ρs) 3 b Dry soil bulk density (g/cm ) 1.5 3 s Soil particle density (g/cm ) 2.65
a Air-filled soil porosity (Lair/Lsoil) η - θw
w Water-filled soil porosity (Lwater/Lsoil) ωρb
Kd Soil-water partition coefficient L/kg) Koc × foc Average soil moisture content (gwater/gsoil) 0.1 (10%) H Henry’s Law constant (atm-m3/mol) Chemical-specific H’ Henry’s Law constant (unitless) H × 41
Koc Soil-organic carbon partition coefficient Chemical-specific foc Organic carbon content of soil (g/g) 0.006 (0.6%)‡
49
Table 5-10 PHC properties Range of Equivalent Carbon Boiling Avg HLC (atm- HLC MW Diffusivity in air Diffusivity in water Number (EC) point (°C) EC m3/mol) (cm3/cm3) (g/mole) (cm2/s) (cm2/s) Aliphatic fractions THPCWG Florid Florida TPHCWG & FL TPHCWG TPHCWG (Al) a Al C5-C6 51 5.5 0.805 33 81 0.1 0.00001 Al >C6-C8 96 7 1.22 50 100 0.1 0.00001 Al >C8-C10 150 9 1.93 80 130 0.1 0.00001 Al >C10- C12 200 11 2.93 120 160 0.1 0.00001 Al >C12- C16 260 14 12.9 520 200 0.1 0.00001 Al >C16- C35 320 18.5 120 4900 270 0.1 0.00001
Aromatic fractions (Ar) Ar C5-C7 (Benzene) 80 6.5 0.00561 0.23 78 0.1 0.00001 Ar >C7-C8 (toluene) 110 7.5 0.00664 0.27 92 0.1 0.00001 Ar >C8-C10 (default) 150 9 0.0117 0.48 120 0.1 0.00001 Ar >C10-C12 200 11 0.00341 0.14 130 0.1 0.00001 Ar >C12-C16 260 14 0.00129 0.053 150 0.1 0.00001 Ar >C16-C21 320 18.5 0.000317 0.013 190 0.1 0.00001 Ar >C21-C35 340 28.5 0.0000163 0.00067 240 0.1 0.00001
50
- continued Volitalization Lechability Volitiliz Lechabil Range of Equivalent Solubility Vapor Koc log Koc foc (mg/mg) foc (mg/mg) Kd (L/Kg) Kd Carbon Number (EC) (mg/L) Pressure (mL/g) (c/c) (L/Kg) (atm) Aliphatic TPHCWG & TPHCWG & Florida TPHCWG fractions (Al) FL FL Al C5-C6 36 0.35 794 2.9 0.006 0.002 4.764 1.588 Al >C6-C8 5.4 0.063 3980 3.6 0.006 0.002 23.88 7.96 Al >C8-C10 0.43 0.0063 31600 4.5 0.006 0.002 189.6 63.2 Al >C10- C12 0.034 0.0006 251000 5.4 0.006 0.002 1506 502 Al >C12- C16 0.00076 5E-05 5010000 6.7 0.006 0.002 30060 10020 Al >C16- C35 0.0000025 1E-06 630000000 8.8 0.006 0.002 3780000 1260000
Aromatic fractions (Ar) Ar C5-C7 (Benzene) 1800 0.13 59 1.9 0.006 0.002 0.354 0.118 Ar >C7-C8 (toluene) 520 0.038 182 2.4 0.006 0.002 1.092 0.364 Ar >C8-C10 (default) 65 0.0063 1580 3.2 0.006 0.002 9.48 3.16 Ar >C10-C12 25 0.0006 2510 3.4 0.006 0.002 15.06 5.02 Ar >C12-C16 5.8 5E-05 5010 3.7 0.006 0.002 30.06 10.02 Ar >C16-C21 0.65 1E-06 15800 4.2 0.006 0.002 94.8 31.6 Ar >C21-C35 0.0066 0.0002 126000 5.1 0.006 0.002 756 252 HLC: Henry's Law Constant MW: Molecular Weight
51
Table 5-11 PHCs toxicity
TPH Fraction Range of Equivalent Carbon GI aborbtion RfDo (mg/kg- RfDd (mg/kg- RfDi (mg/kg- Target Organs/Systems Number (EC) (%) day) day) day) or Effects Aliphatic fractions (Al) Al C5-C6 50 5 2.50 5.257 Neurological Al >C6-C8 50 5 2.50 5.257 Neurological Al >C8-C10 50 0.1 0.05 0.2857 Liver, blood Al >C10- C12 50 0.1 0.05 0.2857 Liver, blood Al >C12- C16 50 0.1 0.05 0.2857 Liver, blood Al >C16- C35 50 2 1.00 1.0 Liver
Aromatic fractions (Ar) Ar C5-C7 (Benzene) 90 0.2 0.180 0.1143 Liver, neurological Ar >C7-C8 (toluene) 80 0.2 0.160 0.1143 Liver, neurological Ar >C8-C10 50 0.04 0.020 0.05714 Body weight Ar >C10-C12 50 0.04 0.020 0.05714 Body weight Ar >C12-C16 50 0.04 0.020 0.05714 Body weight Ar >C16-C21 50 0.03 0.015 0.015 Kidney Ar >C21-C35 50 0.03 0.015 0.015 Kidney from Technical Report Florida Toxicity Values from TPHCWG 1997b Developed using professional judgment based on ATSDR Toxicological Profile for TPH (ATSDR 1999). RfDd values extrapolated from RfDo, using fraction-specific GI absorption RfDi values extrapolated from RfCi values when available RfDi values extrapolated from RfDo, using fraction-specific GI absorption
52
Table 5-12 PHC toxicity (Florida approach)
TPH Fraction Range of Equivalent Carbon Number RfDo (mg/kg- RfDd (mg/kg- RfDi (mg/kg-day) GI aborbtion (EC) day) day) (%) Aliphatic fractions (Al) Al C5-C6 5 2.50 5.257 50 Al >C6-C8 5 2.50 5.257 50 Al >C8-C10 0.1 0.05 0.2857 50 Al >C10- C12 0.1 0.05 0.2857 50 Al >C12- C16 0.1 0.05 0.2857 50 Al >C16- C35 2 1.00 1.0 50 >C35 20 10.000 10 50 Aromatic fractions (Ar) Ar C5-C7 (Benzene) 0.2 0.180 0.1143 90 Ar >C7-C8 (Toluene) 0.2 0.160 0.1143 80 Ar >C8-C10 0.04 0.020 0.05714 50 Ar >C10-C12 0.04 0.020 0.05714 50 Ar >C12-C16 0.04 0.020 0.05714 50 Ar >C16-C21 0.03 0.015 0.015 50 Ar >C21-C35 0.03 0.015 0.015 50
53
- continued
TPH Fraction Range of Equivalent Carbon RfDo RfDd RfDi GI RfC calculation of RfDi from Number (EC) (mg/kg- (mg/kg-day) (mg/kg- aborbtion (mg/m3) knowm RfC day) day) (%) Aliphatic mg/kg.day fractions (Al) Al C5-C6 5 2.50 5.257 50 18.40 5.2571 Al >C6-C8 5 2.50 5.257 50 18.40 5.2571 Al >C8-C10 0.1 0.05 0.2857 50 1.00 0.2857 Al >C10- C12 0.1 0.05 0.2857 50 1.00 0.2857 Al >C12- C16 0.1 0.05 0.2857 50 1.00 0.2857 Al >C16- C35 2 1.00 1.0 50 NA 1.0000 >C35 20 10.000 10 50 NA 10.0000 Aromatic fractions (Ar) Ar C5-C7 (Benzene) 0.2 0.180 0.1143 90 0.400 0.1143 "carcinogenic" Ar >C7-C8 (Toluene) 0.2 0.160 0.1143 80 0.400 0.1143 Ar >C8-C10 0.04 0.020 0.05714 50 0.200 0.0571 Ar >C10-C12 0.04 0.020 0.05714 50 0.200 0.0571 Ar >C12-C16 0.04 0.020 0.05714 50 0.200 0.0571 Ar >C16-C21 0.03 0.015 0.015 50 NA 0.0150 Ar >C21-C35 0.03 0.015 0.015 50 NA 0.0150 NA: There are no appropriate data available for the development of RfCs in this carbon range. Also, the development of an inhalation RfC from this fraction was determined to be inappropriate because the compounds in this carbon range are not volatile and inhalation will not be a relevant exposure pathway."
Table 5-13 site-specific screening values for carcinogens in groundwater Range of Equivalent Carbon Number Boiling point Avg TR BW CF CSFo (mg/Kg- WC GSV (EC) (°C) EC (Kg) (mg/mg) day) (L/day) (mg/L) C5-C7 (Benzene) 80 6.5 1E-06 70 1000 0.055 2 0.63636364
54
Table 5-14 Deriving site-specific screening values for non-carcinogens in groundwater average oral a relative source conversio Groundwater body weight reference contribution n factor GSV dose Range of Equivalent Boiling Avg BW RfDo RSC = (20%) CF WC GSV (mg/L) GSV Carbon Number (EC) point (°C) EC (Algreen et (mg/Kg- (mg/mg) (L/day (mg/L) al.) day) ) Aliphatic THPCWG Florid fractions (Al) a Al C5-C6 51 5.5 70 5 0.2 1000 2 35000 35 Al >C6-C8 96 7 70 5 0.2 1000 2 35000 35 Al >C8-C10 150 9 70 0.1 0.2 1000 2 700 0.7 Al >C10- C12 200 11 70 0.1 0.2 1000 2 700 0.7 Al >C12- C16 260 14 70 0.1 0.2 1000 2 700 0.7 Al >C16- C35 320 18.5 70 2 0.2 1000 2 14000 14
Aromatic fractions (Ar) Ar C5-C7 (Benzene) 80 6.5 70 0.2 0.2 1000 2 1400 1.4 Ar >C7-C8 (toluene) 110 7.5 70 0.2 0.2 1000 2 1400 1.4 Ar >C8-C10 150 9 70 0.04 0.2 1000 2 280 0.28 Ar >C10-C12 200 11 70 0.04 0.2 1000 2 280 0.28 Ar >C12-C16 260 14 70 0.04 0.2 1000 2 280 0.28 Ar >C16-C21 320 18.5 70 0.03 0.2 1000 2 210 0.21 Ar >C21-C35 340 28.5 70 0.03 0.2 1000 2 210 0.21
55
Table 5-15 Freshwater or marine surface water cleanup target levels Non- carcinogens
TPH Fraction Range of Equivalent Carbon RfDo BW RfDo FI BCF CF TR CSFo SWSV Number (EC) (mg/kg-day) (Kg) (MG/kg-day) (Kg/day (L/Kg) (mg/Kg-day) (mg/L) ) Aliphatic Fl fractions (Al) Al C5-C6 5 70 5 0.0175 32 1000 0.00000 625000 1 Al >C6-C8 5 70 5 0.0175 32 1000 0.00000 625000 1 Al >C8-C10 0.1 70 0.1 0.0175 32 1000 0.00000 12500 1 Al >C10- C12 0.1 70 0.1 0.0175 32 1000 0.00000 12500 1 Al >C12- C16 0.1 70 0.1 0.0175 32 1000 0.00000 12500 1 Al >C16- C35 2 70 2 0.0175 32 1000 0.00000 250000 1 >C35 20 70 20 0.0175 1000 Aromatic fractions (Ar) Ar C5-C7 (Benzene) "carcinogenic" 0.2 70 0.2 0.0175 32 1000 0.00000 0.055 25000 1 Ar >C7-C8 (Toluene) 0.2 70 0.2 0.0175 32 1000 0.00000 25000 1 Ar >C8-C10 0.04 70 0.04 0.0175 32 1000 0.00000 5000 1 Ar >C10-C12 0.04 70 0.04 0.0175 32 1000 0.00000 5000 1 Ar >C12-C16 0.04 70 0.04 0.0175 32 1000 0.00000 5000 1
56
Ar >C16-C21 0.03 70 0.03 0.0175 32 1000 0.00000 3750 1 Ar >C21-C35 0.03 70 0.03 0.0175 32 1000 0.00000 3750 1 SWSV: Surface water screening value (μg/L) BW: Body weight (kg) RfDo: Oral reference dose (mg/kg-day) FI: Fish ingestion rate (kg/day) 0.0175 BCF: Bioconcentration factor (mg toxicant/kg fish per mg toxicant/L water) CF: Conversion factor (μg/mg) TR: Target cancer risk (unitless) CSFo: Oral cancer slope factor (mg/kg-day)-1
Table 5-16 Deriving site-specific screening values for non-carcinogens in groundwater average body oral reference a relative source conversion Groundwater SV weight dose contribution factor Range of Equivalent Carbon Boiling Avg EC BW (Kg) RfDo (mg/Kg- RSC = (20%) CF (mg/mg) WC GSV (mg/L) GSV Number (EC) point (°C) day) (L/day) (mg/L) Aliphatic THPCWG Florida fractions (Al) Al C5-C6 51 5.5 70 5 0.2 1000 2 35000 35 Al >C6-C8 96 7 70 5 0.2 1000 2 35000 35 Al >C8-C10 150 9 70 0.1 0.2 1000 2 700 0.7 Al >C10- C12 200 11 70 0.1 0.2 1000 2 700 0.7 Al >C12- C16 260 14 70 0.1 0.2 1000 2 700 0.7 Al >C16- C35 320 18.5 70 2 0.2 1000 2 14000 14 Aromatic fractions (Ar) Ar C5-C7 (Benzene) 80 6.5 70 0.2 0.2 1000 2 1400 1.4 Ar >C7-C8 (toluene) 110 7.5 70 0.2 0.2 1000 2 1400 1.4 Ar >C8-C10 150 9 70 0.04 0.2 1000 2 280 0.28 Ar >C10-C12 200 11 70 0.04 0.2 1000 2 280 0.28 Ar >C12-C16 260 14 70 0.04 0.2 1000 2 280 0.28
57
Ar >C16-C21 320 18.5 70 0.03 0.2 1000 2 210 0.21 Ar >C21-C35 340 28.5 70 0.03 0.2 1000 2 210 0.21
Table 5-17 Freshwater or marine surface water screening values Non- carcinogens
TPH Fraction Range of Equivalent Carbon RfDo BW RfDo FI BCF CF TR CSFo SWSV Number (EC) (mg/kg-day) (Kg) (MG/kg-day) (Kg/day (L/Kg) (mg/Kg-day) (mg/L) ) Aliphatic Fl fractions (Al) Al C5-C6 5 70 5 0.0175 32 1000 0.00000 625000 1 Al >C6-C8 5 70 5 0.0175 32 1000 0.00000 625000 1 Al >C8-C10 0.1 70 0.1 0.0175 32 1000 0.00000 12500 1 Al >C10- C12 0.1 70 0.1 0.0175 32 1000 0.00000 12500 1 Al >C12- C16 0.1 70 0.1 0.0175 32 1000 0.00000 12500 1 Al >C16- C35 2 70 2 0.0175 32 1000 0.00000 250000 1 >C35 20 70 20 0.0175 1000 Aromatic fractions (Ar) Ar C5-C7 (Benzene) "carcinogenic" 0.2 70 0.2 0.0175 32 1000 0.00000 0.055 25000 1 Ar >C7-C8 (Toluene) 0.2 70 0.2 0.0175 32 1000 0.00000 25000 1 Ar >C8-C10 0.04 70 0.04 0.0175 32 1000 0.00000 5000 1 Ar >C10-C12 0.04 70 0.04 0.0175 32 1000 0.00000 5000
58
1 Ar >C12-C16 0.04 70 0.04 0.0175 32 1000 0.00000 5000 1 Ar >C16-C21 0.03 70 0.03 0.0175 32 1000 0.00000 3750 1 Ar >C21-C35 0.03 70 0.03 0.0175 32 1000 0.00000 3750 1 SWSV: Surface water screening values (μg/L) BW: Body weight (kg) RfDo: Oral reference dose (mg/kg-day) FI: Fish ingestion rate (kg/day) 0.0175 BCF: Bioconcentration factor (mg toxicant/kg fish per mg toxicant/L water) CF: Conversion factor (μg/mg) TR: Target cancer risk (unitless) CSFo: Oral cancer slope factor (mg/kg-day)-1
Table 5-18 Particulate Emission Factor (PEF) Q/C (g/m2-s per Kg/m3) V Um Ut (m/s) F(x) PEF (m3/Kg) PEF (m3/Kg) (m/s) Fl 95.51 0.5 4.07 11.32 0.0616 6.671971484 *109 1.241005000 *109
The default PEF is for 0.5 acre sites with undisturbed soil. Site-specific PEFs must be calculated for sites with contaminated areas which are significantly larger in size or if warranted based on site-specific conditions (Center for Environmental & Human Toxicology and Florida 2005)
59
Table 5-19 Volatilization Factor (VF) Carcinogens
TPH Range of Equivalent Carbon Number Q/C (g/m2-s per CF T ED m w b s a w Name (EC) Kg/m3) Benzene C5-C6 95.51 0.0001 946080000 30 0.433962264 0.1 1.5 2.65 0.283962264 0.15
Kd Di Dw H H' Koc foc DA (cm2/s) VF (m3/Kg) 0.354 0.088 0.0000102 0.00555 0.22755 59 0.006 0.0021464 3745.4599
VF (Benzene) (m3/Kg), FL = 3357.2 m3/Kg
Table 5-20 Volatilization Factor (VF) Non-carcinogens Q/C "Las Vega- aggregate average soil moisture dry soil bulk soil particle USA" resident content density density Range of Equivalent Carbon Q/C (g/m2-s per CF T ED (years) m w rb (g/cm3) rs (g/cm3) Number (EC) Kg/m3) TPH Fraction-Aliphatic fractions (Al) C5-C6 95.51 0.0001 9.46E+08 30 0.433962 0.1 1.5 2.65 >C6-C8 95.51 0.0001 9.46E+08 30 0.433962 0.1 1.5 2.65 >C8-C10 95.51 0.0001 9.46E+08 30 0.433962 0.1 1.5 2.65 >C10- C12 95.51 0.0001 9.46E+08 30 0.433962 0.1 1.5 2.65 >C12- C16 95.51 0.0001 9.46E+08 30 0.433962 0.1 1.5 2.65 >C16- C35 95.51 0.0001 9.46E+08 30 0.433962 0.1 1.5 2.65 >C35 0.0001 9.46E+08 30 0.433962 0.1 1.5 2.65 TPH Fraction-Aromatic fractions (Ar) C5-C7 (Benzene) "carcinogenic" 95.51 0.0001 9.46E+08 30 0.433962 0.1 1.5 2.65 >C7-C8 (Toluene) 95.51 0.0001 9.46E+08 30 0.433962 0.1 1.5 2.65 >C8-C10 95.51 0.0001 9.46E+08 30 0.433962 0.1 1.5 2.65
60
>C10-C12 95.51 0.0001 9.46E+08 30 0.433962 0.1 1.5 2.65 >C12-C16 95.51 0.0001 9.46E+08 30 0.433962 0.1 1.5 2.65 >C16-C21 95.51 0.0001 9.46E+08 30 0.433962 0.1 1.5 2.65 >C21-C35 95.51 0.0001 9.46E+08 30 0.433962 0.1 1.5 2.65
Table 5-21 Parameters used for calculating VF:Non-carcinigens
Range of Q/C CF T ED m w b s a w Kd Di Dw H H' Koc foc Equivalent (g/m2-s (years) (g/cm3) (g/cm3) Carbon per Number (EC) Kg/m3) TPH Fraction- Aliphatic Fractions (Al) C5-C6 95.51 0.0001 9.46E+08 30 0.433962 0.1 1.5 2.65 0.283962 0.15 4.764 0.1 0.00001 0.805 33.005 794 0.006
>C6-C8 95.51 0.0001 9.46E+08 30 0.433962 0.1 1.5 2.65 0.283962 0.15 23.88 0.1 0.00001 1.22 50.02 3980 0.006
>C8-C10 95.51 0.0001 9.46E+08 30 0.433962 0.1 1.5 2.65 0.283962 0.15 189.6 0.1 0.00001 1.93 79.13 31600 0.006
>C10- C12 95.51 0.0001 9.46E+08 30 0.433962 0.1 1.5 2.65 0.283962 0.15 1506 0.1 0.00001 2.93 120.13 251000 0.006
>C12- C16 95.51 0.0001 9.46E+08 30 0.433962 0.1 1.5 2.65 0.283962 0.15 30060 0.1 0.00001 12.9 528.9 5010000 0.006
>C16- C35 95.51 0.0001 9.46E+08 30 0.433962 0.1 1.5 2.65 0.283962 0.15 3780000 0.1 0.00001 120 4920 6.3E+08 0.006
>C35 0.0001 9.46E+08 30 0.433962 0.1 1.5 2.65 0.283962 0.15
TPH Fraction- Aromatic Fractions (Ar) C5-C7 95.51 0.0001 9.46E+08 30 0.433962 0.1 1.5 2.65 0.283962 0.15 0.354 0.1 0.00001 0.00561 0.23001 59 0.006 (Benzene) "carcinogenic" >C7-C8 95.51 0.0001 9.46E+08 30 0.433962 0.1 1.5 2.65 0.283962 0.15 1.092 0.1 0.00001 0.00664 0.27224 182 0.006 (Toluene) >C8-C10 95.51 0.0001 9.46E+08 30 0.433962 0.1 1.5 2.65 0.283962 0.15 9.48 0.1 0.00001 0.0117 0.4797 1580 0.006
>C10-C12 95.51 0.0001 9.46E+08 30 0.433962 0.1 1.5 2.65 0.283962 0.15 15.06 0.1 0.00001 0.00341 0.13981 2510 0.006
>C12-C16 95.51 0.0001 9.46E+08 30 0.433962 0.1 1.5 2.65 0.283962 0.15 30.06 0.1 0.00001 0.00129 0.05289 5010 0.006
>C16-C21 95.51 0.0001 9.46E+08 30 0.433962 0.1 1.5 2.65 0.283962 0.15 94.8 0.1 0.00001 0.000317 0.012997 15800 0.006
>C21-C35 95.51 0.0001 9.46E+08 30 0.433962 0.1 1.5 2.65 0.283962 0.15 756 0.1 0.00001 1.63E-05 0.000668 126000 0.006
61
Table 5-22 VF values of aggregate resident Aggregate resident 2 3 Range of Equivalent Carbon Number (EC) DA (cm /s) VF (m /Kg) TPH Fraction-Aliphatic Fractions (Al) C5-C6 0.0158243 1379.41412 >C6-C8 0.0079671 1944.048804 >C8-C10 0.0020597 3823.431077 >C10- C12 0.0004186 8480.895429 >C12- C16 9.343E-05 17952.1606 >C16- C35 6.933E-06 65902.68007 >C35 TPH Fraction-Aromatic Fractions (Ar) C5-C7 (Benzene) "carcinogenic" 0.0024631 3496.365512 >C7-C8 (Toluene) 0.0011664 5080.777226 >C8-C10 0.0002643 10674.00549 >C10-C12 4.905E-05 24775.75961 >C12-C16 9.342E-06 56772.53301 >C16-C21 7.303E-07 203050.666 >C21-C35 4.793E-09 2506413.416
Aggregate resident: The individual exposed both as a child and as an adult is termed the aggregate resident. Average assumed body weights for two broad age intervals (1 to 6 years and 7 to 31 years), actual data from yearly increments from ages 1 to 31 years are averaged.
62
Table 5-23 VF values of Children resident Child Child Range of Equivalent Carbon Number (EC) ED DA VF (m3/Kg) T (years) (cm2/s) TPH Fraction-Aliphatic Fractions (Al) C5-C6 1.89E+08 6 0.0158243 616.8927481 >C6-C8 1.89E+08 6 0.0079671 869.4050557 >C8-C10 1.89E+08 6 0.0020597 1709.890359 >C10- C12 1.89E+08 6 0.0004186 3792.771738 >C12- C16 1.89E+08 6 9.343E-05 8028.450289 >C16- C35 1.89E+08 6 6.933E-06 29472.57451 >C35 1.89E+08 6 0 TPH Fraction-Aromatic Fractions (Ar) C5-C7 (Benzene) "carcinogenic" 1.89E+08 6 0.0024631 1563.622192 >C7-C8 (Toluene) 1.89E+08 6 0.0011664 2272.192651 >C8-C10 1.89E+08 6 0.0002643 4773.560375 >C10-C12 1.89E+08 6 4.905E-05 11080.05654 >C12-C16 1.89E+08 6 9.342E-06 25389.44861 >C16-C21 1.89E+08 6 7.303E-07 90807.01841 >C21-C35 1.89E+08 6 4.793E-09 1120902.155
Child: Children are assumed to experience the greatest daily exposure to soil under residential land use scenarios. When risk is a function of the daily intake rate of a chemical (as in the evaluation of non-cancer health effects), SCTLs must be based on childhood exposure assumptions in order to be protective.
63
Table 5-24 VF values of workers Worker Worker Range of Equivalent Carbon Number (EC) ED DA VF (m3/Kg) T (years) (cm2/s) TPH Fraction-Aliphatic Fractions (Al) C5-C6 7.88E+08 25 0.0158243 1259.227049 >C6-C8 7.88E+08 25 0.0079671 1774.665638 >C8-C10 7.88E+08 25 0.0020597 3490.29908 >C10- C12 7.88E+08 25 0.0004186 7741.962891 >C12- C16 7.88E+08 25 9.343E-05 16388.00553 >C16- C35 7.88E+08 25 6.933E-06 60160.64079 >C35 7.88E+08 25 0 TPH Fraction-Aromatic Fractions (Ar) C5-C7 (Benzene) "carcinogenic" 7.88E+08 25 0.0024631 3191.730434 >C7-C8 (Toluene) 7.88E+08 25 0.0011664 4638.093827 >C8-C10 7.88E+08 25 0.0002643 9743.989312 >C10-C12 7.88E+08 25 4.905E-05 22617.07069 >C12-C16 7.88E+08 25 9.342E-06 51825.99496 >C16-C21 7.88E+08 25 7.303E-07 185359.0501 >C21-C35 7.88E+08 25 4.793E-09 2288031.944
64
Table 5-25 Volatilization Factor (VF) of different land use Aggregate resident Child Worker TPH Fraction Range of Equivalent Carbon Number (EC) VF (m3/Kg) VF (m3/Kg) VF (m3/Kg) Aliphatic Fractions TPH Fraction-Aliphatic Fractions (Al) (Al) Al C5-C6 1379.41412 616.8927481 1259.227049 Al >C6-C8 1944.048804 869.4050557 1774.665638 Al >C8-C10 3823.431077 1709.890359 3490.29908 Al >C10- C12 8480.895429 3792.771738 7741.962891 Al >C12- C16 17952.1606 8028.450289 16388.00553 Al >C16- C35 65902.68007 29472.57451 60160.64079 >C35 Aromatic Fractions TPH Fraction-Aromatic Fractions (Ar) (Ar) Ar C5-C7 (Benzene) "carcinogenic" 3496.365512 1563.622192 3191.730434 Ar >C7-C8 (Toluene) 5080.777226 2272.192651 4638.093827 Ar >C8-C10 10674.00549 4773.560375 9743.989312 Ar >C10-C12 24775.75961 11080.05654 22617.07069 Ar >C12-C16 56772.53301 25389.44861 51825.99496 Ar >C16-C21 203050.666 90807.01841 185359.0501 Ar >C21-C35 2506413.416 1120902.155 2288031.944
Table 5-26 Soil screening values for carcinogens SCTL TPH Fraction Range of Equivalent Carbon Number CSFo (mg/Kg-day)-1 CSFd (mg/Kg-day)- CSFi (mg/Kg-day)- GI aborbtion IUR TR BW AT (EC) 1 1 (%) (mg/m3) (Kg) (days) Ar C5-C7 (Benzene) "carcinogenic" 0.055 0.061111111 0.0273 90 0.0000078 0.000001 51.9 25500
RBA EF Days/years) ED (years) FC IRO (mg/days) SA (cm2) AF (mg/cm2) DA Iri (m3/day) VF (m3/Kg) PEF (m3/Kg) SSV (mg/Kg) 1 350 30 1 120 4810 0.1 0.01 12.2 3745.4599 6671971484 1.315445039
65
Table 5-27 Soil screening values for non-carcinogens (child) Child
TPH Fraction Range of Equivalent Carbon RfDo RfDd RfDi THI BW AT EF ED RBA FC Number (EC) (mg/kg-day) (mg/kg-day) (mg/kg-day) (Kg) (days) (days/yr (years ) ) Aliphatic Fractions (Al) Al C5-C6 5 2.50 5.257 1 16.8 2190 350 6 1 1 Al >C6-C8 5 2.50 5.257 1 16.8 2190 350 6 1 1 Al >C8-C10 0.1 0.05 0.2857 1 16.8 2190 350 6 1 1 Al >C10- C12 0.1 0.05 0.2857 1 16.8 2190 350 6 1 1 Al >C12- C16 0.1 0.05 0.2857 1 16.8 2190 350 6 1 1 Al >C16- C35 2 1.00 1.0 1 16.8 2190 350 6 1 1 >C35 20 10.000 10 1 16.8 2190 350 6 1 1 Aromatic 1 16.8 2190 350 6 1 1 Fractions (Ar) Ar C5-C7 (Benzene) 0.2 0.180 0.1143 1 16.8 2190 350 6 1 1 "carcinogenic" Ar >C7-C8 (Toluene) 0.2 0.160 0.1143 1 16.8 2190 350 6 1 1 Ar >C8-C10 0.04 0.020 0.05714 1 16.8 2190 350 6 1 1 Ar >C10-C12 0.04 0.020 0.05714 1 16.8 2190 350 6 1 1 Ar >C12-C16 0.04 0.020 0.05714 1 16.8 2190 350 6 1 1 Ar >C16-C21 0.03 0.015 0.015 1 16.8 2190 350 6 1 1 Ar >C21-C35 0.03 0.015 0.015 1 16.8 2190 350 6 1 1
Table 5-28 Soil screening values for non-carcinogens (child)
Range of RfDo RfDd RfDi THI BW AT EF (d/yr) ED RBA FC IRo SA AF DA IRi VF (m3/kg) PEF (m3/Kg) SSVs Child Equivalent (mg/kg.d) (mg/kg.d) (mg/kg.d) (Kg) (days) yr (mg/day) (cm2/d) (mg/cm2) (m3/day) (mg/Kg) Carbon Number (EC) Aliphatic fractions (Al)
66
C5-C6 5 2.50 5.257 1 16.8 2190 350 6 1 1 200 2960 0.2 0.01 8.1 616.89275 6671971484 6897.497753
>C6-C8 5 2.50 5.257 1 16.8 2190 350 6 1 1 200 2960 0.2 0.01 8.1 869.40506 6671971484 9654.925658
>C8-C10 0.1 0.05 0.2857 1 16.8 2190 350 6 1 1 200 2960 0.2 0.01 8.1 1709.8904 6671971484 936.9362877
>C10- C12 0.1 0.05 0.2857 1 16.8 2190 350 6 1 1 200 2960 0.2 0.01 8.1 3792.7717 6671971484 1826.232215
>C12- C16 0.1 0.05 0.2857 1 16.8 2190 350 6 1 1 200 2960 0.2 0.01 8.1 8028.4503 6671971484 3101.009606
>C16- C35 2 1.00 1.0 1 16.8 2190 350 6 1 1 200 2960 0.2 0.01 8.1 29472.575 6671971484 46014.0838
>C35 20 10.000 10
Aromatic fractions (Ar) C5-C7 0.2 0.180 0.1143 1 16.8 2190 350 6 1 1 200 2960 0.2 0.01 8.1 1563.6222 6671971484 377.9553651 (Benzene) "carcinogenic" >C7-C8 0.2 0.160 0.1143 1 16.8 2190 350 6 1 1 200 2960 0.2 0.01 8.1 2272.1927 6671971484 543.6696848 (Toluene) >C8-C10 0.04 0.020 0.05714 1 16.8 2190 350 6 1 1 200 2960 0.2 0.01 8.1 4773.5604 6671971484 500.6812538
>C10-C12 0.04 0.020 0.05714 1 16.8 2190 350 6 1 1 200 2960 0.2 0.01 8.1 11080.057 6671971484 968.4953245
>C12-C16 0.04 0.020 0.05714 1 16.8 2190 350 6 1 1 200 2960 0.2 0.01 8.1 25389.449 6671971484 1610.393537
>C16-C21 0.03 0.015 0.015 1 16.8 2190 350 6 1 1 200 2960 0.2 0.01 8.1 90807.018 6671971484 1346.854027
>C21-C35 0.03 0.015 0.015 1 16.8 2190 350 6 1 1 200 2960 0.2 0.01 8.1 1120902.2 6671971484 2322.631221
Table 5-29 Soil screening values for non-carcinogens (aggregate resident) Aggregate Resident TPH Range of Equivalent Carbon Number RfDo (mg/kg-day) RfDd (mg/kg-day) RfDi (mg/kg-day) THI BW AT EF ED RBA FC Fraction (EC) (Kg) (days) (days/yr) (years) Aliphatic Fractions (Al) Al C5-C6 5 2.5 5.257 1 51.9 10950 350 30 1 1 Al >C6-C8 5 2.5 5.257 1 51.9 10950 350 30 1 1 Al >C8-C10 0.1 0.05 0.2857 1 51.9 10950 350 30 1 1 Al >C10- C12 0.1 0.05 0.2857 1 51.9 10950 350 30 1 1 Al >C12- C16 0.1 0.05 0.2857 1 51.9 10950 350 30 1 1 Al >C16- C35 2 1 1 1 51.9 10950 350 30 1 1 >C35 20 10 10 1 51.9 10950 350 30 1 1 Aromatic Fractions (Ar)
67
Ar C5-C7 (Benzene) "carcinogenic" 0.2 0.18 0.1143 1 51.9 10950 350 30 1 1 Ar >C7-C8 (Toluene) 0.2 0.16 0.1143 1 51.9 10950 350 30 1 1 Ar >C8-C10 0.04 0.02 0.05714 1 51.9 10950 350 30 1 1 Ar >C10-C12 0.04 0.02 0.05714 1 51.9 10950 350 30 1 1 Ar >C12-C16 0.04 0.02 0.05714 1 51.9 10950 350 30 1 1 Ar >C16-C21 0.03 0.015 0.015 1 51.9 10950 350 30 1 1 Ar >C21-C35 0.03 0.015 0.015 1 51.9 10950 350 30 1 1
-continued Aggregate Resident
TPH Range of RfDo RfDd RfDi THI BW AT EF ED RBA FC IRo SA AF DA IRi VF PEF SSVs Fraction Equivalent (mg/kg- (mg/kg- (mg/kg- (Kg) (days) (days/yr) (years) (mg/day) (cm2/day) (mg/cm2) (m3/day) (m3/kg) (m3/Kg) Aggregate Carbon day) day) day) (mg/Kg) Number (EC) Aliphatic Fractions (Al)
Al C5-C6 5 2.5 5.257 1 51.9 10950 350 30 1 1 120 4810 0.1 0.01 12.2 1379.414 6.672E+09 31682.8243
Al >C6-C8 5 2.5 5.257 1 51.9 10950 350 30 1 1 120 4810 0.1 0.01 12.2 1944.049 6.672E+09 44375.88325
Al >C8-C10 0.1 0.05 0.2857 1 51.9 10950 350 30 1 1 120 4810 0.1 0.01 12.2 3823.431 6.672E+09 4342.189793
Al >C10- C12 0.1 0.05 0.2857 1 51.9 10950 350 30 1 1 120 4810 0.1 0.01 12.2 8480.895 6.672E+09 8548.679204
Al >C12- C16 0.1 0.05 0.2857 1 51.9 10950 350 30 1 1 120 4810 0.1 0.01 12.2 17952.16 6.672E+09 14728.22133
Al >C16- C35 2 1 1 1 51.9 10950 350 30 1 1 120 4810 0.1 0.01 12.2 65902.68 6.672E+09 216554.9343
>C35 20 10 10 1 51.9 10950 350 30 1 1 120 4810 0.1 0.01
Aromatic Fractions (Ar)
Ar C5-C7 0.2 0.18 0.1143 1 51.9 10950 350 30 1 1 120 4810 0.1 0.01 12.2 3496.366 6.672E+09 1737.279201 (Benzene) "carcinogenic" Ar >C7-C8 0.2 0.16 0.1143 1 51.9 10950 350 30 1 1 120 4810 0.1 0.01 12.2 5080.777 6.672E+09 2501.351419 (Toluene) Ar >C8-C10 0.04 0.02 0.05714 1 51.9 10950 350 30 1 1 120 4810 0.1 0.01 12.2 10674.01 6.672E+09 2328.58773
Ar >C10-C12 0.04 0.02 0.05714 1 51.9 10950 350 30 1 1 120 4810 0.1 0.01 12.2 24775.76 6.672E+09 4564.270034
Ar >C12-C16 0.04 0.02 0.05714 1 51.9 10950 350 30 1 1 120 4810 0.1 0.01 12.2 56772.53 6.672E+09 7730.559424
Ar >C16-C21 0.03 0.015 0.015 1 51.9 10950 350 30 1 1 120 4810 0.1 0.01 12.2 203050.7 6.672E+09 6500.35614
Ar >C21-C35 0.03 0.015 0.015 1 51.9 10950 350 30 1 1 120 4810 0.1 0.01 12.2 2506413 6.672E+09 11651.43452
68
Table 5-30 Soil screening values for non-carcinogens (worker) worker TPH Fraction Range of Equivalent Carbon RfDo RfDd (mg/kg.d) RfDi (mg/kg.d) THI BW AT EF ED RBA FC Number (EC) (mg/kg.d) (Kg) (d) (d/yr) (Meyer et al.) Aliphatic fractions (Al) Al C5-C6 5 2.5 5.257 1 76.1 9125 250 25 1 1 Al >C6-C8 5 2.5 5.257 1 76.1 9125 250 25 1 1 Al >C8-C10 0.1 0.05 0.2857 1 76.1 9125 250 25 1 1 Al >C10- C12 0.1 0.05 0.2857 1 76.1 9125 250 25 1 1 Al >C12- C16 0.1 0.05 0.2857 1 76.1 9125 250 25 1 1 Al >C16- C35 2 1 1 1 76.1 9125 250 25 1 1 >C35 20 10 10 1 76.1 9125 250 25 1 1 Aromatic fractions (Ar) Ar C5-C7 (Benzene) "carcinogenic" 0.2 0.18 0.1143 1 76.1 9125 250 25 1 1 Ar >C7-C8 (Toluene) 0.2 0.16 0.1143 1 76.1 9125 250 25 1 1 Ar >C8-C10 0.04 0.02 0.05714 1 76.1 9125 250 25 1 1 Ar >C10-C12 0.04 0.02 0.05714 1 76.1 9125 250 25 1 1 Ar >C12-C16 0.04 0.02 0.05714 1 76.1 9125 250 25 1 1 Ar >C16-C21 0.03 0.015 0.015 1 76.1 9125 250 25 1 1 Ar >C21-C35 0.03 0.015 0.015 1 76.1 9125 250 25 1 1
69
-continued worker
TPH Range of RfDo RfDd RfDi THI BW AT EF ED RBA FC IRo SA AF DA IRi VF (m3/kg) PEF SSVs Fraction Equivalent (mg/kg- (mg/kg.d) (mg/kg- (Kg) (d) (d/yr) (years) (mg/d) (cm2/day) (mg/cm2) (m3/day) (m3/Kg) worker Carbon day) day) (mg/Kg) Number (EC) Aliphatic fractions (Al)
Al C5-C6 5 2.5 5.257 1 76.1 9125 250 25 1 1 50 3500 0.1 0.01 20 1109.585891 6797921000 32297.19269
Al >C6-C8 5 2.5 5.257 1 76.1 9125 250 25 1 1 50 3500 0.1 0.01 20 1563.771962 6797921000 45455.71997
Al >C8-C10 0.1 0.05 0.2857 1 76.1 9125 250 25 1 1 50 3500 0.1 0.01 20 3075.526862 6797921000 4762.064709
Al >C10- C12 0.1 0.05 0.2857 1 76.1 9125 250 25 1 1 50 3500 0.1 0.01 20 6821.941125 6797921000 10257.64362
Al >C12- C16 0.1 0.05 0.2857 1 76.1 9125 250 25 1 1 50 3500 0.1 0.01 20 14440.52503 6797921000 20507.88187
Al >C16- C35 2 1 1 1 76.1 9125 250 25 1 1 50 3500 0.1 0.01 20 53011.40748 6797921000 273808.313
>C35 20 10 10 1 76.1 9125 250 25 1 1 50 3500 0.1 0.01
Aromatic fractions (Ar)
Ar C5-C7 0.2 0.18 0.1143 1 76.1 9125 250 25 1 1 50 3500 0.1 0.01 20 2812.438837 6797921000 1778.115106 (Benzene) "carcinogenic" Ar >C7-C8 0.2 0.16 0.1143 1 76.1 9125 250 25 1 1 50 3500 0.1 0.01 20 4086.922589 6797921000 2578.699862 (Toluene) Ar >C8-C10 0.04 0.02 0.05714 1 76.1 9125 250 25 1 1 50 3500 0.1 0.01 20 8586.055287 6797921000 2633.413857
Ar >C10-C12 0.04 0.02 0.05714 1 76.1 9125 250 25 1 1 50 3500 0.1 0.01 20 19929.35472 6797921000 5851.391106
Ar >C12-C16 0.04 0.02 0.05714 1 76.1 9125 250 25 1 1 50 3500 0.1 0.01 20 45667.21532 6797921000 12223.45216
Ar >C16-C21 0.03 0.015 0.015 1 76.1 9125 250 25 1 1 50 3500 0.1 0.01 20 163331.7732 6797921000 11040.44962
Ar >C21-C35 0.03 0.015 0.015 1 76.1 9125 250 25 1 1 50 3500 0.1 0.01 20 2016132.011 6797921000 43374.88349
70
Table 5-31 Soil screening values for non-carcinogens (child, aggregate, worker) Industrial TPH Fraction Range of Equivalent Carbon Number (EC) SSVs Child (mg/Kg) SSVs Aggregate (mg/Kg) SSVs worker (mg/Kg) Aliphatic Fractions (Al) Al C5-C6 6897.497753 31682.8243 36636.48787 Al >C6-C8 9654.925658 44375.88325 51553.5482 Al >C8-C10 936.9362877 4342.189793 5386.539392 Al >C10- C12 1826.232215 8548.679204 11558.97585 Al >C12- C16 3101.009606 14728.22133 22948.00583 Al >C16- C35 46014.0838 216554.9343 307818.672 >C35 Aromatic Fractions (Ar) Ar C5-C7 (Benzene) "carcinogenic" 377.9553651 1737.279201 2016.742611 Ar >C7-C8 (Toluene) 543.6696848 2501.351419 2923.980373 Ar >C8-C10 500.6812538 2328.58773 2975.010074 Ar >C10-C12 968.4953245 4564.270034 6573.983828 Ar >C12-C16 1610.393537 7730.559424 13584.70347 Ar >C16-C21 1346.854027 6500.35614 12218.24996 Ar >C21-C35 2322.631221 11651.43452 44747.71747
71
Table 5-32 Comparison between calculated SSVs for Libya and SCTLs for Florida-USA Resident Resident Resident Resident Industrial Industrial
SVs Child SVs Child SVs Aggregate SVs Aggregate SVs Worker SVs Worker TPH fraction (mg/Kg)-Libya (mg/Kg)-Fl (mg/Kg)-Libya (mg/Kg)-Fl (mg/Kg)-Libya (mg/Kg)-Fl C5-C6 Aliphatic 6897 6200 31682 36636 33000 >C6-C8 Aliphatic 9654 8700 44375 51553 46000 >C8-C10 Aliphatic 936 850 4342 5386 4800 >C10- C12 Aliphatic 1826 1700 8548 11558 10000 >C12- C16 Aliphatic 3101 2900 14728 22948 21000 >C16- C35 Aliphatic 46014 42000 216554 307818 280000 C5-C7 Aromatic 377 340 1737 2016 1800 >C7-C8 Aromatic 543 490 2501 2923 3700 >C8-C10 Aromatic 500 460 2328 2975 2700 >C10-C12 Aromatic 968 900 4564 6573 5900 >C12-C16 Aromatic 1610 1500 7730 13584 12000 >C16-C21 Aromatic 1346 1300 6500 12218 11000 >C21-C35 Aromatic 2322 2300 11651 44747 40000
72
Table 5-33 Soil screening values (SSVs) based on leachability Leachability
Range of Equivalent GSV CF (mg/mg) DAF Koc (mL/g) foc w rb rs h qa qw HLC (atm- H' SSVs (mg/Kg) Carbon Number (EC) (mg/mg) m3/mol) Aliphatic Fl Fl Fl Fl Fl Fl Florida fractions (Al) Al C5-C6 5000 0.001 20 794 0.002 0.2 1.5 2.65 0.433962 0.133962 0.3 0.805 33.005 473.5616352
Al >C6-C8 5000 0.001 20 3980 0.002 0.2 1.5 2.65 0.433962 0.133962 0.3 1.22 50.02 1262.719497 Al >C8-C10 5000 0.001 20 31600 0.002 0.2 1.5 2.65 0.433962 0.133962 0.3 1.93 79.13 7046.695597 Al >C10- C12 5000 0.001 20 251000 0.002 0.2 1.5 2.65 0.433962 0.133962 0.3 2.93 120.13 51292.85912 Al >C12- C16 5000 0.001 20 5010000 0.002 0.2 1.5 2.65 0.433962 0.133962 0.3 12.9 528.9 ------
Al >C16- C35 5000 0.001 20 630000000 0.002 0.2 1.5 2.65 0.433962 0.133962 0.3 120 4920 ------
Aromatic fractions (Ar) Ar C5-C7 (Benzene) 5000 0.001 20 59 0.002 0.2 1.5 2.65 0.433962 0.133962 0.3 0.00561 0.23001 33.85417736
Ar >C7-C8 (toluene) 5000 0.001 20 182 0.002 0.2 1.5 2.65 0.433962 0.133962 0.3 0.00664 0.27224 58.83132579 Ar >C8-C10 (default) 5000 0.001 20 1580 0.002 0.2 1.5 2.65 0.433962 0.133962 0.3 0.0117 0.4797 340.2841132 Ar >C10-C12 5000 0.001 20 2510 0.002 0.2 1.5 2.65 0.433962 0.133962 0.3 0.00341 0.13981 523.2486176 Ar >C12-C16 5000 0.001 20 5010 0.002 0.2 1.5 2.65 0.433962 0.133962 0.3 0.00129 0.05289 1022.472351 Ar >C16-C21 5000 0.001 20 15800 0.002 0.2 1.5 2.65 0.433962 0.133962 0.3 0.000317 0.012997 3180.116074 Ar >C21-C35 5000 0.001 20 126000 0.002 0.2 1.5 2.65 0.433962 0.133962 0.3 0.0000163 0.000668 25220.00597
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Table 5-34 Parametrs used for determining soil saturation concentration (Csat.) (mg/kg) TPH Range of Equivalent S h (Lpore/Lsoil) qa qw w rb rs Kd H (atm- H' Koc foc Csat Fraction Carbon Number (EC) (mg/L) (Lair/Lsoil) (Lwater/Lsoil) (Kgwater/Kgsoil) (g/cm3) (g/cm3) (cm3/g) m3/mol) (L/Kg) (g/g) (mg/Kg) Aliphatic Fractions (Al)
Al C5-C6 36 0.433962264 0.283962264 0.15 0.1 1.5 2.65 4.764 0.805 33.005 794 0.006 400.0361887
Al >C6-C8 5.4 0.433962264 0.283962264 0.15 0.1 1.5 2.65 23.88 1.22 50.02 3980 0.006 180.6256528
Al >C8-C10 0.43 0.433962264 0.283962264 0.15 0.1 1.5 2.65 189.6 1.93 79.13 31600 0.006 88.01238107
Al >C10- C12 0.034 0.433962264 0.283962264 0.15 0.1 1.5 2.65 1506 2.93 120.13 251000 0.006 51.9806141
Al >C12- C16 0.00076 0.433962264 0.283962264 0.15 0.1 1.5 2.65 30060 12.9 528.9 5010000 0.006 22.92177107
Al >C16- C35 2.5E-06 0.433962264 0.283962264 0.15 0.1 1.5 2.65 3780000 120 4920 630000000 0.006 9.452328741
>C35 0.433962264 0.283962264 0.15 0.1 1.5 2.65 0
Aromatic Fractions (Ar)
Ar C5-C7 (Benzene) 1800 0.433962264 0.283962264 0.15 0.1 1.5 2.65 0.354 0.00561 0.23001 59 0.006 895.5769925 "carcinogenic" Ar >C7-C8 (Toluene) 520 0.433962264 0.283962264 0.15 0.1 1.5 2.65 1.092 0.00664 0.27224 182 0.006 646.6393741
Ar >C8-C10 65 0.433962264 0.283962264 0.15 0.1 1.5 2.65 9.48 0.0117 0.4797 1580 0.006 628.6027236
Ar >C10-C12 25 0.433962264 0.283962264 0.15 0.1 1.5 2.65 15.06 0.00341 0.13981 2510 0.006 379.6616794
Ar >C12-C16 5.8 0.433962264 0.283962264 0.15 0.1 1.5 2.65 30.06 0.00129 0.05289 5010 0.006 174.9860726
Ar >C16-C21 0.65 0.433962264 0.283962264 0.15 0.1 1.5 2.65 94.8 0.000317 0.012997 15800 0.006 61.68659928
Ar >C21-C35 0.0066 0.433962264 0.283962264 0.15 0.1 1.5 2.65 756 0.0000163 0.000668 126000 0.006 4.990260835
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Table 5-35 Q/C values : VF values (Carcinogens) Q/C (g/m2-s per Kg/m3) VF (m3/Kg) 97.75 3833.3024 95.51 3745.4599 90.74 3558.4026 85.4 3348.9926 79.24 3107.4259 75.59 2964.2898 69.25 2715.6643 64.06 2512.1366
Table 5-36 Q/C values : VF values (Non-carcinogens) Range of Equivalent Carbon Number (EC) VF Aggregate Resident TPH Fraction-Aliphatic Fractions (Al) Q/C 97.75 Q/C 95.51 Q/C 90.74 Q/C 85.4 Q/C 79.24 Q/C 75.59 Q/C 69.25 Q/C 64.06 C5-C6 1411.766 1379.414 1310.523 1233.399 1144.433 1091.717 1000.151 925.1939 >C6-C8 1989.643 1944.049 1846.958 1738.266 1612.883 1538.589 1409.542 1303.903 >C8-C10 3913.102 3823.431 3632.48 3418.71 3172.115 3025.999 2772.198 2564.433 >C10- C12 8679.798 8480.895 8057.339 7583.169 7036.186 6712.081 6149.115 5688.265 >C12- C16 18373.19 17952.16 17055.59 16051.87 14894.03 14207.98 13016.3 12040.79 >C16- C35 67448.3 65902.68 62611.34 58926.7 54676.25 52157.72 47783.07 44201.92 >C35 TPH Fraction-Aromatic Fractions (Ar) C5-C7 (Benzene) "carcinogenic" 3578.366 3496.366 3321.749 3126.265 2900.764 2767.148 2535.057 2345.065 >C7-C8 (Toluene) 5199.937 5080.777 4827.031 4542.963 4215.274 4021.107 3683.843 3407.754 >C8-C10 10924.34 10674.01 10140.92 9544.132 8855.703 8447.786 7739.241 7159.217 >C10-C12 25356.83 24775.76 23538.4 22153.18 20555.24 19608.41 17963.79 16617.48 >C12-C16 58104.02 56772.53 53937.18 50763 47101.41 44931.8 41163.21 38078.2 >C16-C21 207812.8 203050.7 192909.8 181557.2 168461.3 160701.5 147222.9 136189.1 >C21-C35 2565196 2506413 2381237 2241103 2079449 1983664 1817287 1681089
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5.6 State of the art “Risk assessment, Toxicity assessment, Exposure assessment” A stressor is released into the environment from a source and transported through space and time into different media, such as air, soil, water, and so forth. Different transformations may occur, for example, volatilization, degradation, chemical reaction, deposition, and others. These transport and transformation processes result in different concentrations of the stressor (chemical) within environmental media as functions of time. Exposure is a process which includes steps which occur when humans contact the pollutant-bearing media in the course of human activities. If the chemical of interest subsequently crosses the outer boundary and enters the human body, a dose is absorbed. The dose may then cause adverse health effects. It is important to consider that exposure does not automatically include a dose, but exposure is pivotal for a dose (JR 2001). Figure 5-6 shows a sequence of steps undergone by a stressor. Figure 5-7 describes the overall risk assessment process.
Figure 5-6 Stages of exposure process
(JR 2001)
Figure 5-7 The exposure assessment process in the comprehensive risk assessment method according to NRC 2009 (USEPA 2016)
5.6.1 The exposure to the human body and the environment “Human exposure means contact with the chemical or agent”, but it is debatable whether such contact is with exterior or interior boundaries of the body (USEPA 1992b). (USEPA 1992b) guidelines considered, exposure to the chemical is the contact of that agent with the outer boundary. An exposure assessment evaluates such contact in a quantitative and qualitative method, in addition, it involves the studies of disease occurrence, causes of disease and occupational exposure (USEPA 1992b). An exposure assessment evaluates the amount of the actual/potential human exposure, the frequency, duration of these exposures, and the pathways through which a human is subjected to current and future exposures (USEPA 1989). The exposure assessment process is depicted by (USEPA 1989) in the next sections:
1- analysis of contaminant releases from a source into environmental media
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2- assessment of the fate and transport of the contaminants released into the environment 3- identification, listing, and characterization of potentially exposed populations 4- combined exposure analysis, and 5- uncertainty analysis. The further steps of exposure assessment are (USEPA 1989):
1- Characterization of exposure setting: a. physical environment: climate, meteorology, geology, hydrogeology, hydrology, vegetation, soil, and location b. potentially exposed populations: location of current populations, current and future land-uses and populations of potential concern 2- Identification of exposure pathways: a. chemical source: sources and receiving media b. fate & transport in release media: transportation, transformation, accumulation c. exposure point & route: to potentially exposed populations, greatest concentration d. integration of information on sources, releases, fate and transport, exposure points, and exposure routes into exposure pathways e. summary of information on all complete exposure pathways 3- Quantification of exposure: a. exposure concentration: evaluation of exposure concentrations in groundwater, soil, air, surface water, sediment, food, Summary of exposure concentration for each pathway b. exposure evaluation of chemical intake: calculate of exposure intake from groundwater and surface water, soil sediment or dust, air, food 4- Integration of chemical intakes across pathways 5- Evaluation of uncertainty 6- Presentation of the summary and the exposure assessment results
Figure 5-8 The exposure assessment method (USEPA 1989)
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5.6.2 General concepts
Figure 5 -9 Exposure science as the basic foundation of sustainability, risk analysis and human and environmental protection (Cohen Hubal et al. 2011)
Exposure science deals with questions concerning the protection of human health. It informs decisions relating to smart and sustainable design, prevention and mitigation of adverse exposures, and ultimately health protection.
(Paul J. Lioy and Rappaport 2011) encourage exposure scientists to use and exercise the advantages of monitoring approaches for assessing human exposures. The source-to-dose framework required by the environmental health sciences is supported. (NRC 2010) Studies and observations led John Groten to conclude that negative health impacts were caused by chemical mixtures and were particularly related to certain interactions at the molecular level. A further conclusion was that the application of functional genomics (sequencing, genotyping, transcriptomics, proteomics, and metabolomics) will bring new findings and advance the risk assessment of chemical mixtures. Thomas Hartung observed that regulatory toxicology is a business. Toxicity testing on animals in the European Union is a $800 million/year businesses that employs approximately 15,000 people. However, the acquired data is not necessarily conducive for reaching correct conclusions on toxicity. He stipulates that the current system leaves unanswered questions to which each health scare adds new open questions. A further problem is that animal tests are not always applicable to humans. However, cell cultures for tests are limited; the outcome of test compounds is unknown, and dedifferentiation a potential problem. Thus, the current system is far from excellent. Hartung concluded that instead of a simple replacement of individual parts, a complete revolution is called for and that the worst mistake would be to integrate small advances into the existing system. The new technologies offer enormous chances for a new system. (REACH 2011) The risk assessment of adverse health impacts includes both the knowledge of the source and nature of the environmental hazards and an understanding of the relationship of the exposure to the disease. Currently, interest is focused on potential gene-environment interactions to determine the combined genetic and environmental influences on disease risks. REACH states that it is important to know the mechanism of action (the dose- response) in order to interpret the epidemiological studies for risk characterization. REACH also reported also that threshold and non-threshold mechanisms of action have important consequences for risk assessment developments.
(NRC 2012), NRC examined methods for improving risk assessments and identified the necessity for better tools in order to address exposures in cumulative risk assessments. The focus is on acquiring more and better exposure data in order to understand dose-effect relationships, and stressing the importance of understanding both chemical and nonchemical stressors and their interactions. There is also a need for investments in exposure biomarkers and appropriate defaults in order to account for individual susceptibility and population vulnerability when stressor-specific data is not available. Finally, the characterization of exposures in the context of cumulative risk assessment must be improved. The essence of scientific decisions is to improve risk assessments so that vulnerabilities are apprehended, and dose-response models upgraded. A further important aspect is the observation that vulnerability arises both from former and from current exposures which delivers further data for exposure science.
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Figure 5 -10 REACH method of hazard assessment process (NRC 2012)
Exposure science addresses the intensity and duration of contact of humans or other organisms with agents, such as chemical, physical, or biologic stressors1 and the consequences for living systems. Exposure science is applied in the public health system and ecosystem protection, and in commercial, military, and policy contexts. It is central to tracking chemicals and other stressors introduced into global commerce and the environment at increasing rates, often with little information about their hazard potential. A simplified definition of exposure science is that it is the study of stressors, receptors, and their contacts in the context of space and time. Exposure assessment has been instrumental in helping to forecast, prevent, and mitigate exposures that lead to adverse health effects or negative ecologic outcomes. To identify populations those have high exposures, to assess and manage human health and ecosystem risks, and to protect vulnerable and susceptible populations. Exposure information is crucial for predicting, preventing, and reducing risks to human health and the ecosystem. Exposure science has historically been limited by the availability of methods, technologies, and resources, but recent advances present an unprecedented opportunity to develop more rapid, cost-effective, and relevant exposure assessments. Research supported by such federal agencies as EPA and NIEHS has provided valuable partnership opportunities for increasing capacities in order to develop the technologies, resources, and educational the structure that will be needed to achieve the committee’s vision for exposure science in the 21st century. Sustainable decisions and actions are those that improve the current health of individuals and communities without compromising the health and welfare of future generations. Such decisions are supported by overall environmental assessments so that, for example, the risk is not merely shifted from water to air or from one population to another. Exposure information is required to support this holistic approach to deal with emerging trends and strength public health policies (NRC 2012).
Figure 5 -11 The classic environmental-health continuum (NRC 2012)
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Figure 5 -12 Core elements of exposure science (NRC 2012)
Figure 5 -13 Modeling exposure at different levels from source to dose (NRC 2012)
5.6.3 Exposome (Wild 2005) stated that “The imbalance in measurement precision of genes and environment has consequences, most fundamentally in compromising the ability to fully derive public health benefits from expenditure on the human genome and the aforementioned cohort studies. There is a desperate need to develop methods with the same precision for an individual’s environmental exposure as we have for the individual’s genome. I would like to suggest that there is a need for an ‘‘exposome’’ to match the ‘‘genome.’’ This concept of an exposome may be useful in drawing attention to the need for methodologic developments in exposure assessment“. The further development, validation, and application of biomarkers of exposure in this context are a critical part of the future cancer epidemiology in the 21st century (Wild 2009). (Wild 2012a) presented “Importance of environmental exposure assessment” and stated that, Most major common diseases have an environmental aetiology, currently exposure measurement is problematic in many areas, leading to misclassification, large prospective cohort studies (e.g. UK Biobank) are predicated on the availability of accurate exposure assessment, and exposure biomarkers can contribute to several areas in addition to elucidating disease aetiology. (Wild 2012b). The
80 exposome comprises of every exposure to which an individual is subjected from conception to death. Therefore, it requires consideration of both the nature of those exposures and their changes over time. There are, three broad categories of non-genetic exposures: internal, specific external and general external as shown in Figure 5-14. The specific environment of a child in the earliest stages of life is very important, namely the body of its mother, and in a small proportion of individuals, the additional early life exposure to in vitro cell culture.
Figure 5 -14 Three different domains of the exposome (Wild 2012b)
Figure 5 -15 The exposome would require measurement of exposures over time across the lifespan of an individual (Wild 2012b)
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Figure 5 -16 Characterizing the exposome for an individual over life course from external and internal sources (Wild et al. 2013)
(Ewa and Danuta 2016), Investigations on the impact of chemicals on the environment and human health have led to the development of an exposome concept. The exposome refers to the totality of exposures received by a person during life, including exposures to lifestyle factors, from the prenatal period to death. The major advantage of measuring chemical-specific DNA adducts is the assessment of a biologically effective dose. (Dennis et al. 2016) Stated that exposome research could serve to improve understanding of the mechanistic connections between exposures and health through linking exposures to specific biological responses to help in mitigation adverse health outcomes across the lifespan. (Cui et al. 2016) stated that environmental exposures are ubiquitous and play a fundamental role in the development of complex human diseases. The exposome, which is defined as the totality of environmental exposures over the life course, allows for systematic evaluation of the relationship between exposures and associated biological consequences and represents a powerful approach for discovery in environmental health research. Implementing the exposome concept is challenged by the ability to accurately assess multiple exposures and the ability to integrate information across the exposure-disease continuum. It is well recognized that both genetic and environmental factors contribute to complex human diseases, and environmental contributions play a major role in disease burden. Dr. Wild described three distinct, but complementary, exposomes: the internal (the within the body measures), specific external (the immediate local environment, radiation, diet, lifestyle, pollution), and general external (societal, economic, psychological). Models of chemical mixtures have to be currently adapted and examined with regard to the Adverse Outcome Pathways (AOP) concepts and exposome concepts. Characterization of the exposome through untargeted measurement of an internal chemical environment promotes data-driven discoveries of causal factors for human diseases or impacts on the ecosystem. To identify the sources and to develop prevention strategies, the main exposures have to be characterized and validated by targeted techniques. Moreover, the discrimination of various exposures also provides the basis for hypothesis-driven research to promote mechanistic understanding. A promising approach to further develop such a mechanistic understanding will be the use of the AOP concept as long as it is evolving further from a linear pathway analysis to a tool to organize the complex networks of toxicity pathways (Escher et al. 2017).
5.7 Discussion & Conclusion Risk assessment helps set scientific and objective priorities for environmental protection. It is an extremely useful and helpful tool to engage an objective basis for decision making and to meet the dangers and hazards. Most countries have a common framework for a risk assessment procedure for contaminated sites which
82 endanger human health, bear ecological risk, and risks to water resources and construction materials. Usually, risk assessment of contaminated sites is triggered by suspicions soil or groundwater contamination. This is followed by an in-depth investigation by using Thresholds Values (TVs) and, finally, remediation. TVs specify generic quality standards for contaminated sites. The application of TVs varies from adjusting long- term quality objectives, through making further investigations, to applying remedial actions. Derivation methods of TVs have scientific, geographical, socio-cultural, regulatory and political categories. They therefore differ from country to country, and TVs numerical values change consequently. Here, I am proposing to use TVs in Libyan sites that take into account the specific climatic and environmental conditions. This guideline is based on the USEPA soil screening guidance. The climate information used is by Köppen−Geiger climate classification. Climate parameters and soil properties influence the calculation of the Volatilization Factor (VF) and Particulate Emission Factor (PEF). Therefore, regional climate and soil parameters are used to determine required Screening Values (SVs) for the risk assessment process.
Various parameters influence the calculations of soil screening values and thus the risk assessment evaluation, of source characteristics, such as contaminated site area, length of contamination source to groundwater flow direction, or the depth of contamination source. Soil characteristics are also important parameters which include soil texture, dry soil bulk density, soil moisture content, soil organic carbon, soil PH, moisture retention exponent, saturated hydraulic conductivity, and average soil moisture content. Another significant parameter, which reflects the geographical characteristics, is the meteorological data where the air dispersion factor (Q/C) is a site-specific value reflecting the corresponding area (temperature, wind). It is also significant to consider hydrogeological characteristics which explain the conceptual site model, infiltration and recharge, hydraulic conductivity, hydraulic gradient, and aquifer thickness. Contaminant properties, such as vapor pressure, Henry’s law constant, solubility in soil water, solubility in soil organic matter are also very important parameters particularly regarding their effects on volatilization.
When Q/C increases, VF increases. Thus the Q/C value is much greater in the arid and semi-arid climatic conditions than other values. Therefore, volatilization is faster in such zones.
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6 Sustainability assessment: Al-Wahat region, Libya Groundwater is the most vital natural resource for life on earth. Groundwater is crucial for human survival and the ecosystem. However, why is groundwater of such importance for drinking, irrigation, and the industry? Groundwater is the largest reservoir of fresh water, unsurpassed by surface water. Increased human activities in the industrial and commercial sectors and expanding urbanization have negative impacts and risk of groundwater contamination. Our modern lifestyle and living standards put a singular strain on the environment. There are many substances and sources of contamination which pollute the groundwater, such as disposal of hazardous wastes, different petroleum facilities and chemical plants. The contamination by these hazardous substances can extend to the aquifer and pollute the subsurface environment for a long period of time. Accordingly, the contaminants compose different phases, vapor, separate (plumes with high concentrations), and non-aqueous phases in the subsurface, which are continuously transported to the passing groundwater. Agents can also slowly diffuse into the low permeable aquifer matrix and stay in the subsurface environment for a long time (Bayer and Finkel 2006). The oases area Al-Wahat in Libya (W100Km*L90Km is located in the south of the Cyrenaica region. It contains the three oases Jalu, Awjila, and Jakharrah and is surrounded by many oil fields, the local population amounts to 40,000 to 45,000 inhabitants. This oases district is a sub-region of the Libyan Desert (Sirt basin) with one of the highest oil reserves in the world (DLIFLC 2012). The region is very important for the economy of the country, as it is one of the major oil production areas of Libya (Alamin 2012). It is also an agricultural area with the biggest production of dates and tomatoes in Libya. Over the years it has suffered major impacts from high PHC contaminations. Figure 7-1 shows the location of the Al-Wahat region in Libya and some pictures of Produced Water (PW) lagoons in the Al-Wahat region. In recent years the local people have started to protest against such contamination. They claim that many fatal diseases, such as carcinogenic diseases, breathing diseases, skin diseases, and blood diseases have evolved from the contamination just as the agriculture areas have suffered from the growing pollution as can be seen in the number of date trees which are falling (JWC 2012). The disposal of produced water causes harmful environmental effects such as the degradation of soils, groundwater, surface water, and ecosystems. Most of the produced water contains elevated rates of dissolved ions (salts), hydrocarbons, and trace elements, untreated produced water discharges may be harmful to the surrounding environment (Katie Guerra et al. 2011). The chemical composition of produced water differs substantially between oilfield locations. However, the general chemical composition which causes environmental impacts come from inorganic compounds (heavy metals), Volatile Aromatic Compounds (VOCs) (Benzene, Toluene, Ethylbenzene, Xylenes), Polycyclic Aromatic Hydrocarbons (PAHs) (e.g. naphthalene), phenols, Naturally Occurring Radioactive Material (NORM), organic acids and additives (Katie Guerra et al. 2011, Laurie 2010, A.M. Allen and Robinson 1993, Biltayib 2006, Neff et al. 2011, Kenneth Lee and Neff 2011).
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Figure 6 -1 Location of Al-Wahat region in Libya (Bauer et al. 2017)
N
Figure 6 -2 Locations of the PW lagoons to the three Oasis (Jalu, Awjila, and Jakharrah)
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Figure 6 -3 lagoon of PW at Al-Wahat
Figure 6 -4 lagoon of PW at Al-Wahat
Figure 6 -5 lagoon of PW at Al-Wahat
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Figure 6 -6 Disposal of oil wastes at Al-Wahat
Figure 6 -7 lagoon of PW at Al-Wahat
6.1 Introduction of assessment This study will present a sustainable remediation assessment of curative actions at the Al-Wahat site. Remediation actions should protect human health and the environment at the site. The site was selected by the National Oil Corporation (Viscarra Rossel et al.) in Libya for applying the sustainable risk-based land management approach. The sustainability approach in the management of the Al-Wahat site should help the decision makers to improve their decision-making process in which they must bear in mind the current economic conditions in the country, the site, and the time scale. Applying the sustainable remediation approach at Al- Wahat site improved the environmental situation by providing a protection to the ecosystems. It was also beneficial to society in general as it provided a better living environment to the locals and other stakeholders. And finally, it was a boost to the economy as it augmented investment opportunities The sustainable risk-based land management approach provides guidance to NOCs, regulators and different stakeholders so that their environmental regulations & laws avoid litigation and improve their reputation.
6.2 Site context Groundwater is the main water source for agriculture in the Al-Wahat region; farmers drilled their own wells at depths of between 60m and more than 100m. The quality of water depends on the locations of the wells and the depth. The shallow wells have poor quality at the Al-Wahat district, while drilled wells that are more than 60 m
87 deep at Awjila and Jalu have good quality. Generally in Jakharrah (North-East), north of Alwahat, the water quality is too poor, while the groundwater is of good quality in Awjila (North-West) and Jalu (South-West). The reason is that the aquifer is close to the sources of natural recharge from the Sirir Basin Aquifer. The total irrigated area is approximately 3500 ha large and the major crops date palms and tomatoes can grow with brackish water.(Alamin et al. 2010). Oil was discovered in the Al-Wahat district in the Sirt basin in1961; therefore, pipelines cross the region between the oilfields. The Libyan oilfields are of great significance for the economy especially for the transportation sector. The oil exploration and production emits waste and pollutants into the environment which has an adverse effect on the entire vicinity. The petroleum wastes include hydrocarbons, solids contaminated with hydrocarbon, produced water with a variety of dissolved and suspended solids, and a wide variety of chemicals which have adverse impacts on the environment (Alamin et al. 2010). Figure 7-1 shows PW lagoons which surround the oases and affect human life and ecosystem (JWC 2012). The overall geology of the Al-Wahat region is dominated by two great sedimentary basins – the Sirte Basin to the north and the Kufra Basin to the south. The basins are sediment-filled troughs, the latter including Mesozoic and Palaeozoic formations, the former Mesozoic and Tertiary. Thicknesses in both basins exceed 3000 m. The sedimentary successions were deposited on the foreland between the stable African Shield and the mobile Tethys belt (Swei 2010, Ahmad 1983). The principal aquifer systems are developed in the continental Nubian formations, mainly the post-Eocene sequence of the Sirte Basin and sandstones in the Kufra Basin. Both aquifer systems have maximum thicknesses in the order of 1000 m but the post-Eocene sequence is distinguished by a wide variable lithology ranging from sands and clays, continental in origin to the south and to sands, clays, and carbonates of mixed continental to the marine origin in the north. Main sub-divisions of the post-Eocene include the Post-Middle Miocene (PMM), the Lower and Middle Miocene (LMM) and the Oligocene, as shown in Figure 7-3. (W.M. EDMUNDS and WRIGHT 1979, Benfield 1974, E. P. Wright et al. 1973, 1974, Wright 1975). The surface soil contains sand, gravel or rock, and is widely devoid of vegetation except in the vicinity of a few largely scattered oases. Dominant features are the Calanscio sand seas and the great Rebiana. To the west of longitude, 22 ° 15'E are extensive flat or gently undulating plains overlain by coarse sand or gravel, which have the local name of "Sarir". More dissected terrain with rocky outcrops occurs in the NW and SE. The general relief is low to moderate. (W.M. EDMUNDS and WRIGHT 1979, E. P. Wright et al. 1973, 1974, Wright 1975). The main groundwater flow direction in the Kufra Basin is to the NE to join the main Nubian Artesian Basin, as shown in Figure 7-4, in which flow is northwards to discharge areas in Mediterranean coastal sabkhats. The groundwater flow direction is northwards into the Sirte Basin also with discharge occurring in coastal sabkhats in the vicinity of the Gulf of Sirte. The two major aquifer systems appear largely independent even where they overlap. A convergence of piezometric head levels does occur on the southern margins of the Sirte Basin and the Nubian aquifer is here probably providing some recharge to the post-Eocene. In general, the hydrogeological considerations indicate that both aquifers are in a transient state of change with current discharge certainly exceeding current recharge. (W.M. EDMUNDS and WRIGHT 1979, E. P. Wright et al. 1973, 1974, Wright 1975, E. P. Wright et al. 1982).
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NW Awjila SE Jalu
Awjil Jalu a
Figure 6 -8 Cross-sections through the post-Eocene succession of Al-Wahat region (from Awjila to Jalu): There are two aquifer systems which have maximum thicknesses in the order of 1000 m but the post-Eocene sequence is distinguished by a wide variable lithology ranging from sands and clays. (after (E. P. Wright et al. 1982))
Figure 6 -9 The main directions of groundwater flow in the Al-Wahat site (E. P. Wright et al. 1982)
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6.3 Conceptual site model
Source of soil and groundwater contamination
The three Oases
Oilfields
Farms
Figure 6 -10 CSM of the Al-Wahat site (many oilfields surround the three oases) (KeyCSM2-Keynetix)
Figure 6 -11 CSM of the Al-Wahat site (KeyCSM2-Keynetix)
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Figure 6 -12 Pollution linkage on the Al-Wahat site (source of contaminants, pathways and receptors) (KeyCSM2-Keynetix)
Figure 6 -13 Matrix samples of source of contaminants to receptors (KeyCSM2-Keynetix)
Groundwater is present at depths of approximately 30 – 35 m-bgl at the south near to J-59 oilfield, with the flow generally towards the north, while at a depth of approximately 5-6 m-bgl at Jakharrah oasis and 0 m in the sabkhat area (discharge area) to the north of the Al-Wahat region (Appendix G)
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6.4 Risk assessment & remediation investigation and plan
6.4.1 Risk assessment process The site is exposed to long-term pollution by the disposal of produced water (more than 30 years). Table 7-2 shows the most important oilfields and the date of production of oil, which started in the 1960s. This indicates which means unfortunately to the long period of environmental pollution in the Al-Wahat region. Land use on the site can be subdivided into residential use (child, aggre. Adult), agricultural use, and commercial/industrial use. The climate condition is arid/dry. Accordingly, a detailed investigation is highly recommended. Locations of PW lagoons are hot spot areas of contaminated soil with a high concentration of contamination in both soil and groundwater (Source of contamination which is lagoons of produced water draw Total Petroleum Hydrocarbon Concentration (TPHC)>5000 mg/l), and High TPH values for soil (up to 24,000 ppm)). Therefore, the petroleum hydrocarbon such as BTEX, PAH, Phenols, and TPH fractions are the main concern of contaminants in this study. Petroleum Vapor Intrusion (PVI) is also a significant problem which should be considered in the Al-Wahat site management. The media of interest here is sand and sandy gravel with clay lenses (pathway).
Not enough soil and groundwater investigations have been undertaken at the site. It is known that the PW disposes to the ground surface at all of the oilfields locations at the Al-Wahat site but the quantity of PW disposed to the ground surface is unknown. The literature shows that the subsurface soil and groundwater beneath the site are extremely impacted by different Total Petroleum Hydrocarbons (TPHC) fractions. High concentrations of BTEX, PAH, Phenols, and TPH are believed to be in the soil and groundwater. The migration of PHC to the subsurface occurred through un-isolated PW lagoons. Lateral migration and spreading of PHC are also likely to have occurred at the groundwater surface. It is assumed that PHC were spread in the past through drilling random private irrigation wells. The area between Awjila and Jakharrah (Awjilah Nafurah oilfield) is considered a high priority area for treatment as it is very close to the oases and the farms. Rakb oilfield & Jalu-59 has 2nd priority, and the 103A&103D oilfields 3rd, Abu Attifle oilfield is the 4th priority whereas Amal oilfield has last priority with the least effects. PHC impact could be up to 3-4 m-bgl. The soil is influenced by the very high concentration of PHC (Crude oil base). The soil is saline and sodic (high concentration of cations and anions exist in the soil: sodium, magnesium, calcium, potassium, sulfate, and chloride (Abdol Hamid et al. 2008). The contaminated soil occurs in very big quantities. Table 6-1 shows selected features of PW lagoons.
Table 6 -1 General characterization of some produced water lagoons at AlWahat region (JWC 2012)
Lagoons no. circumference (Beames Area (Ha) Location to the Oases et al.) L1 3.72 7.35 west L2 3.17 4.36 west L3 5.95 4.91 west L4 3.92 6.93 middle L5 1.07 3.41 South L6 1.06 1.01 South L7 2.18 5.07 South L8 1.31 8.88 South L9 8.18 4.18 south L10 5.90 7.54 south L11 6.84 7.53 Middle L12 1.76 9.19 Middle L13 2.81 3.63 middle L14 7.09 3.08 West L15 2.08 1.5 North L16 2.47 2.11 North L17 1.68 1.29 North L18 2.07 1.46 North
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L19 3.93 5.84 South-east
The future end use of the site is multi-uses. Therefore; a number of alternative risk assessment scenarios should be considered according to potential expansion and growth plans of Al-Wahat region. The current master plan for the site includes a mix of residential (with & without gardens), commercial, agricultural and industrial uses. A potential human health inhalation risk by Petroleum Vapour Intrusion (PVI) into buildings applies for all the potential scenarios considered the current use which means also for this situation unrestricted end use scenario. Maximum contaminant levels (MCLS) for drinking water is recommended to be as a basis for remediation objectives.
NOC should undertake a convenient programme of remedial actions which managed all unacceptable technical risks (to human health and the environment). The objective of this study was, therefore, to identify a range of alternative remedial approaches, taking greater account of sustainability factors applied by SURF-UK and to establish if ranking options to treat the site, therefore, may have more favorable economic, environmental and social impacts. According to current risk assessment process, the study considers two scenarios for the site:
1st site category is the site is normal contaminated site and the 2nd category is the site is the complex site. The complex site is defined as a “site where remedial approaches are not anticipated to bring the site to closure or facilitate transitioning to sustainable long-term management within a reasonable time frame” (ITRC).
Further site investigation should be very convenient prior to the development of a detailed implementation plan for remediation projects at the site. However, the available existing data set was considered to be sufficient for the performance of the sustainability assessment stage.
The future end use of the site is multi-uses. Therefore, a number of alternative risk assessment scenarios should be drawn up according to potential expansion and growth plans for the Al-Wahat region. The current master plan for the site includes a mix of residential (with & without gardens), commercial, agricultural and industrial uses. At present there is a potential human health inhalation risk by Petroleum Vapour Intrusion (PVI) into buildings which would also apply for the unrestricted end use scenario. Maximum contaminant levels (MCLS) for drinking water is recommended as a basis for remediation objectives.
NOC should launch a suitable program of remedial actions which manages all unacceptable technical risks (to human health and the environment). The objective of this study is, therefore, to identify a range of alternative remedial approaches, taking greater account of sustainability factors applied by SURF-UK and to establish ranking options to treat the site, which may have more favorable economic, environmental and social impacts.
Further analyses of a site are expedient prior to the development of a detailed implementation plan for remediation projects at the site. However, the available data was considered to be sufficient for the performance of the sustainability assessment stage.
Table 6-2 History of the most of oil and gas fields in Libya (Hallett 2002)
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Amal, Wahah, Jalu, Awjilah-Nafurah, Abu Attifle, Intisar A, Intisar D and As Sarah are the oilfields which are located in the Al-Wahat region
6.4.2 Ranking of risk Using of fuzzy logic technique for zoning and ranking of the different contaminated sites at Al-Wahat region
Toxicity, concentration, land use, and the location of the contamination source are the criteria for ranking the different contaminated sites in the Al-Wahat. The oases have the same land use and therefore, the suspected contaminated sites have the same land use. The considered contaminants are the same at all sites, therefore the toxicity are the same for all suspected contaminated sites. The concentration should have different values which can be expressed as high, average and low. Table 6-3 shows the different zones with their characterization related to the criterion.
Table 6-3 Different zones with their characteristics at the Al-Wahat region Criterion weight Z1 Z2 Z3 Z4 Z5 Z6 Z7 Z8 Z9 comments Toxicity X=0.8 S S S S S S S S S Concentration X=0.6 H H A H HA L AL L L effect Land use X=1 Y5 Y5 Y4 Y5 Y2 Y1 Y2 Y3 Y1 Toxicity: S: Sever, M: Middle,L: Low; Concentration: H: high, HA: High-Average, A: Average, AL: Average-Low, L:Low; X: weight considered, Y (Y1, Y2, Y3, Y4, Y5): land use levels Y1 is low important and far from current and future Y5 very important and used by human activities.
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N Z9
Z2 Z8 Z3 Jakharrah Oasis
Awjila Oasis Z1
Z4 Z7 Jalu Oasis
Z6 Z5
Z: Zone Groundwater flow direction
Figure 6 -14 Zoning of contamination resources and contaminated sites at the Al-Wahat region
Figure 6 -15 Input and output method for ranking contaminated sites by using fuzzy technique (MATLAB R2015a)
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Figure 6 -16 Rules of fuzzy logic (MATLAB R2015a)
Figure 6 -17 Rules of fuzzy technique to find out values of Z1, Z2 and Z4 (MATLAB R2015a)
Table 6-4 The result of ranking for the contaminated sites at Al-Wahat region by using Fuzzy logic method Zones of contaminated sites Criterion weight comments Z1 Z2 Z3 Z4 Z5 Z6 Z7 Z8 Z9 S: Same Toxicity X=0.8 S S S S S S S S S high toxicity Concentration X=0.6 H H A H HA L AL L L effect Land use X=1 Y5 Y5 Y4 Y5 Y2 Y1 Y2 Y3 Y1 The Result 4.18 4.18 3.0 4.18 2.45 2.45 2.45 2.59 2.45 The Ranking 1 1 2 1 4 4 4 3 4
6.4.3 Screening remediation options process The alternatives and associated technologies are screened to identify those that would be effective for the contaminants and media of interest at the Al-Wahat site. Risk assessment or risk-based calculations that set
96 concentration limits using carcinogenic and/or noncarcinogenic toxicity values under specific exposure conditions are considered the basis for introducing remediation goals. The screening process is done by identifying the environmental media, remediation process objectives, remedial response actions and remediation technologies options. The development and screening process of the remediation technologies is done for The Al-Wahat site according to (USEPA 1988a, 1989, 1991a, b, 1996d, 1997b) as follows:
6.4.3.1 Soil medium Contaminated soil at Al-Wahat site can be classified to the next:
1. Bottom of PW lagoons: they contain PHC, Inorganics and NORM; 2. Banks of PW lagoons: they contain PHC and Inorganics; and 3. Oil pits: soil contaminated with just PHC
Soil of bottom PW lagoons: PHC, Inorganics and Naturally Occurring Radioactive materials (NORM) or radionuclide contaminants Remediation Technologies:
In Situ Physical/Chemical Treatment: Solidification/Stabilization (In Situ Vitrification); Ex Situ Physical/Chemical Treatment (assuming excavation): Solidification/Stabilization (Vitrification)
Soil Bank of PW lagoons: PHC and Inorganics Remediation Technologies:
In Situ Physical/Chemical Treatment: Electrokinetic Separation (Electrokinetics; Electromigration); In Situ Physical/Chemical Treatment: Solidification/Stabilization (In Situ Vitrification); Ex Situ Physical/Chemical Treatment (assuming excavation): Chemical Extraction (Acid Extraction) & (Solvent Extraction); Ex Situ Physical/Chemical Treatment (assuming excavation): Chemical Reduction /Oxidation; Ex Situ Physical/Chemical Treatment (assuming excavation): Separation; Ex Situ Physical/Chemical Treatment (assuming excavation): Soil Washing; Ex Situ Physical/Chemical Treatment (assuming excavation): Solidification/Stabilization (Vitrification); Other Treatment: Excavation, Retrieval, Off-Site Disposal (Removal, Waste Removal-Soils, Waste Removal-Sludges, Waste Removal-Non-soil Solids)
PHC contaminated soil Remediation Technologies:
In-Situ Biological Treatment: Bioventing; In-Situ Biological Treatment: Enhanced Bioremediation; In-Situ Biological Treatment: Phytoremediation; In Situ Physical/Chemical Treatment: Chemical Oxidation; In Situ Physical/Chemical Treatment: Electrokinetic Separation (Electrokinetics; Electromigration); In Situ Physical/Chemical Treatment: Fracturing; In Situ Physical/Chemical Treatment: Soil Flushing; In Situ Physical/Chemical Treatment: Soil Vapor Extraction; In Situ Physical/Chemical Treatment: Solidification/Stabilization (In Situ Vitrification); In-Situ Thermal Treatment: Thermally Enhanced SVE; Ex-Situ Biological Treatment (assuming excavation); Biopiles; Ex-Situ Biological Treatment (assuming excavation); Composting Ex-Situ Biological Treatment (assuming excavation); Landfarming; Ex-Situ Biological Treatment (assuming excavation); Slurry Phase Bio. Treatment Ex Situ Physical/Chemical Treatment (assuming excavation): Chemical Extraction (Acid Extraction) & (Solvent Extraction); Ex Situ Physical/Chemical Treatment (assuming excavation): Chemical Reduction /Oxidation; Ex Situ Physical/Chemical Treatment (assuming excavation): Separation; Ex Situ Physical/Chemical Treatment (assuming excavation): Soil Washing;
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Ex Situ Physical/Chemical Treatment (assuming excavation): Solidification/ Stabilization; Ex-Situ Thermal Treatment (assuming excavation): Incineration; Ex-Situ Thermal Treatment (assuming excavation): Pyrolysis; Ex-Situ Thermal Treatment (assuming excavation): Thermal desorption; and Other Treatment: Excavation, Retrieval, Off-Site Disposal (Removal, Waste Removal-Soils, Waste Removal-Sludges, Waste Removal-Non-soil Solids)
6.4.3.2 Groundwater medium Groundwater at Al-Wahat site are widely contaminated with PHC and Inorganics which are mostly leached from PW lagoons. Therefore; contaminated groundwater at Al-Wahat region is classified as:
Groundwater contaminated by PHC and Inorganics; and Groundwater contaminated only by PHC
Contaminated groundwater: PHC, Inorganics and NORM Remediation Technologies:
Ex Situ Physical/Chemical Treatment (assuming pumping): Separation; and Containment: Deep Well Injection
Contaminated groundwater: PHC and Inorganics Remediation Technologies:
In-situ biological treatment: Phytoremediation (Vegetation-enhanced bioremediation); In Situ Physical/Chemical Treatment: Directional Wells (Enhancement) (Horizontal Wells); In Situ Physical/Chemical Treatment: Passive/Reactive Treatment Walls (Permeable reactive barrier walls; In place bioreaction; In-situ chemical filters); Ex Situ Biological Treatment: Constructed Wetlands; Ex Situ Physical/Chemical Treatment (assuming pumping): Adsorption/ Absorption (Liquid phase adsorption); Ex Situ Physical/Chemical Treatment (assuming pumping): Separation; Containment: Physical Barriers (Vertical cutoff walls; Hydrodynamic barriers; Slurry Trenches, Slurry Walls, Slurry Walls/Underground Barriers); and Containment: Deep Well Injection (Subsurface injection, Underground injection, Class I injection wells).
Contaminated groundwater: PHC and Inorganics Remediation Technologies:
In-situ biological treatment: Enhanced Biodegradation; In-situ biological treatment: Natural Attenuation In-situ biological treatment: Phytoremediation; In Situ Physical/Chemical Treatment: Air Sparging; In Situ Physical/Chemical Treatment: Bioslurping; In Situ Physical/Chemical Treatment: Chemical Oxidation; In Situ Physical/Chemical Treatment: Directional Wells (enhancement); In Situ Physical/Chemical Treatment: Dual Phase Extraction; In Situ Physical/Chemical Treatment: Thermal Treatment; In Situ Physical/Chemical Treatment: Hydrofracturing Enhancements; In Situ Physical/Chemical Treatment: In Well Air Stripping; In Situ Physical/Chemical Treatment: Passive Treatment Walls; Ex Situ Biological Treatment: Bioreactors; Ex Situ Biological Treatment: Constructed Wetlands; Ex Situ Physical/Chemical Treatment (assuming pumping): Adsorption/Absorption; Ex Situ Physical/Chemical Treatment (assuming pumping): Advanced Oxidation Processes; Ex Situ Physical/Chemical Treatment (assuming pumping): Air Stripping;
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Ex Situ Physical/Chemical Treatment (assuming pumping): Granulated Activated Carbon (GAC)/Liquid Phase Carbon Adsorption; Ex Situ Physical/Chemical Treatment (assuming pumping): Ground Water Pumping; Ex Situ Physical/Chemical Treatment (assuming pumping): Ion Exchange; Ex Situ Physical/Chemical Treatment (assuming pumping): Prec./Coag./Flocc.; Ex Situ Physical/Chemical Treatment (assuming pumping): Separation; Ex Situ Physical/Chemical Treatment (assuming pumping): Sprinkler Irrigation; Containment: Physical Barriers; and Containment: Deep Well Injection
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Table 6-5 Screening matrix of Remediation technologies used for Soil (vadose zone), Sediment, Bedrock, and Sludge (https://frtr.gov/)
High Relative overall cost & Performance
Medium
Low
Effectiveness on site-specific
Development Status Development train Treatment O&M Capital System & reliability maintainabili ty Time Availability Nonhalogenated VOCs VOCs Halogenated Nonhalogenated SVOCs Halogenated SVOCs Fuels Inorganics Radionuclides Explosives
Relative costs Relative In-situ biological treatment Bioventing Enhanced Bioremediation Phytoremediation (Vegetation-enhanced bioremediation) In Situ Physical/Chemical Treatment Chemical Oxidation Electrokinetic Separation (Electrokinetics; Electromigration) Fracturing (Pneumatic Fracturing Enhancement) Soil Flushing (Cosolvents Enhancement; Surfactant Flooding) Soil Vapor Extraction (SVE) (In situ soil venting; In situ volatilization; Enhanced volatilization) Solidification/Stabilization (In Situ Vitrification) In Situ Thermal Treatment Thermal Treatment
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(Thermally Enhanced Soil Vapor Extraction) Ex Situ Biological Treatment (assuming excavation) Biopiles (Heap pile bioremediation; Bioheaps; Biomounds; Static-pile composting) (Controlled Solid-Phase Bioremediation)
Composting (Solid-phase soil treatment, Ex situ treatment) Landfarming (Solid phase biodegradation) Slurry Phase Biological Treatment (Slurry biodegradation) Ex Situ Physical/Chemical Treatment (assuming excavation) Chemical Extraction (Acid Extraction) & (Solvent Extraction) Chemical Reduction /Oxidation Dehalogenation Separation Soil Washing Solidification/Stabilization (Vitrification) Ex Situ Thermal Treatment (assuming excavation) Hot Gas Decontamination Incineration Open Burn/Open
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Detonation Pyrolysis Thermal Desorption Containment Landfill Cap (Cap; Landfill cover; Surface cover, Containment, Capping) Landfill Cap Enhancements/Alternatives Other Treatment Excavation, Retrieval, Off- Site Disposal (Removal, Waste Removal-Soils, Waste Removal-Sludges, Waste Removal-Non-soil Solids) (https://frtr.gov/)
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Table 6-6 Screening matrix of Remediation technologies used for Ground Water, Surface Water, and Leachate (https://frtr.gov/)
High Relative overall cost & Performance
Medium
Low
Effectiveness on site-specific
pital
Development Development Status train Treatment O&M Ca System & reliability maintainabil ity Time Availability Nonhalogenated VOCs VOCs Halogenated Nonhalogenated SVOCs Halogenated SVOCs Fuels Inorganics Radionuclides Explosives
Relative costs Relative 2.1 In Situ Biological Treatment Enhanced Bioremediation (Biostimulation, bioaugmentation) Monitored Natural Attenuation (Farhad Analoui et al.), (Intrinsic Remediation; Bioattenuation; Intrinsic Bioremediation) Phytoremediation (Vegetation-enhanced bioremediation ) In Situ Physical/Chemical Treatment Air Sparging (In-situ air sparging, in-situ aeration) Bioslurping (Free product recovery) Chemical Oxidation (Chemical Reduction/Oxidation) Directional Wells (enhancement) (Horizontal Wells) Dual Phase Extraction (Multi-phase extraction;
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Vacuum-enhanced extraction; Free product recovery; Liquid-Liquid Extraction) Thermal Treatment (Hydrous pyrolysis/oxidation; In situ steam extraction, (Hot water/steam flushting) Hydrofracturing Enhancements In-Well Air Stripping (Vacuum vapor extraction; In-well aeration; Vacuum vaporizer well; ground water circulating wells) Passive/Reactive Treatment Walls (Permeable reactive barrier walls; In place bioreaction; In-situ chemical filters) Ex Situ Biological Treatment Bioreactors (Rotating Biological Reactor; Rotating Biological Contactors (RBC)) Constructed Wetlands Ex Situ Physical/Chemical Treatment (assuming pumping) Adsorption/ Absorption (Liquid phase adsorption) Advanced Oxidation Processes (UV oxidation)
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Air Stripping Granulated Activated Carbon/Liquid Phase Carbon Adsorption (Activated carbon; Carbon filtration) Groundwater Pumping/Pump & Treat (Waste Removal - Liquids) Ion Exchange Precipitation/Coagulation/ Flocculation Separation Sprinkler Irrigation Containment Physical Barriers (Vertical cutoff walls; Hydrodynamic barriers; Slurry Trenches, Slurry Walls, Slurry Walls/Underground Barriers) Deep Well Injection (Subsurface injection, Underground injection, Class I injection wells) (https://frtr.gov/)
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Table 6-7 Screening and development of remediation technologies options of Soil medium Remediation process objectives General response actions Remediation technologies options Remediation process options
For human health: Preventing the ingestion and direct contact No action / / Institutional actions: No action/Institutional options: with soil which have non-carcinogens more - No action - Institutional engineering: than the reference doses. - Institutional control fencing - Monitoring - Deed restrictions Preventing the ingestion and direct contact with soil which have carcinogens, cancer Containment technologies: risk level from (10-4 to 10-7) - Vertical barriers Slurry wall, sheet piling - Horizontal barriers Liners, grout injection Preventing the inhalation of soil which has - Capping Clay cap, synthetic membrane, multi-layer -4 carcinogens, cancer risk level from (10 to - Surface control Paving, soil stabilization, diversion/collection, 10-7) grading
For environmental protection (Ecology): Remediation actions/Excavation: - Dust control Revegetation, capping Preventing the migration of contaminants - Remediation/disposal - Sediment control barriers Coffer dams, curtain barriers which would cause groundwater - In situ remediation contamination, therefore high concentration - Disposal excavation Remediation options: of contaminants. - Stabilization, Immobilization - Solidification, fixation - Dewatering - Physical treatment - Chemical treatment - Biological treatment - In situ treatment - Thermal treatment
Removal technologies: - Excavation Solids excavation (USEPA 1988a)
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Table 6-8 Screening and development of remediation technologies options of Groundwater medium Remediation process objectives General response actions Remediation technologies options Remediation process options
For human health: Preventing the ingestion of water which No action / / Institutional actions: No action/Institutional options: have non-carcinogens more than the - No action - Institutional engineering: reference doses or Maximum Concentration - Alternative water source fencing Levels (MCLs). for resedential - Deed restrictions - Institutional control Preventing the ingestion of water which - Monitoring Containment technologies: Slurry wall, sheet piling have carcinogens, cancer risk level more Containment actions: - Vertical barriers Liners, grout injection than (10-4 to 10-7 )or more than MCLs of - containment - Horizontal barriers Clay cap, synthetic membrane, multi-layer carcinogens - Capping Collection/Remediation actions: Preventing the inhalation of soil which has - Collection/remediation Extraction Technologies: Wells, subsurface or leachate collection -4 -7 carcinogens, cancer risk level (10 to 10 ) discharge/In situ - Collection of GW/pumping solution mining, vapour extraction, enhanced groundwater remediation - Enhanced removal oil recovery For environmental protection (Ecology): - Individual units for home Restoring groundwater aquifer to use Remediation options: background concentrations - Physical treatment Coagulation/ flocculation, oil-water separation, air stripping, adsorption - Chemical treatment Neutralization, precipitation, ion exchange oxidation/reduction - In situ treatment Subsurface bioreclamation
Disposal Technologies: - Discharge after remediation to pit - Discharge after remediation to surface water (USEPA 1988a)
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Table 6-9 Screening and development of remediation technologies options of Liquid wastes Remediation process objectives General response actions Remediation technologies options Remediation process options
For human health: Prevention the ingestion and direct contact No action / / Institutional actions: No action/Institutional options: with wastes which have non-carcinogens - No action - Institutional engineering: more than the reference doses. - Institutional control fencing - Monitoring - Deed restrictions Prevention the ingestion and direct contact with soil which have carcinogens, cancer Containment technologies: risk level from 10-4 to 10-7. - Vertical barriers Slurry wall, sheet piling - Horizontal barriers Liners, grout injection Prevention the inhalation of soil which has - Capping Clay cap, synthetic membrane, multi-layer -4 carcinogens, cancer risk level from 10 to - Surface control (paving) Paving, soil stabilization, diversion/collection, 10-7. grading
For environmental protection (Ecology): Remediation actions/Excavation: - Dust control Revegetation, capping Preventing the migration of contaminants - Remediation/disposal - Sediment control barriers Coffer dams, curtain barriers which would cause groundwater - In situ remediation contamination, therefore high concentration - Disposal excavation Remediation options: of contaminants. - Stabilization, Immobilization - Solidification, fixation - Dewatering - Physical treatment - Chemical treatment - Biological treatment - In situ treatment - Thermal treatment
Removal technologies: - Excavation Solids excavation (USEPA 1988a)
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Primary remediation technologies considered:
Table 6-10 Soil of contaminated by PHC, Inorganics and NORM (Radionuclides): Remediation technology type Function Availability of Rate of use Applicability Reliability Removal time comments technology In Situ Physical/Chemical Treatment: Extract/Destruct Full Limited Average Average Average Solidification/Stabilization (In Situ Vitrification) Immobilization Full Limited Better Average Better Immobilization Full Limited Better Average Average Ex Situ Physical/Chemical Treatment (assuming Immobilization Full Limited Average Better Worse excavation): Solidification/Stabilization (Vitrification) Immobilization Full Limited Average Average Better Extract/Immob. Full Limited Better Better Better (https://frtr.gov/), Function: PHC, Inorganics and NORM (Radionuclides)
Table 6-11 Soil contaminated by PHC and Inorganics: Remediation technology type Function Availability of Rate of use Applicability Reliability Removal time comments technology In Situ Physical/Chemical Treatment: Electrokinetic Destruct Full Limited Average Average Average Separation (Electrokinetics; Electromigration) Extract Full Limited Average Average Average In Situ Physical/Chemical Treatment: Extract/Destruct Full Limited Better Better Better Solidification/Stabilization (In Situ Vitrification) Immobilization Full Limited Better Average Better Ex Situ Physical/Chemical Treatment (assuming Extract/Destruct Full Limited Average Average Average excavation): Chemical Extraction (Acid Extraction) & Extract/Destruct Full Limited Average Average Average (Solvent Extraction) Ex Situ Physical/Chemical Treatment (assuming Destruct Full Limited Average Better Average excavation): Chemical Reduction /Oxidation Extract Full Limited Average Better Better Ex Situ Physical/Chemical Treatment (assuming Extract Full Limited Average Better Worse excavation): Separation Extract Full Limited Average Average Better Ex Situ Physical/Chemical Treatment (assuming Extract Full Limited Average Better Average excavation): Soil Washing Extract Full Limited Average Average Better Ex Situ Physical/Chemical Treatment (assuming Immobilization Full Limited Average Better Worse excavation): Solidification/Stabilization (Vitrification) Immobilization Full Limited Average Average Better Other Treatment: Excavation, Retrieval, Off-Site Extract/Immob NA Wide Average Average Better Disposal (Removal, Waste Removal-Soils, Waste Extract/Immob. NA Wide Average Better Better Removal-Sludges, Waste Removal-Non-soil Solids) (https://frtr.gov/), Function: PHC, Inorganics and NORM (Radionuclides)
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Table 6-12 Groundwater contaminated by PHC, Inorganics and NORM: Remediation technology type Function Availability of Rate of use Applicability Reliability Removal time comments technology Ex Situ Physical/Chemical Treatment (assuming Extract Full Limited Better Better Better pumping): Separation Extract Full Limited ??????? Average Better Extract Full Limited ??????? Average Better Containment: Deep Well Injection Immob Full Limited Average Better Better
Immob. Full Limited Average Avergae NA (https://frtr.gov/), Function: PHC, Inorganics and NORM (Radionuclides)
Table 6-13 Groundwater contaminated by PHC and Inorganics: Remediation technology type Function Availability of Rate of use Applicability Reliability Removal time comments technology In-situ biological treatment: Phytoremediation Extract Full Limited Average Average Worse (Vegetation-enhanced bioremediation) Extract Full Limited Average Better Worse In Situ Physical/Chemical Treatment: In Wells Air Extract Full Limited Average Average Worse Stripping Extract Full Limited NA Better Worse In Situ Physical/Chemical Treatment: Passive/Reactive Destruct Full Limited Average Average Worse Treatment Walls (Permeable reactive barrier walls; In Extract Full Limited Better NA Worse place bioreaction; In-situ chemical filters) Ex Situ Biological Treatment: Constructed Wetlands Immob/Destruct Full Limited Average Average Worse Extract Full Wide Average ??????? ??????? Ex Situ Physical/Chemical Treatment (assuming Extract Full Limited Average Worse Worse pumping): Adsorption/ Absorption (Liquid phase Extract Full Limited Average NA NA adsorption) Ex Situ Physical/Chemical Treatment (assuming Extract Full Limited Better Better Better pumping): Separation Extract Full Limited ??????? Average Better Containment: Physical Barriers (Vertical cutoff walls; Immob Full Limited Better Better Worse Hydrodynamic barriers; Slurry Trenches, Slurry Walls, Immob Full Limited Average Better Better Slurry Walls/Underground Barriers) Containment: Deep Well Injection (Subsurface Immob Full Wide Average Average NA injection, Underground injection, Class I injection wells). (https://frtr.gov/), Function: PHC, Inorganics and NORM (Radionuclides)
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6.4.4 Screening remediation technologies options process for the Al-Wahat site by using Fizzy logic technique There are three cases of contamination: a. Soil contaminated with PHC, Inorganics and NORM (bottom of PW lagoons) b. Soil contaminated with PHC and Inorganics (banks of PW lagoons); and c. Groundwater contaminated with PHC and Inorganics Fuzzy logic technique for screening remediation technologies options is used for:
1. 1st step choosing one remediation technology option from the same general remediation technology action (Preliminary assessment) 2. 2nd step choosing one remediation technology option from different remediation technologies actions by applying the next criteria: a. Detailed analysis of alternatives recommended by (USEPA 1988a) and b. Sustainable remediation approach recommended by SURF-UK (www.claire.co.uk/surfuk) Summary of screening for the three cases of contamination:
1st case, Soil contaminated with PHC, Inorganics and NORM: (bottom of PW lagoons)
There is no need for the 1st step because just two technologies from different remediation technologies actions are the result.
Table 6-14 Application of 1st step (preliminary analysis) of alternatives recommended by (USEPA 1988a) Remediation option Contaminant Criteria weight comments 1 2 Applicability 5 1.0 Better Average PHC Reliability 3 0.6 Better Better Cleanup Time 1 0.2 Better Worse Better: < 1 yr. In-situ, Worse:>1 yr. for Ex-situ Applicability 5 1.0 Better Average Inorganics Reliability 3 0.6 Average Average Cleanup Time 1 0.2 Better Better Better: < 1 yr. In-situ, Better: < 0.5 yr. Ex-situ Applicability 5 1.0 Better Better NORM Reliability 3 0.6 Average Better Cleanup Time 1 0.2 Average Better Average: 1-3 yrs. In-situ, Better: < 0.5 yr. Ex- situ 1: In Situ Physical/Chemical Treatment: Solidification/Stabilization (In Situ Vitrification); 2: Ex Situ Physical/Chemical Treatment (assuming excavation): Solidification/Stabilization (Vitrification)
Time is an important boundary condition between the different remediation technologies for contaminated soil. Therefore, different time scenarios should be considered from less than two years (short-term) to more than three years to six years (medium-term) and finally from six years to more than ten years (long-term) as explained in Teble 6-24.
Application of Fuzzy logic:
Output of option 1: Effectiveness = 2.4 & Cleantime = 2.56;
Output of option 2: Effectiveness = 2.35 & Cleantime = 2.00
From figures 6-18 & 6-19, the 1st option: In Situ Physical/Chemical Treatment: Solidification/Stabilization (In Situ Vitrification) is quite much better in both effectiveness and time of cleanup than the 2nd option: Ex Situ Physical/Chemical Treatment (assuming excavation): Solidification/Stabilization (Vitrification)
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Figure 6 -18 Input & Output of assessment of effectiveness and cleanup time of In Situ Physical/Chemical Treatment: Solidification/Stabilization (In Situ Vitrification) remediation technology for treatment of contaminated soil by PHC, Inorganics and Radionuclides
Figure 6 -19 Input & Output of assessment of effectiveness and cleanup time of Ex Situ Physical/Chemical Treatment (assuming excavation): Solidification/Stabilization (Vitrification) remediation technology for treatment of contaminated soil by PHC, Inorganics and Radionuclides.
2nd case, Soil contaminated with PHC and inorganics: (banks of PW lagoons)
1st step: selecting one remediation technology option from the same general remediation technology action
Table 6-15 1st group of In Situ Physical/Chemical Treatment Technologies: Remediation option Contaminant Criteria weight comments 1 2 Applicability 5 1.0 Average Better PHC Reliability 3 0.6 Average Better Cleanup Time 1 0.2 Average Better Applicability 5 1.0 Average Better Inorganics Reliability 3 0.6 Average Average Cleanup Time 1 0.2 Average Better 1: In Situ Physical/Chemical Treatment: Electrokinetic Separation (Electrokinetics; Electromigration); 2:In Situ Physical/Chemical Treatment: Solidification/Stabilization (In Situ Vitrification)
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Figure 6 -20 Input & Output of assessment of effectiveness and cleanup time of In Situ Physical/Chemical Treatment: Electrokinetic Separation (Electrokinetics; Electromigration) remediation technology for treatment of contaminated soil by PHC and Inorganics
Figure 6 -21 Input & Output of assessment of effectiveness and cleanup time of In Situ Physical/Chemical Treatment: Solidification/Stabilization (In Situ Vitrification) remediation technology for treatment of contaminated soil by PHC and Inorganics.
Output of option 1: Effectiveness = 2.00 & Cleantime = 2.0;
Output of option 2: Effectiveness = 2.40 & Cleantime = 3.05
From figures 6-20 & 6-21, the 2nd option: In Situ Physical/Chemical Treatment: Solidification/Stabilization (In Situ Vitrification) remediation technology is superior in both effectiveness and time of cleanup to the 1st option: In Situ Physical/Chemical Treatment: Electrokinetic Separation (Electrokinetics; Electromigration) remediation technology.
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Table 6-16 The 2nd group of Ex Situ Physical/Chemical Treatment Technologies: Remediation options Contaminant Criteria weight comments 1 2 3 4 Applicability 5 1.0 Average Average Average Average PHC Reliability 3 0.6 Average Better Better Better Cleanup Time 1 0.2 Average Average worse Average Applicability 5 1.0 Average Average Average Average Inorganics Reliability 3 0.6 Average Better Average Average Cleanup Time 1 0.2 Average Better Better Better 1:Ex-Situ Physical/Chemical Treatment (assuming excavation): Chemical Extraction (Acid Extraction) & (Solvent Extraction); 2:Ex-Situ Physical/Chemical Treatment (assuming excavation): Chemical Reduction /Oxidation; 3:Ex-Situ Physical/Chemical Treatment (assuming excavation): Separation; 4:Ex-Situ Physical/Chemical Treatment (assuming excavation): Soil Washing
Figure 6 -22 Input & Output of assessment of effectiveness and cleanup time of Ex-Situ Physical/Chemical Treatment (assuming excavation): Chemical Extraction (Acid Extraction) & (Solvent Extraction) remediation technology for treatment of contaminated soil by PHC and Inorganics
Figure 6 -23 Input & Output of assessment of effectiveness and cleanup time of Ex-Situ Physical/Chemical Treatment (assuming excavation): Chemical Reduction /Oxidation remediation technology for treatment of contaminated soil by PHC and Inorganics
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Figure 6 -24 Input & Output of assessment of effectiveness and cleanup time of Ex-Situ Physical/Chemical Treatment (assuming excavation): Separation remediation technology for treatment of contaminated soil by PHC and Inorganics
Figure 6 -25 Input & Output of assessment of effectiveness and cleanup time of Ex-Situ Physical/Chemical Treatment (assuming excavation): Soil Washing remediation technology for treatment of contaminated soil by PHC and Inorganics
Output of option 1: Effectiveness = 2.00 & Cleantime = 2.0;
Output of option 2: Effectiveness = 2.25 & Cleantime = 1.44;
Output of option 3: Effectiveness = 2.25 & Cleantime = 2.0; and
Output of option 4: Effectiveness = 2.25 & Cleantime = 2.56
From figures 6-22 & 6-23 & 6-24 & 6-25, the 4th option: Ex-Situ Physical/Chemical Treatment (assuming excavation): Soil Washing remediation technology is the best in time of cleanup than the other options: 1:Ex-Situ Physical/Chemical Treatment (assuming excavation): Chemical Extraction (Acid Extraction) & (Solvent Extraction); 2:Ex-Situ Physical/Chemical Treatment (assuming excavation): Chemical Reduction /Oxidation; 3:Ex-Situ Physical/Chemical Treatment (assuming excavation): Separation. While it has the same effectiveness with the 2nd and 3rd options.
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- 2nd step: choosing one remediation technology option from different remediation technologies actions by applying the next criteria:
1. Long-term effectiveness in preserving human health and the environment 2. Reduction of toxicity, mobility and volume 3. Short-term effectiveness in protection of human health and the environment 4. Implementability and 5. Cost (the capital and operation and maintenance (O&M) costs
6.4.5 Detailed analysis of alternatives recommended by (USEPA 1988a) . Contaminated soil Table 6-17 2nd step, a- Detailed analysis of alternatives recommended by (USEPA 1988a) Remediation options Contaminant Criteria weight comments 1 2 3 4 Long-term 4 0.8 Average Average- Average- High High High Reduction 5 1.0 Average High High High 3 Low- Low- Low- Low- PHC Short-term 0.8 Average Average Average Average Implement 5 0.6 High Average High High Cost (O&M) 4 0.8 Average High Average- Average High Long-term 4 0.8 High Average High Average Reduction 5 1.0 High High High Average Short-term 3 0.8 Average Average Low- Low- Inorganics Average Average Implement 5 0.6 High Average High High Cost (O&M) 4 0.8 Average High Average- Average High 1: In Situ Physical/Chemical Treatment: Solidification/Stabilization (In Situ Vitrification); 2: Ex-Situ Physical/Chemical Treatment (assuming excavation): Soil Washing; 3: Ex Situ Physical/Chemical Treatment (assuming excavation): Solidification/Stabilization (Vitrification); 4: Other Treatment: Excavation, Retrieval, Off-Site Disposal (Removal, Waste Removal-Soils, Waste Removal-Sludges, Waste Removal- Non-soil Solids) (https://frtr.gov/ , USEPA 2006)
Figure 6 -26 Input and output method for evaluation remediation technologies for contaminated soil at Al-Wahat site by using fuzzy technique
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Figure 6 -27 Rules of fuzzy technique to find out values of different remediation alternatives
Table 6-18 The result of assessment by using fuzzy technique to evaluate remediation technologies alternatives for contaminated soil at Al-Wahat region Remediation technologies options comments 1 2 3 4 The Score 2.53 2.54 2.55 2.53 The Rank 2 2 1 2
. Contamination of groundwater
When the groundwater is contaminated with PHC, Inorganics and NORM, the assessment should be applied between the next remediation technologies: the 1st option is the Ex Situ Physical/Chemical Treatment (assuming pumping) Separation technology and the 2nd option which known as the Containment: Deep Well Injection option. The 1st option is the best because the 2nd option is unlikely applied in Inorganics and NORM.
3rd case, groundwater contaminated with PHC and inorganics:
Table 6-19 1st step of preliminary assessment of two options Remediation option Contaminant Criteria weight comments 1 2 Applicability 5 1.0 Average Average PHC Reliability 3 0.6 Average Average Cleanup Time 1 0.2 Worse Worse Applicability 5 1.0 NA/ Better Worse Inorganics Reliability 3 0.6 Better NA/ Worse Cleanup Time 1 0.2 Worse Worse 1: In Situ Physical/Chemical Treatment: In Wells Air Stripping; 2: In Situ Physical/Chemical Treatment: Passive/Reactive Treatment Walls (Permeable reactive barrier walls; In place bioreaction; In-situ chemical filters)
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Figure 6 -28 Input & Output of assessment of effectiveness and cleanup time of In Situ Physical/Chemical Treatment: In Wells Air Stripping remediation technology for treatment of contaminated soil by PHC and Inorganics
Figure 6 -29 Input & Output of assessment of effectiveness and cleanup time of In Situ Physical/Chemical Treatment: Passive/Reactive Treatment Walls (Permeable reactive barrier walls; In place bioreaction; In-situ chemical filters) remediation technology for treatment of contaminated groundwater by PHC and Inorganics
Output of option 1: Effectiveness = 1.9 & Cleantime = 0.941;
Output of option 2: Effectiveness = 2.1 & Cleantime = 0.941;
From Figures 6-29 & 6-30,the 2nd option: In Situ Physical/Chemical Treatment: Passive/Reactive Treatment Walls (Permeable reactive barrier walls; In place bioreaction; In-situ chemical filters) remediation technology is better in effectiveness and same in time of cleanup than the 1st option: In Situ Physical/Chemical Treatment: In Wells Air Stripping remediation technology
Table 6-20 1st step of preliminary assessment of two options Remediation option Contaminant Criteria weight comments 1 2 Applicability 5 1.0 Average Better PHC Reliability 3 0.6 Worse Better
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Cleanup Time 1 0.2 Worse Better Applicability 5 1.0 Average Worse Reliability 3 0.6 NA/ Average Inorganics Worse Cleanup Time 1 0.2 NA/ Better Worse 1: Ex Situ Physical/Chemical Treatment (assuming pumping): Adsorption/ Absorption (Liquid phase adsorption); 2: Ex Situ Physical/Chemical Treatment (assuming pumping): Separation
Figure 6 -30 Input & Output of assessment of effectiveness and cleanup time of Ex Situ Physical/Chemical Treatment (assuming pumping): Adsorption/ Absorption (Liquid phase adsorption) remediation technology for treatment of contaminated groundwater by PHC and Inorganics
Figure 6 -31 Input & Output of assessment of effectiveness and cleanup time of Ex Situ Physical/Chemical Treatment (assuming pumping): Separation remediation technology for treatment of contaminated groundwater by PHC and Inorganics
Output of option 1: Effectiveness = 1.75 & Cleantime = 0.941;
Output of option 2: Effectiveness = 2.0 & Cleantime = 3.06;
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From Figures 6-30 & 6-31, the 2nd option: Ex Situ Physical/Chemical Treatment (assuming pumping): Separation remediation technology is much better in both effectiveness and time of cleanup than the 1st option: Ex Situ Physical/Chemical Treatment (assuming pumping): Adsorption/ Absorption (Liquid phase adsorption) remediation technology
Table 6-21 1st step of preliminary assessment of two options Remediation option Contaminant Criteria weight comments 1 2 Applicability 5 1.0 Better Average Reliability 3 0.6 Better Average PHC Cleanup Time 1 0.2 Worse NA/ Worse Applicability 5 1.0 Average xxxxx Inorganics Reliability 3 0.6 Better xxxxx Cleanup Time 1 0.2 Better xxxxx 1: Containment: Physical Barriers (Vertical cutoff walls; Hydrodynamic barriers; Slurry Trenches, Slurry Walls, Slurry Walls/Underground Barriers); 2: Containment: Deep Well Injection (Subsurface injection, Underground injection, Class I injection wells) xxxx: unlikely to use From Table, the 1st option: Containment: Physical Barriers (Vertical cutoff walls; Hydrodynamic barriers; Slurry Trenches, Slurry Walls, Slurry Walls/Underground Barriers) remediation technology is the best, because the 2nd option is unlikely applied for Inorganics.
2nd step detailed screening by using (USEPA 1988a) Table 6-22 2nd step, a- Detailed analysis of alternatives recommended by (USEPA, 1988a) Remediation options Contaminant Criteria weight comments 1 2 3 4 5 Long-term 4 0.8 Av.Hi Av.Hi Lo.Av. Average High Reduction 5 1.0 Av..Hi Av.Hi.. High High Av.Hi. PHC Short-term 4 0.8 Av.Hi High Lo.Av. Average Average Implement 3 0.6 High Average High Av.Hi. Low Cost (O&M) 4 0.8 Low High High High High Long-term 4 0.8 Average Average Lo.Av. Averag High Reduction 5 1.0 Average Av.Hi. High Average Av.Hi. Inorganics Short-term 4 0.8 Average High Lo.Av. Lo.Av. Average Implement 3 0.6 High Average High Av.Hi. Low Cost (O&M) 4 0.8 Low High High High High 1: In-situ biological treatment: Phytoremediation (Vegetation-enhanced bioremediation); 2: In Situ Physical/Chemical Treatment: Passive/Reactive Treatment Walls (Permeable reactive barrier walls; In place bioreaction; In-situ chemical filters); 3: Ex Situ Biological Treatment: Constructed Wetlands; 4: Ex Situ Physical/Chemical Treatment (assuming pumping): Separation; 5: Containment: Physical Barriers (Vertical cutoff walls; Hydrodynamic barriers; Slurry Trenches, Slurry Walls, Slurry Walls/Underground Barriers) (https://frtr.gov/ , USEPA 2006) Table 6-23 The result of assessment by using fuzzy technique to evaluate remediation technologies aternatives for contaminated soil at Al-Wahat region Remediation technologies options comments 1 2 3 4 5 The Score 2.9 2.5 2.55 2.53 2.5 The Rank 1 4 2 3 4
The 1st option has the biggest score while the other alternatives have only small differences in the total score. The 1st option has limitation in application such as the groundwater table shouldn’t exceed three meter.
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6.5 Sustainable remediation approach recommended by SURF-UK (www.claire.co.uk/surfuk)
The sustainability assessment process
6.5.1 General The sustainability assessment process is proposed by NOC with SuR expert (International consultant) for the Al- Wahat site and should involve the following steps:
Primary data collection which is relevant to assist the first workshop (identifying stakeholders, outline the main business/region objectives, reporting site characterization findings) The first workshop is a substantial base for the project team (establishing the assessment context, agreement on the objectives and boundaries of the assessment) Collation of the desired additional data to perform the assessment Completion of the assessment process and Reporting the assessment conclusion
6.5.2 Objectives of the sustainability assessment The objective of the sustainable remediation assessment was to identify a favored remediation (soil & groundwater remediation) technology, which is super deep on broad sustainability factors (environment, social, economy) with respect to the overall business objectives for the region. The sustainability assessment process is useful for deciding which remediation technology to use especially which screening process for identifying the best remediation technology to treat contaminated soil .
6.5.3 Stakeholder engagement
The following stakeholders were identified:
National Oil Corporation (Viscarra Rossel et al.) Environmental General Authority (Meyer et al.) of Libya and branch of Al-Wahat Libyan Petroleum Institute (LPI) Oil companies (owners and operators of oilfields Environmental consultant in decision making (SuR expert) Risk assessor (international experts) Environmental consultants (international & native experts) Tribal leaders Farmers Union Affected people Investors Remediation technology expert (Environmental contractor) Local councils and Land owners The sustainability assessment should be undertaken by NOC with Env. Consultants. Stakeholders engagement should be also managed in a proper and practical process. Therefore, the assessment team should respect and take into account all stakeholders views and opinions in the decision-making process. Figure 4-2 explains stakeholder interaction and engagement method. The next views are just a conception: NOC & Oil companies & LPI: The main interests are to protect human health and the environment, gaining experience in sustainability approach, economical issues (financing, a well-known budget), training technical people to create environmental staff especially for human & environmental protection, and remediation technologies transfer.
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EGA, branch of Al-Wahat: The major interest is to preserve public health in the region and to protect the environment. Their demand is to ensure full compliance with the regulatory environmental requirements ensuring that no future issues arise from residual contamination. Local councils: interest in the development of the site is in full compliance with respect to local regulations, and should guarantee no risks arising from residual contamination. Affected neighbors & Neighbors nearby: (farmers, land owners, tribal leaders, residential) the main interests are to keep the environment clean without any pollution (health, safety, and environment are first). renewable energy is recommended and should be applied, employment of Al-Wahat people, applying the sustainability approach, construction of Nature reserves and entertainments, Conducting a complete health survey (many diseases are found on the region such as carcinogenic diseases, frequent infertility, congenital malformations, difficulty during delivery, hearth diseases, different skin diseases) and filling unit of cooking gas. Investors: interest in ensuring that there will not be any future trouble from residual contamination and that the site is left in a state that is fit for the proposed future use. Reduced time scales may also be of interest. approach, construction of Nature reserve and entertainments, Conducting a complete health survey (many diseases are found on the region such as carcinogenic diseases, frequent infertility, congenital malformations, difficulty during delivery, hearth diseases, different skin diseases) and filling unit of cooking gas. Investors: interest in ensuring that there will not be any future trouble from residual contamination and that the site is left in a state that is fit for the proposed future use. Reduced time scales may also be of interest.
6.5.4 Scope The investment in such region and countries is not an easy process but it is possible and may be providing an advantage because of no a defined or specific time period is strictly required. Moreover, the existing and future master plans for the development of the region are not known. It is therefore clear that there are uncertainties relating to both the time frame for the finishing of remediation projects and the remediation actions standards (soil & groundwater standards). Accordingly, the project team should develop a number of scenarios to be examined within the assessment method. Table 6-24 shows these scenarios
Table 6-24 The scenarios considered within the assessment Duration of remediation projects Type of End use Short term Long-term (>10 contaminated site Mid-term (6 years) (<2years) years) According to Scenario 1 Scenario 2 Scenario 3 current master plan Normal site Updated site master Scenario 4 Scenario 5 Scenario 6 plan
The current master plan for the region includes a mix of residential, commercial/industrial use and agricultural use which means also residential properties with gardens. The updated master plan means a special plan for use. Remediation targets/soil and groundwater treatment standards should be derived for the previous scenarios, therefore applicable remediation standards would vary according to the development scenario. There are different locations where the soil is contaminated and those are found on the locations of PW lagoons surrounding the whole region. Contaminated groundwater is considered for the overall the region.
6.5.5 Boundaries & Limitation The project team should agree on some boundaries to schedule the assessment process, therefore the following boundaries would be perfect for the assessment:
Time: should be limited for treatment of remediation works for soil especially to the close PW lagoons sites to oases and agricultural land.
Financial: The financing is highly important aspect especially for NOC and oil companies
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Lifecycle: it should be related to the start and close the project including mobilization and demobilization of specialized equipment to the region.
Spatial: if there is spatial boundary limited to the region. Remedial actions for soil will take place at PW lagoons
Indicators: SURF-UK indicators
6.5.6 Options considered The project team should agree about the application of in situ and ex-situ technologies at every site for contaminated soil (PW lagoons sites) in the Al-Wahat region. The technologies are (defined in the section 7.2.2.2 Screening remediation options process). A total of four soil remediation technologies were screened as being potentially applicable for the remediation of soils at the Al-Wahat site. While a total of five groundwater remediation technologies were screened as also being potentially applicable for the remediation of groundwater at the Al-Wahat site. But one soil remediation technology was screened as being highly applicable for the remediation of bottom soils of the PW lagoons at the Al-Wahat site. Tables 7-25 & 7-26 & 7-27 summarised these alternatives with their major actions.
Table 6-25 Technology identified for treatment of bottom soils of PW lagoons at the Al-Wahat site Technology option Major features In Situ Physical/Chemical Treatment: - Mobilization of Mechanical tool and equipment Solidification/Stabilization (In Situ (Auger/caisson systems and injector head systems) to the Vitrification) site; (In situ S/S is short- to medium-term; - Construction of the cover that consists of: an intermediate In situ ISV is typically short-term) cover layer (Oil sand) and an upper cover layer (deposit consisting of sand or clay impregnated with crystalline salts) - For In Situ Vitrification: Mobilization of Elektro equipment (to melt soil or other earthen materials) Demobilization of equipment from the site Table 6-26 Technologies screened for treatment of soils of PW lagoons banks Technology option Major features 1: In Situ Physical/Chemical - Mobilization of mechanical tools and equipment Treatment: Solidification/Stabilization (Auger/caisson systems and injector head systems) to the (In Situ Vitrification) site; (In situ S/S is short- to medium-term; - Construction of the cover that consists of : an intermediate In situ ISV is typically short-term) cover layer (oil sand) and an upper cover layer (deposit consisting of sand or clay impregnated with crystalline salts) - For In Situ Vitrification: Mobilization of electro equipment (to melt soil or other earthen materials) - Demobilization of equipment from the site 2: Ex-Situ Physical/Chemical - Mobilization, set up and commissioning of soil washing Treatment (assuming excavation): Soil plant at the site; Washing; - Excavation of soils and transfer to stockpiling location (Soil washing is short- to medium- adjacent to remediation unit; term) - Load soils to the soil washing unit and treatment (screening, scrubber and washer units and associated separation); - Stockpiling of remediated soils; - Back fill and compaction of remediated soils; - Disposal of filter cake material; and - Demobilization of plant and equipment from the site. 3: Ex Situ Physical/Chemical - Mobilization of excavation equipment to the site; Treatment (assuming excavation): - Mobilization of mechanical tools and equipment Solidification/Stabilization (Auger/caisson systems and injector head systems) to the (Vitrification) Solidification/Stabilization (S/S) site;
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(Ex situ S/S is a short- to medium-term - Excavation of soils and direct loading onto off site waste technology) haulage vehicles; - Transfer of material from the site to the S/S site; - Construction of the cover that consists of : an intermediate cover layer (Oil sand) and an upper cover layer (deposit consisting of sand or clay impregnated with crystalline salts) - For In Situ Vitrification: Mobilization of electro equipment (to melt soil or other earthen materials) to the S/S site - Solidify and stabilize soils in the S/S site; and - Demobilization of equipment from the site 4: Other Treatment: Excavation, - Mobilization of plant and equipment to the site; Retrieval, Off-Site Disposal (Removal, - Excavation of soils and direct loading onto off site waste Waste Removal-Soils, Waste haulage vehicles; Removal-Sludges, Waste Removal- - Transfer of material from the site to the landfill site (likely Non-Soil Solids) north the site); (Duration of operation and - Stock piling of materials at landfill site; maintenance lasts as long as the life of - Import of clean backfill material to the site from the the facility) surrounded areas and backfill and compaction of this material within excavation; and - Demobilization of plant and equipment from site.
Table 6-27 Technologies screened for treatment of groundwater at the Al-Wahat site Technology option Major features 1: In-situ biological treatment: - Construction of treatment farm/s of series of treatment Phytoremediation (Vegetation- plants; enhanced bioremediation) - Irrigate plants by direct groundwater beneath roots for more (long-term) than one growing season (groundwater less than 3 m from the surface); - Harvest plants and grow a new season 2: In Situ Physical/Chemical - Mobilization of mechanical tools and equipment to the site; Treatment: Passive/Reactive - Mobilization of walls and materials needed; Treatment Walls (Permeable reactive - Construction of permeable walls in their locations; barrier walls; In place bioreaction; In- - Monitoring of treatment process of permeable reactive walls situ chemical filters) (long-term operation to control migration of contaminants in ground water) (Long-term) 3: Ex Situ Biological Treatment: - Mobilization of equipment to construct wetland/s; Constructed Wetlands - Construction of wetland according to special designs; (Wetland treatment is a long-term - Growth selected plants and trees to treat contaminated areas technology intended to operate - Transfer of the contaminated water to constructed wetland/s; continously for years) - Monitoring of the constructed wetland/s 4: Ex Situ Physical/Chemical - Mobilisation of plant and equipment to the site; Treatment (assuming pumping): - Set up the separation plant/s to the source of contaminated Separation water; (duration of short-term) - Control and monitor the process 5: Containment: Physical Barriers - Mobilization of mechanical tools and equipment to the site; (Vertical cutoff walls; Hydrodynamic - Construction of trenches, barriers; Slurry Trenches, Slurry - Monitoring of treatment process Walls, Slurry Walls/Underground Barriers)
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(In general long-term technology) (https://frtr.gov/ , www.claire.co.uk/surfuk , USEPA 2006)
6.5.7 Sustainability assessment process Fuzzy logic is used here to assess the sustainability due to its capacity to understand, compile translate and deal with qualitative and linguistic values. Certain options are screened and then evaluated on the basis of a time frame. They are predicted and estimated upon proposed costs as described in tables 7-28 & 7-29, the time frame of the 2nd and 3rd scenarios in case of contaminated soil and contaminated groundwater.
The SuRF-UK approach is recommended as a methodology for sustainability assessments. It involves three assessment classes: tier 1-qualitative assessment, tier2-semi-quantitative assessment and tier3-quantitative assessment. Tier1 approach is the 1st and simplest tier of appraisal and appropriate for assessment. This approach involves the identification of relevant 'categories of indicators' (assessment criteria) for each of the three pillars of sustainability (economic, environmental and social). The SuRF-UK Sustainable Remediation Indicators are used as the basis for this tier. Table 6-30 shows the SuRF-UK indicators as assessment criteria with associated weightings, comments related to the site and applicable indicators.
Table 6-28 Remediation options and time scenarios for contaminated soil Masterplan with Duration of remediation projects “scenarios” Type of masterplan Existing master plan of the site Comments on costs Time duration Long-term (6 & >10 O&M Capital Relative Short term (<2years) Mid-term (3-6 years) years) costs Scenario 1 2 3 Remediation alternatives Solidification/Stabilization PHC: Fit PHC: Fit PHC: Fit Middle High Low (S/S) (In Situ Inorganics: Fit Inorganics: Fit Inorganics: Fit Vitrification) Soil Washing PHC: Fair PHC: Fit PHC: Fit High High Middle Inorganics: Fit Inorganics: Fit Inorganics: Fit Solidification/Stabilization PHC: Unfit PHC: Fit PHC: Fit Middle High Low (S/S) (Vitrification) Inorganics: Fit Inorganics: Fit Inorganics: Fit Excavation, Disposal PHC: Fit PHC: Fit PHC: Fit Low Low Depends on Inorganics: Fit Inorganics: Fit Inorganics: Fit Agents&site (https://frtr.gov/)
Table 6-29 Remediation options and time scenarios for contaminated groundwater Masterplan with Duration of remediation projects “scenarios” Type of masterplan Existing master plan of the site Comments on costs Long-term (6 & >10 O&M Capital Relative Time duration Short term (<2yrs) Mid-term (3-6 years) years) costs Scenario 4 5 6 Remediation alternatives Phytoremediation PHC: Unfit PHC: Fair PHC: Fit Low Low Low Inorganics: Unfit Inorganics: Fair Inorganics: Fit Permeable reactive PHC: Unfit PHC: Fair PHC: Fit Middle High Middle barrier walls Inorganics: Unfit Inorganics: Fair Inorganics: Fit Constructed Wetlands PHC: Unfit PHC: Fair PHC: Fit Middle High Middle Inorganics: Unfit Inorganics: Fair Inorganics: Fit Separation PHC: Fit PHC: Fit PHC: Fit High High High Inorganics: Fit Inorganics: Fit Inorganics: Fit Slurry Trenches, Slurry PHC: Unfit PHC: Fair PHC: Fit Middle High Low Walls Inorganics: Fit Inorganics: Fit Inorganics: Fit (https://frtr.gov/)
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Table 6-30 The SuRF-UK indicators (Assessment criteria) and the proposed related weightings for remediation options at Al-Wahat site Theme Indicator (Criteria) Weight Comments related the site Applicable indicators
Emissions to air: 1 Less emissions of (CO2, decrease CO2 emissions and GHG ENV1 GHG) from technology (e.g. NOx, Sox, VOCs) Soil and ground 0 Contaminated soils outside Reduce emissions to soil and conditions: ENV2 the Oases improve the functionality of soil Groundwater & 0 Any impacts will be the Restrain spills and leaks, lower Surface Water: same for all technologies release of contaminated leach ENV3
Ecology: ENV4 0 During any remediation Preservation of biodiversity of study there is EIA ecosystem Natural resources 0.8 Impacts on landfills and Lower using of: water, natural and waste: ENV5 water resources resources, fossil fuel and minimize ironmental production of waste. Rise of waste
Env recovery Direct economic 1 The cost of remediation Minimize cost, avoid wastage, costs and benefits: activities and improve the improve information and data ECON1 site value (can work as goal gathering and finding the proper with indirect economic) solution Indirect economic 0 general economic Support long-term investment, costs and benefits: performance of the area infrastructure measures ECON2 Employment and 1 Chances and priority of Local employment with training and employment employment for neighbors improve skills capital: ECON3 Induced economic 0 Excluded now (unstable Foreign economic interests costs and benefits: country)
ECON4 Project lifespan and 0.6 Flexibility of option to adapt Mitigation of climate change and
nomic flexibility: ECON5 with new circumstances setting long-term institutional
Eco control Human health and 1 Safe remedy site for people Safe workers health and life safety: SOC1 for health and life Ethics and equality: 0 Same for all options Compilation with regulations, SOC2 participation of community and Equality of impact assessment Neighborhoods and 1 Prevent all impacts (dust, reduce impacts on amenity (e.g. locality: SOC3 noise, light, odour, dust, odour, noise), lower traffic & vibrations) on local disruption, particularly in residential communities areas Communities and 0 Use the properties of NOC efficient communication with local community without any disturbance of community and involvement of
involvement: SOC4 communities (same for all) Stakeholder in decision-making
ial Uncertainty and 0.4 Compliance with regulations Optimize data and information
Soc evidence: SOC5 and variations of CSM collection (Bardos et al. 2016, Bardos 2014, www.claire.co.uk/surfuk)
6.5.8 Uncertainties When deciding on an appropriate sustainability process, many different opinions are voiced by the various interested parties originating mainly from uncertainties in evaluating the many factors involved. In order to deal with these uncertainties, fuzzy logic, which can deal with these ambiguities, is applied.
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6.6 The sustainability assessment summary Based on the fuzzy logic approach for sustainable remediation assessment, the In Situ Physical/Chemical Treatment: Solidification/Stabilization (S/S) (In Situ Vitrification) is deemed the most sustainable and convenient remedial solution for contaminated soil at the Al-Waha site. In contrast, the Ex Situ Biological Treatment: Constructed Wetlands is deemed the most sustainable and suitable remedial solution for contaminated groundwater at the Al-Waha site. In scenario 2 for contaminated soil, the in situ S/S hast the greatest environmental score (4/5), while it has the same social score with the ex situ S/S and the ex situ S/S has t the greaest economic score. As a result, the environmental pillar is the guidance for this scenario. In scenario 3 for contaminated soil, the same procedure is applied without any apparent difference to scenario 2 except that the ex situ S/S decreases the social pillar while the excavation and disposal option increases the environmental pillar. Scenario 2 and 3 for contaminated groundwater contain five alternatives for every scenario. The constructed wetland has the greatest scores on both scenarios. In scenario 2, the environmental and economic pillars of the constructed wetland option receive the greatest scores, while the social pillar of the phytoremediation and constructed wetland has the same. In the long-term scenario 3 for contaminated groundwater, the total score of the phytoremediation increases by the long-term influence of the economic pillar, while the score of the separation option decreases due to the influence of the environmental pillar. (See the figures in Appendix F). The ex situ S/S for contaminated soil was the preferred technology option as a result of the thorough screening to select the appropriate remediation technology for contaminated soil. However, the outcome of the sustainable remediation assessment produced another option known as in situ S/S which should provide more benefits to the whole system (environment, economy, society). With respect to the contamination of groundwater, the Phytoremediation technology was the preferred technology option as a result of the detailed screening to select the remediation technology. However, the outcome of the sustainable remediation assessment produced another option known as constructed wetland which should provide more benefits to the studied system (environment, economy, society). There are many benefits created from sustainability measures such as: a. A reduction in gas emissions (CO2, GHG) due to less consumption of energy b. A reduction of costs c. A reduction in neighbourhood disturbance and d. Potential for local employment.
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Table 6-31 Scoring summary scenario 2 (Mid-term (3-6 years)) of contaminated soil Remediation alternatives Theme Assessment criteria (indicators) Weight Reason of value estimation (linguistic or number) 1 2 3 4 Averag potential emissions of CO2 and VOC emission especially VOC Emissions to air 1 Good Bad Bad e using of fuel increase GHG
Soil and ground conditions 0
Groundwater & Surface Water 0
Ecology 0
Environmental
Averag Very Impacts on waste resources such as landfill Natural resources and waste 0.7 Good Good e Bad Use of fuel Very Averag Based on estimation of cost, remediation works Direct economic costs and benefits 1 Good Bad Good e Value of the site
Indirect economic costs and benefits 0
Averag Very Long term employment Employment and employment capital 1 Bad Good e Good
Economic
Induced economic costs and benefits 0
Averag Some uncertainties is related with excavation and higher quantities and contaminants type Project lifespan and flexibility 0.6 Good Good Good e Very Averag Very Safety of workers and people on the work site Human health and safety 1 Good Good e Good
Ethics and equality 0
Very Averag Impacts on local community (dust, noise, odor, light): The duration of remedial works and working Neighborhoods and locality 1 Good Good Good e hours
Social Communities and community 0 involvement Very Very Very Potential change in CSM and contaminants therefore remediation process Uncertainty and evidence 0.4 Good Good Good Good 1: In Situ Physical/Chemical Treatment: Solidification/Stabilization (In Situ Vitrification); 2: Ex-Situ Physical/Chemical Treatment (assuming excavation): Soil Washing; 3: Ex Situ Physical/Chemical Treatment (assuming excavation): Solidification/Stabilization (Vitrification); 4: Other Treatment: Excavation, Retrieval, Off-Site Disposal (Removal, Waste Removal-Soils, Waste Removal-Sludges, Waste Removal-Non-soil Solids) 1: very bad, 2: bad, 3: average, 4: good, 5: very good
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Table 6-32 Scoring summary scenario 3 (Long-term (6 & >10 years)) of contaminated soil Remediation alternatives Reason of value estimation (linguistic or number) Theme Assessment criteria (indicators) Weight 1 2 3 4 Averag potential emissions of CO2 and VOC emission especially VOC Emissions to air 1 Good Bad Bad e using of fuel increase GHG
Soil and ground conditions 0
ental
Groundwater & Surface Water 0
Ecology 0
Environm
Averag Increase time period for excavation and disposal alternative can improve bio-remediation at the landfill Natural resources and waste 0.7 Good Good Bad e site, Impacts on waste resources such as landfill, Use of fuel Very Averag Based on estimation of cost, remediation works Direct economic costs and benefits 1 Good Bad Good e Value of the site
Indirect economic costs and benefits 0
Averag Very Long term employment Employment and employment capital 1 Bad Good e Good
Economic
Induced economic costs and benefits 0
Averag Some uncertainties is related with excavation and higher quantities and contaminants type Project lifespan and flexibility 0.6 Good Good Good e Very Averag Very Safety of workers and people on the work site Human health and safety 1 Good Good e Good
Ethics and equality 0
Very Averag Impacts on local community (dust, noise, odor, light): The duration of remedial works and working Neighborhoods and locality 1 Good Good Good e hours
Social Communities and community Long term employment 0 involvement Very Very Very Excavation & disposal alternative is improved by increase period of remediation (bio-remediation) Uncertainty and evidence 0.4 Good Good Good Good Potential change in CSM and contaminants therefore remediation process 1: In Situ Physical/Chemical Treatment: Solidification/Stabilization (In Situ Vitrification); 2: Ex-Situ Physical/Chemical Treatment (assuming excavation): Soil Washing; 3: Ex Situ Physical/Chemical Treatment (assuming excavation): Solidification/Stabilization (Vitrification); 4: Other Treatment: Excavation, Retrieval, Off-Site Disposal (Removal, Waste Removal-Soils, Waste Removal-Sludges, Waste Removal-Non-soil Solids)
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Table 6-33 Scoring summary scenario 5 (Mid-term (3-6 years)) of contaminated groundwater Remediation alternatives Reason of value estimation (linguistic or number) Theme Assessment criteria (indicators) Weight 1 2 3 4 5 Very potential emissions of CO2 and VOC emission especially VOC Emissions to air 1.0 Good Good Good Good Good using of fuel increase GHG
Soil and ground conditions 0
Groundwater & Surface Water 0
ronmental Very Very Very Very Improvement the ecosystem of the site Ecology 1.0 Good Envi Bad Good Bad Bad Very Averag Averag Increase time period for excavation and disposal alternative can improve bio-remediation at Natural resources and waste 0.6 Good Good Good e e the landfill site, Impacts on waste resources such as landfill, Use of fuel Averag Averag Averag Based on estimation of cost, remediation works Direct economic costs and benefits 1.0 Bad Good e e e Value of the site
Indirect economic costs and benefits 0
Averag Very Long term employment Employment and employment capital 1.0 Bad Bad Bad e Good
Economic
Induced economic costs and benefits 0
Averag Averag Very Some uncertainties is related with excavation and higher quantities and contaminants type Project lifespan and flexibility 0.6 Good Good e e Good Equal effect of all alternatives Human health and safety 0
Ethics and equality 0
Very Very Impacts on local community (dust, noise, odor, light): The duration of remedial works and Neighborhoods and locality 1.0 Good Good Good Good Good working hours
Social Communities and community Leisure and education 1.0 Good Bad Good Bad Bad involvement Long term employment Excavation & disposal alternative is improved by increase period of remediation (bio- Uncertainty and evidence 0.4 Good Bad Good Good Bad remediation) , Potential change in CSM and contaminants therefore remediation process 1: In-situ biological treatment: Phytoremediation (Vegetation-enhanced bioremediation); 2: In Situ Physical/Chemical Treatment: Passive/Reactive Treatment Walls (Permeable reactive barrier walls; In place bioreaction; In-situ chemical filters);
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3: Ex Situ Biological Treatment: Constructed Wetlands; 4: Ex Situ Physical/Chemical Treatment (assuming pumping): Separation; 5: Containment: Physical Barriers (Vertical cutoff walls; Hydrodynamic barriers; Slurry Trenches, Slurry Walls, Slurry Walls/Underground Barriers)
Table 6-34 Scoring summary scenario 6 (Long-term (6 & >10 years)) of contaminated groundwater Remediation alternatives Theme Assessment criteria (indicators) Weight Reason of value estimation (linguistic or number) 1 2 3 4 5 Very potential emissions of CO2 and VOC emission especially VOC Emissions to air 1.0 Good Good Good Good Good using of fuel increase GHG
Soil and ground conditions 0
Groundwater & Surface Water 0
Very Very Very Very Improvement the ecosystem of the site Ecology 1.0 Good Environmental Bad Good Bad Bad Averag Increase time period for excavation and disposal alternative can improve bio-remediation at Natural resources and waste 0.6 Good Bad Good Bad e the landfill site, Impacts on waste resources such as landfill, Use of fuel Averag Averag Very Based on estimation of cost, remediation works Direct economic costs and benefits 1.0 Bad Good e e Good Value of the site
Indirect economic costs and benefits 0
Very Long term employment Employment and employment capital 1.0 Good Bad Bad Bad Good
Economic
Induced economic costs and benefits 0
Averag Averag Very Some uncertainties is related with excavation and higher quantities and contaminants type Project lifespan and flexibility 0.6 Good Good e e Good Equal effect of all alternatives Human health and safety 0
Ethics and equality 0
Averag Very Averag Very Impacts on local community (dust, noise, odor, light): The duration of remedial works and Neighborhoods and locality 1.0 Good e Good e Good working hours
Social Communities and community Leisure and education 1.0 Good Bad Good Bad Bad involvement Long term employment Very Averag Very Averag Excavation & disposal alternative is improved by increase period of remediation (bio- Uncertainty and evidence 0.4 Good Good e Good e remediation) , Potential change in CSM and contaminants therefore remediation process 1: In-situ biological treatment: Phytoremediation (Vegetation-enhanced bioremediation); 2: In Situ Physical/Chemical Treatment: Passive/Reactive Treatment Walls (Permeable reactive barrier walls; In place bioreaction; In-situ chemical filters);
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3: Ex Situ Biological Treatment: Constructed Wetlands; 4: Ex Situ Physical/Chemical Treatment (assuming pumping): Separation; 5: Containment: Physical Barriers (Vertical cutoff walls; Hydrodynamic barriers; Slurry Trenches, Slurry Walls, Slurry Walls/Underground Barriers)
Table 6-35 The output score for contaminated soil remediation technologies of scenario 2 Scenario 2 (3-6 years) Alternatives 1 2 3 4 Pillars scores (Env. 4.0 3.66 4.18 3.0 2.5 3.5 2.91 4.0 4.18 1.4 3.16 3.58 Econ., Soc.) Env. Econ. Soc. Env. Econ. Soc. Env. Econ. Soc. Env. Econ. Soc. Over 5 Total scores 3.68 3.0 3.22 2.56 Over 5 Rank 1 3 2 4
Table 6-36 The output score for contaminated soil remediation technologies of scenario 3 Scenario 3 Long-term Alternatives (6 & >10 years) 1 2 3 4 Pillars scores (Env. 4.0 3.66 4.18 3.0 2.5 4.0 2.91 4.0 3.58 2.19 3.0 3.0 Econ., Soc.) Env. Econ. Soc. Env. Econ. Soc. Env. Econ. Soc. Env. Econ. Soc. Over 5 Score (3-6 yrs) 3.68 3.0 3.18 3.13 Over 5 Rank 1 4 2 3
1: In Situ Physical/Chemical Treatment: Solidification/Stabilization (S/S) (In Situ Vitrification);
2: Ex-Situ Physical/Chemical Treatment (assuming excavation): Soil Washing;
3: Ex Situ Physical/Chemical Treatment (assuming excavation): Solidification/Stabilization (Vitrification);
4: Other Treatment: Excavation, Retrieval, Off-Site Disposal (Removal, Waste Removal-Soils, Waste Removal-Sludges, Waste Removal-Non-soil Solids)
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Table 6-37 The output score for contaminated groundwater remediation technologies of scenario 2 Scenario 2 (3-6 years) Alternatives 1 2 3 4 5 Pillars scores (Env. 4.0 3.0 4.0 2.05 2.5 2.92 4.68 3.66 4.0 2.19 2.8 3.09 2.19 3.0 3.0 Econ., Soc.) Env. Econ. Soc. Env. Econ. Soc. Env. Econ. Soc. Env. Econ. Soc. Env. Econ. Soc. Over 5 Total Score 3.5 2.38 3.68 2.35 2.16 Over 5 Final Rank 2 3 1 4 5
Table 6-38 The output score for contaminated groundwater remediation technologies of scenario 3 Scenario 3 Long-term Alternatives (6 & >10 years) 1 2 3 4 5 Pillars scores (Env. 4.0 3.5 3.57 2.08 2.5 3.0 4.21 4.21 3.57 2.08 2.8 3.09 2.19 3.0 3.0 Econ., Soc.) Env. Econ. Soc. Env. Econ. Soc. Env. Econ. Soc. Env. Econ. Soc. Env. Econ. Soc. Over 5 Total Score 3.57 2.38 3.68 2.29 2.16 Over 5 Final Rank 2 3 1 4 5
1: In-situ biological treatment: Phytoremediation (Vegetation-enhanced bioremediation);
2: In Situ Physical/Chemical Treatment: Passive/Reactive Treatment Walls (Permeable reactive barrier walls; In place bioreaction; In-situ chemical filters);
3: Ex Situ Biological Treatment: Constructed Wetlands;
4: Ex Situ Physical/Chemical Treatment (assuming pumping): Separation;
5: Containment: Physical Barriers (Vertical cutoff walls; Hydrodynamic barriers; Slurry Trenches, Slurry Walls, Slurry Walls/Underground Barriers)
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7 Summary Every country might become afflicted by petroleum hydrocarbons contamination. Petroleum hydrocarbons often have detrimental effects on human life and health, and the ecosystem due to their dangerous toxicological features. Additionally they might also cause severe economic problems to the local or national economy. Therefore, it is essential to find appropriate solutions for managing and decontaminating the land polluted with petroleum hydrocarbons. Petroleum hydrocarbons encompass aliphatic and aromatic fractions - “crude oil, petroleum fuel mixture, light non-aqueous phase liquids (LNAPL), dense non-aqueous phase liquids” - which tend to dissolve in water or evaporate in the air. These substances cause undesirable effects due to their biological, chemical and toxicological characteristics. Therefore, it is important to know the properties of these compounds in order to protect human life and the environment. It is conducive to alleviating the impacts of the substances if the transport routes and destinations can be identified. There have been many studies on the toxicological impacts of these mixed chemicals on human life and the environment, such as the Massachusetts Department of Environmental Protection (MADEP) approach and Total Petroleum Hydrocarbon Criteria Working Group (TPHCWG) approach. One of the significant findings derived from studies on petroleum hydrocarbons is the analysis of Total Petroleum Hydrocarbon (TPH). It reflects the overall concentration of petroleum hydrocarbons in an environmental media such as water and soil. The environmental media is described by the geological and hydrogeological characteristics, the clear view of different material contents inside and at the surface of the earth and their properties in addition to the water properties and features, such as the flow direction and water table. It is essential to know the details of these chemical compounds and the environmental media in order to successfully manage the sites contaminated with petroleum hydrocarbons. The management of these contaminated sites is a complex affair and entails high costs, time delays, and other unpredictable uncertainties. It is therefore crucial to adopt a clear management method for the rehabilitation of the contaminated land. In the recent past, many approaches and frameworks for the treatment and management of contaminated sites were developed, particularly in the developed countries. The risk management framework comprises two main components. The first component is known as the risk assessment process which is the core element of the risk management procedure. The second component is known as risk management or remediation action. In the risk assessment process, it is essential to determine threshold levels of contamination which are defined as screening values, screening levels, or thresholds values. These values are used to identify the contamination and differ from country to country. The remediation action is the contamination removal process (risk reduction process) which is directly connected and dependent on the risk assessment process. Various remediation technologies have developed in order to treat different types of contamination. It requires expert knowledge and experience about the origins of contamination, the pathways, and receptors (pollution linkage) in order to be able to use risk assessment and remediation technologies successfully. This knowledge is gained by collecting and analyzing data and including and understanding the pollution or contamination linkage and leads to plans and designs for a suitable and comprehensive rehabilitation system. Currently, the modern sustainable remediation method is strongly recommended for Libya. This would entail significant guidelines regulating a cost-efficient, consistent, and effective contaminated land management. This concept should follow the sustainability concept in remediation projects. Understanding and applying the sustainable remediation approach will provide an efficient regulatory framework leading to soil protection, which in turn will safeguard the health and safety of the involved parties and will also protect the environment. The sustainability approach comprises a robust integrated risk management system known also as sustainable- risk based land management. The fundamental objectives of this method are to realize an acceptable risk management whose impacts, should be planned and managed in a transparent decision making process including all stakeholders from the beginning of the project. Additionally, it is essential that the results are balanced between the sustainability pillars “environmental, economic, and social”. If the object is to realize a risk-based site management, there are many methods to achieve this goal. One possibility would be to “borrow” a management procedure from another country and adjust it the national conditions regarding the specific political and geographic situation. Various international standards, guidelines, and procedures can point the implementation of a sustainable-risk based land management in the right direction. Libya lacks appropriate procedures for handling and managing contaminated sites. This situation must be met with international
134 management procedures which nonetheless must take into account the individual situation in Libya with regards to land use, and specific political and geographical issues. The regional land use and distinctive activities in the different districts should be documented and included when the respective management method is chosen. Geographic parameters such as soil properties and climate conditions are also very important items to consider. The threshold levels for exposure to carcinogens and non-carcinogens substances is a matter of political opinion and must be observed. Libya can find help and guidance from many European countries and North-America whose international standards offer suitable sustainable-risk based land management systems. The core of this approach to handle the contamination in a scientific technical method is the risk management process and the core of the risk management process is the risk assessment process. The risk assessment process encompasses hazard identification, dose-response assessment, exposure assessment and risk characterization. For the process to be successful it is pivotal to know the type of land use in the area and what activities the local people accomplish there. The entire assessment process relies strongly on the screening levels or values which define the level of contamination on the site, i.e. without finding such values there is no way of defining the hazards and risk. It is therefore of the utmost importance that countries identify such thresholds values. To derive these values scientific, political and geographic parameters are applied. However, the risk management method also includes a remediation process in which the contamination is reduced or removed by one or more technological options. These technologies are classified to two main categories, vadose zone “soil” and saturated zone “water” This system can be defined now as the sustainable remediation approach. This approach allows and promotes public participation and stakeholders’ involvement in the decision making process. It produces transparent decisions with a clear plan of the remediation projects. Another important element of the system is to develop effective funding sources for remediation projects. Stakeholders can be land owners, regulators, risk assessors, investors, local people and councils who are afflicted by pollution and remediation technologies. It is very significant to identify and evaluate the stakeholders’ perspectives in the early stages of the remediation project. Finding a suitable sustainability system to perform contaminated site management in a sustainable manner requires the sustainability assessment method. Sustainable remediation and sustainable assessment are always based on quantitative and qualitative (mixed) data. Therefore, the decision should be made on the bases of quantitative and qualitative analyses of mixed data with a certain degree of uncertainty. A qualitative analysis method is always a subjective scoring process Sustainability indicators are criteria for helping to evaluate the sustainable remediation. The criteria are grouped according to the main pillars of sustainability which are environmental, economic and social. The remediation technology option scores are based on the impacts the options have on all contributors. This is obviously an area with a lot of uncertainties. Therefore, the fuzzy logic system is implemented in order to make the scoring more scientific and well sensed. Fuzzy logic is an approach which is widely used in various fields of scientific research and real world applications. Its main benefit is that it can simulate human reasoning which often subjective and qualitative. Therefore, fuzzy logic can deal with incomplete information, missing data and uncertainties in the risk assessment process which requires the use of experience, knowledge and scientific judgment. It is used in cases where an approximate, but fast solution must be presented. With fuzzy logic a procedure can be realized even when there is no model. Fuzzy logic discovers standards or ambiguous conclusions and thus makes sense of the data. Political decisions should be supported by fuzzy logic and based on expert knowledge.
The fuzzy logic method can effectively rank various contaminated sites according to different priorities of classifications and in agreement with scientific criteria. Various remediation technologies are graded efficiently by applying suitable criteria. The fuzzy logic approach returns significant results and is used successfully as an assessment tool to classify different treatment options related to the sustainability criteria or other criteria. The sustainable remediation assessments undertaken by using fuzzy logic illustrate that a given option may score significantly differently on specific criteria. Therefore, the overall scores typically show a more balanced picture, with fewer differences between the options. Weights of indicators play an important role in the assessment process; therefore, it is a crucial step during the identification and evaluation of the sustainability indicators.
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8 Outlook The long history of oil and gas industry in Libya has led to the contamination of air, soil and water in many places (downstream, upstream) and created hazardous situations growing from these pollution sources. The important key step for Libya is to adopt a more coherent and effective contaminated land management framework. It should involve the following:
1. Identifying the appropriate regulatory context 2. Using priority list 3. Using risk assessment to inform risk management 4. Applying sustainability as the regulating criteria for risk management 5. Facilitating stakeholder acceptance 6. Communicating stakeholders 7. Making a transparency decision
Libya should establish the regulatory framework of Land contamination management (soil protection legislation). The key issue of the legislation is to protect soil against contamination; it will make a generic distinction between harmful soil variations and contaminated land. Soil protection legislation should rule screening systems and evaluation of potentially dangerous sites, permissible remediation options and supplementary regulations relating to remediation screening and planning. The soil protection legislation should also include detailed supplements on sampling, analysis and quality assurance to prepare site studies which cover the conclusion of risk characterization and remedial implementation. The legislation present obligations to avoid risks, presents liabilities about awareness of the contamination for site owners.
Libya should establish a priority approach which include record of all suspected contaminated sites (inventory sites) and rehabilitation time plan. The approach should explain how national priorities list is established and the criteria used. All suspected contaminated sites should follow extensive investigation to find out enough data and information about every site. These collected data and information will be subjected to hazard scoring method criteria to find out priorities for all contaminated sites in a region, country or connected to any sector, therefore; more detailed investigation is recommended to give preference to manage these contaminated site in specific time as described in Figure 9.1. Time frame and financial support are very important factors in developing and managing projects, Libya needs to establish action plans framed by time periods and for rehabilitation projects of contaminated sites. Libyan government can adopt the next time frame for management periods. Figure 9.1 explains the major activities which are proposed to implement during a period of time for managing contaminated sites in Libya.
8.1 Short-term management program (1.5 to 2 years) In this term, an effective national management policy (an act, regulation, ordinance, and standard) must be established at national, regional, and local scales to deal with land contamination problems, which intends to fulfill soil protection considerations. In Libya there are some basic laws and legislations which can be used as a base for the comprehensive management plan; therefore, this term focus more in the general national condition. A fund should be presented to cover the cost of short-term activities and can also use to manage any urgent rehabilitation project in hot spots locations (Al-Wahat region). Collaboration with international experts is a key issue to facilitate and improve the action plan from short-term to long-term. These experts introduce technical advices and recommendations for Libyan government and the other authorities about the management approach. They explain stakeholder engagement method and communication process which should be started in this term. International experts can report the progress and outcomes during and after every term.
8.2 Mid-term management program (2 to 3 years) The main focus in the mid-term period is to start introducing the management framework to the regional authorities, where the legislation and regularity approaches are ready to use. Some activities in this term could start in parallel with some activities in the short-term; therefore, national agencies can send and receive data and information (cultural, economic, political, and social) which are stored in the national data base system. The regional agencies should collaborate with international experts to establish site-specific standards, the regional data base network, to recognize management method, sustainability approach and the stakeholders’ engagement
136 process. The financial support is always a key issue to facilitate performing the activities and future projects in an exact time.
8.3 Long-term management program (after 4 to 5 years) Long-term program starts approximately in or after the 4th year with building capacity and sharing with stakeholders’ activity. After the 5th year some pilot projects should be started in most of oil industry locations which will provide experience and knowledge to Libya, especially environmental department in the oil and gas sector. Remediation projects should be implement from the 6th year at different contaminated sites locations based on the national priority list.
Time period 1st year 2nd year 3rd year 4th year 5th year 6th year 7th year Description Short-term management program:(National) Establishing the legislation approach Developing the financing program (1) Collaboation with international experts Establishing National data base system Communicating various stakeholders Reporting the implementing plan Mid-term management program:(Regional) Managing and assessing sustainability Starting stakeholders meetings Developing regional management criteria Developing regional information systems Developing the financing program (2) Long-term management program Implementing the management plan Building capacity and sharing with Stakeholders Starting pilot projects Starting Rehabilitation projects
Figure 8 -1 A proposed time period frame to apply sustainable risk-based contamination management in Libya
8.4 Knowledge and experience base Various international initiatives from different countries and organizations have now released a number of standards, frameworks, guidelines, authoritative reports, and road-maps with similarities and differences in the approaches to sustainable remediation. Some of the initiatives are (Common Forum, NICOLE, SuRF-UK, SuRF-Italy, SuRF-NL, ASTM, ITRC, SURF, SuRF-Brazil, SuRF- Canada, SuRF-Colombia, SuRF-Taiwan, SuRF-Australia and NewZealandICCL, ISO). Libya would benefit from similar platform to establish (SuRF-Libya), which would be used to introduce and facilitate the inclusion of sustainability conception into managing for site contamination in Libyan authorities and agencies. Such a forum should be established at all of Libya covering national authorities, ministries and agencies to regional and local authorities and agencies of management of contaminated sites.
8.5 Financing, investment, and funding method Libya should develop several funding methods, and such methods should be included in Libyan policy and legislation of site management contamination. A variety of financing mechanism is developed in the United States and EU is oriented broadly to countries looking for potential funding tools for rehabilitation of contaminated sites. Many Libyan investment companies and investment banks could contribute in different rehabilitation projects in Libya.
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8.6 Information management system There are many environmental problems in Libya which need a practical solution by establishing scientific sound environmental management systems, supported by policy and legislation framework. In Libya, there is no awareness and experience at the national, regional, and local levels in the management information system about their services and benefits to organizations and public in environmental contamination management. Such information system can help widely in risk assessment process, transparency decision making process and in management and assessment of sustainable remediation method.
8.7 Sustainable development indicators Sustainable development indicators are considered significant requirements for Libya. Finding indicators of sustainable development are identified as follows: a. Indicators of sustainable development are needed for Libya to guide policies and decisions at all levels of society: village, town, city, county, state, region, nation, continent, and the world. b. These indicators must represent all important concerns: An ad hoc collection of indicators that just seem relevant is not adequate. A more systematic approach must look at the interaction of systems and their environment. c. The number of indicators should be as small as possible, and as large as necessary. That is, the indicator set must be comprehensive and compact, covering all relevant aspects. d. The process of finding an indicator set must be participatory to ensure that the set encompasses the visions and values of the community or region for which it is developed. e. Indicators must be clearly defined, reproducible, unambiguous, understandable and practical. They must reflect the interests and views of different stakeholders in the region. f. From a look at these indicators, it must be possible to deduce the viability and sustainability of current developments and to compare them with alternative development paths. g. A framework, process, and criteria for finding an adequate set of indicators of sustainable development are needed h. Assign weights and ranks to the indicators based on the regional context
8.8 Awareness and training of stakeholders The issue of involving the public and of including the interests of all stakeholders in the management of contaminated land in Libya is of crucial importance. There is a need to “empower people in Libya, especially public stakeholders “tribal, women, affected people, community, .etc.”, through an engagement process of contamination management. There are many methods might be used for raising awareness of public stakeholders such as social learning where individuals are empowered to see their private concerns connected with the shared concerns of their citizens (Webler, Kastenholz, & Renn, 1995). Such tools are cultural events, women’s clubs, workshops, charrettes, Interviews, and open space meetings, .etc.
8.9 Different opinions inputs “public stakeholder perspective” An equitable and transparent decision is the target of risk management process of contamination land. Public stakeholder should understand the potential risks existing, decisions and next remedial actions to remove such risks to keep human health and environment safe in Libya. Libya should notify to public stakeholders that they are invested and engaged in the scoping, planning, site characterization and the selected remediation option. During the engagement process, information such as harmful substances and toxicity, sampling process, exposure assessment study information (pathways, etc.), remediation options and their impacts present in a concise and understandable style. In Libya, public stakeholders should be encouraged to present their Inputs which include for example, information about particular species, consumption, and location in the site. These inputs are very useful for risk assessors in developing risk assessment process.
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Appendices
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Appendix A General Properties of Petroleum Hydrocarbon (PHC)
Figure A-1 Approximate Carbon and Boiling Ranges of some petroleum hydrocarbons “TPHCWG” (Weisman 1998a, b)
Table A-1 MADEP petroleum fractions and compounds Massachusetts Petroleum Fractions and Compounds VPH EPH Aliphatic Aromatic Aliphatic Aromatic C5–C8 C9-C10 C9-C18 C9-C22 C9-C12 Benzene C19-C36 PAHs Toluene Ethylbenzene Xylene MTBE MADEP assigned reference compounds to carbon ranges C5–C8, C9–C18, and C19–C36 for alkanes/cycloalkanes and C9-C22 for aromatic compounds.
Table A-2 MADEP toxicity criteria for petroleum fractions Toxicity criteria for MADEP petroleum fractions Carbon range Alkanes/Cycloalkanes C5–C8 n-hexane neurotoxicity 0.06 C9–C18 n-nonane neurotoxicity 0.6 C19–C36 eicosane irritation 6 Aromatics/Alkenes C9–C22 pyrene neurotoxicity 0.03
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Figure A-2 Chemical structures of some selected PHC (MENZ 1999)
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Table A-3 Fate and transport properties of TPH fractions linked to EC number TPHCWG V.5 (Weisman 1998b)
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Figure A-3 TPH Compounds classification
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EVALUATION OF AROMATIC FRACTIONS (D.A. Edwards et al. 1997)
Table A-4 Evaluation of aromatic fractions according TPHCWG Fraction Inhalation Equivalent Carbon Compounds w/Toxicity Fraction Oral RfD Measures Comments on measures (mg/kg/day) RfC (mg/m3) Oral mg/kg Oral mg/kg/day Ranges Data Inhal. mg/kg Inhal. mg/kg/day C>7 - C8 Toluene (C7) 0.2 0.4 Thus, an oral RfD of 0.2 This surrogate value represents the fraction- Ethylbenzene (C8) 0.1 1.0 mg/kg/day was deemed protective specific RfD for aromatics in the C5 - C8 (C5 to C8 aromatic C>7 - C8 Styrene (C8) 0.2 1.0 Toluene (C7): NOAEL (223 carbon range Xylenes (o-, m- ,and p-) (C8) 2.0 NA mg/kg/day) fraction) Ethylbenzene (C8): NOAEL (97.1 0.2 0.4 mg/kg/day) C>7 - C8 Styrene (C8): NOAEL (200 mg/kg/day) Xylenes (o-, m- ,and p-) (C8): NOAEL (179 mg/kg/day) C>8 - C10 Isopropylbenzene (C9) 0.04 0.09 The RfDs range from 0.03 to 0.3 C>10 - C12 Naphthalene (C10) 0.04 0.0013 mg/ kg/day C>12 - C16 Acenaphthene (C12) 0.06 NA This value supports the 0.04 Biphenyl (C12) 0.05 NA mg/kg/day value. Because TPH is (C9 to C16 aromatic Fluorene (C13) 0.04 NA a mixture, emphasis needs to be Anthracene (C14) 0.3 NA placed on these available mixtures fraction) Fluoranthene (C16) 0.04 0.04 NA 0.2 data. Pyrene (C16) 0.03 NA The more conservative value, 0.2 mg/m3, was determined NA 0.2 to be representative of this entire Data from this mixture (naphthalenes/ C9 Aromatics 0.03 NA fraction methylnaphthalenes) were used to develop Naphthalenes/ NOEL = 900 mg/m3 an RfD which was included in determining Methylnaphthalenes RfC = 0.2 mg/m3 the fraction-specific RfD C>16 - C21 NA NA NA This value (0.03 mg/kg/day) Pyrene is considered a conservative C>21 - C35 NA represents the fraction-specific surrogate because it has a lower carbon 0.03 the fraction is RfD for the C17+ carbon number than any of the compounds in this (C17 to C35 aromatic not volatile range. fraction fraction) NA - None Available
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EVALUATION OF AROMATIC FRACTIONS (D.A. Edwards et al. 1997)
Table A-5 Evaluation of aromatic fractions according to TPHCWG Fraction Oral RfD Fraction Inhalation RfC NOAEL LOAEL Equivalent Carbon Compounds w/Toxicity (mg/kg/day) (mg/m3) Ranges Data Oral mg/kg Inhal. mg/kg Oral Inhal. mg/kg/day mg/m3 C>7 - C8 Toluene (C7) 0.2 0.4 312 LOAEL 119 Ethylbenzene (C8) 0.1 1.0 mg/kg(average mg/m3 C>7 - C8 Styrene (C8) 0.2 1.0 5 days) = (IRIS 1987a) (C5 to C8 aromatic fraction) 0.2 0.4 Xylenes (o-, m- ,and p-) (C8) 2.0 NA (223 mg/kg/day) Uf=1000 C>8 - C10 Isopropylbenzene (C9) 0.04 0.09 C>10 - C12 Naphthalene (C10) 0.04 0.0013 C>12 - C16 Acenaphthene (C12) 0.06 NA Biphenyl (C12) 0.05 NA (C9 to C16 aromatic Fluorene (C13) 0.04 NA Anthracene (C14) 0.3 NA fraction) Fluoranthene (C16) 0.04 0.04 NA 0.2 <400 =400 Pyrene (C16) 0.03 NA
NA 0.2 C9 Aromatics 0.03 NA <300 =300 Naphthalenes/ Uf=10000 Methylnaphthalenes C>16 - C21 NA NA NA The NOAEL the LOAEL C>21 - C35 NA (75 was 125 0.03 the fraction mg/kg/day) for mg/kg/day for is not (C17 to C35 aromatic Pyrene Pyrene volatile fraction) NA - None Available
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EVALUATION OF AROMATIC FRACTIONS (IRIS USEPA)
TableA-6 The shown data are from IRIS USEPA Fraction Inhalation Equivalent Carbon Compounds w/Toxicity Fraction Oral RfD Measures Comments on measures (mg/kg/day) RfC (mg/m3) Oral mg/kg Oral mg/kg/day Ranges Data UF MF UF MF Inhal. mg/kg Inhal. mg/kg/day C>7 - C8 Toluene (C7) 0.08 3000 5.0 10 Oral RfD 0.08 mg/kg-day (IRIS 1987a) Ethylbenzene (C8) 0.1 1000 1 1.0 300 1 (IRIS 1987b)
(C5 to C8 aromatic fraction) C>7 - C8 Styrene (C8) 0.2 1000 1 1.0 30 1 (IRIS 1987c) Xylenes (o-, m- ,and p-) (C8) 0.2 1000 1 0.1 300 1 (IRIS 1987d) C>8 - C10 Isopropylbenzene (C9) 0.1 1000 1 0.4 1000 1 (IRIS 1988) C>10 - C12 Naphthalene (C10) 0.02 3000 1 0.003 1000 1 (IRIS 1990a) C>12 - C16 Acenaphthene (C12) 0.06 1000 1 NA (IRIS 1990b) Biphenyl (C12) 0.5 30 10 NA (IRIS 1987e) (C9 to C16 aromatic fraction) Fluorene (C13) 0.04 3000 10 NA (IRIS 1990c) Anthracene (C14) 0.3 3000 1 NA (IRIS 1990d) Fluoranthene (C16) 0.04 3000 1 NA (IRIS 1990e) Pyrene (C16) 0.03 3000 1 NA (IRIS 1990f)
C9 Aromatics Naphthalenes/ Methylnaphthalenes 0.004 1000 1 NA (IRIS 2003) C>16 - C21 NA C>21 - C35
(C17 to C35 aromatic fraction)
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EVALUATION OF AROMATIC FRACTIONS
Table A-7 MaDEP Approach Fraction Oral RfD Fraction Inhalation RfC NOAEL LOAEL Equivalent Carbon Compounds w/Toxicity (mg/kg/day) (mg/m3) Ranges Data Oral mg/kg Inhal. mg/kg Oral Inhal. mg/kg/day mg/m3 C>7 - C8 Toluene (C7) Ethylbenzene (C8)
(C5 to C8 aromatic fraction) C>7 - C8 Styrene (C8) Xylenes (o-, m- ,and p-) (C8) C>8 - C10 Isopropylbenzene (C9) C>10 - C12 Naphthalene (C10) C>12 - C16 Acenaphthene (C12) Biphenyl (C12) (C9 to C16 aromatic Fluorene (C13) Anthracene (C14) fraction) Fluoranthene (C16) Pyrene (C16)
C9 Aromatics Naphthalenes/ Methylnaphthalenes C>16 - C21 NA C>21 - C35
(C17 to C35 aromatic fraction)
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EVALUATION OF ALIPHATIC FRACTIONS
Table A-8 Evaluation of aliphatic fractions according TPHCWG Fraction Inhalation Equivalent Carbon Compounds w/Toxicity Fraction Oral RfD Measures Comments on measures (mg/kg/day) RfC (mg/m3) Oral mg/kg Oral mg/kg/day Ranges Data Inhal. mg/kg Inhal. mg/kg/day
C5 - C6 AND C>7- C8 n-hexane 0.06 0.2 0.2 RfC is based on neurotoxic effects n-Hexane has RfC in this fraction aliphatic fraction n-heptane 2 --- in humans. overestimates the health risks of Commercial Hexane 5 18.4 RfD of n-heptane should be 38 hydrocarbons in this fraction. It is proposed Other C5-C8 times higher than the RfD of n- that the health-based criteria for the C5-C8 Alkane/Cycloalkane Compounds hexane. alkane fraction be based on a percentage basis of n-hexane in relation to the rest of the hydrocarbons in this fraction. n-heptane is considered to have a neurotoxic risk that is 38 times lower than that of n-hexane. Finally, utilize the hexane RfD(0.06 these data provide further evidence that the mg/kg/day) for the n-hexane presence of other petroleum Proposed Composition-Weighted 18.4 portion and the n-heptane RfD (2.0 compounds influences the toxicity of n- RfD for TPH Fraction 5 mg/kg/day) for the remainder hexane and that mixture data should Containing C5-C8 or C6-C8 of the mass. be utilized to evaluate the risk of petroleum Aliphatics mixtures. evaluate the hexane concentration separately. If the n- hexane concentration is less than 53% as found in commercial hexane, then the RfD applied should be 5mg/kg/day. If it is greater than 53%, the RfD should be developed utilizing 0.06 for the n-hexane portion and 2.0 for the remaining mass.
C>8 - C10, Composition: C10-C11 St1 = 0.9 The data which were utilized to develop Isoparaffinic solvent; aromatic oral and inhalation criteria for this fraction
C>10 - C12, content: <0.01% were studies on JP-8 (C9-C16).
Composition: dearomatized
white spirit; C7-C11 0.1 isoparaffins/n- St3 = 1.0 1.0 alkanes/napthenes; typical aromatic content: 0.1%
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St5 = 1.0
JP-8 Jet Fuel Composition: dearomatized aliphatic; C10-
C13 isoparaffins/naphthenes/n-alkanes; typical aromatic content: 0.1% (St7)
Composition: dearomatized aliphatic; C15-
C18; typical aromatic content 0.6-1.5% (St8) Studies on Petroleum Streams and JP-8: Composition: C11-C17 isoparaffinic solvent; contains 22% naphthenes; typical and Composition: dearomatized St6 = 0.1 aromatic C>12 - C16 aliphatic; C -C isoparaffins/n- content <0.05% (St9) 9 12 aliphatic fraction alkanes/ naphthenes; typical
aromatic content: 0.1% JP-8 Jet Fuel (St10)
C10 - C13 St7 = 0.1
C15 - C18 St8 = ---
C11 - C17 St9 = 0.1
JP-8 (C9 - C16) St10=0.75
n-Nonane (C9) On going
C>16 - C21 C17-34 MHC 2 the RfD for TPH fractions containing an AND C MHC 20 aliphatic carbon range of C - C MHC is 2 >34 2 17 34 C - C NA mg/kg/day; for fractions containing aliphatic >21 35 20 Aliphatic fraction fractions C>34 , the RfD is 20 mg/kg/day. St: study MHC:
Toluene:The NOAEL (average) of 34 ppm (128 mg/m3) was adjusted from an occupational exposure scenario to continuous exposure conditions as follows: Where: VEho = human occupational default minute volume (10 m3 breathed during the 8 hour workday) VEh = human ambient default minute volume (20 m3 breathed during the entire day) I.B.3. Uncertainty and Modifying Factors (Inhalation RfC): UF = 10, A total uncertainty factor of 10 was applied to the adjusted average NOAEL (i.e., 10 for consideration of intraspecies variation). Isopropylbenzene (C9)=ISOPROPYLBENZENE (CUMENE) (C9): The NOAEL (110 mg/kg/day) to obtain 0.04 mg/kg/day Naphthalene (C10): The NOEL 35.7 mg/kg/day, the RfD of 0.04 mg/kg/day Acenaphthene (C12): The NOAEL (175 mg/kg/day) to obtain 0.06 mg/kg/day Biphenyl (C12): the NOAEL (50 mg/kg/day) to obtain 0.05 mg/kg/day Fluorene (C13): The NOAEL of 125 mg/kg/day, RfD of 0.04 mg/kg/day, The LOAEL is 250 mg/kg/day Anthracene (C14): The NOAEL (1000 mg/kg/day) to obtain 0.3 mg/kg/day
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Fluoranthene (C16): The NOAEL (125 mg/kg/day) to obtain 0.04 mg/kg/day Pyrene (C16): The NOAEL (75 mg/kg/day), the LOAEL was 125 mg/kg/day, an oral RfD of 0.03 mg/kg/day C9 Aromatics: Naphthalenes/ Methylnaphthalenes : The NOEL <300 mg/kg, LOAEL = 300 mg/kg/day, an oral RfD = 0.03 mg/kg/day
Table A-9 Description of toxicological properties of some substances Equivalent Carbon Ranges Compounds w/Toxicity Data NOAEL Fraction Oral RfD Fraction Inhalation RfC LOAEL BUTENE (C4) The NOAEL was 5.7 g/m3 for the P generation and > 11.5 g/m3 for the F1 generation. CYCLOPENTENE (C5) - 99.8% The NOEL was 1139 ppm TOLUENE (C7) The RfD of 0.2 mg/kg/day was 0.2 mg/kg/day calculated using the NOAEL of 312 mg/kg, which was converted to 223 mg/kg/day based on the gavage schedule of 5 days/week. An uncertainty factor of 1000 (10 for animal to human; 10 for most sensitive; and 10 for subchronic) was applied to the NOAEL (223 mg/kg/day) to obtain 0.2 mg/kg/day. CYCLOHEXANE (C6) NO 1-HEXENE (C6) The NOAEL for this study was determined to be 350 mg/kg body weight/day. METHYLCYCLOHEXANE (C7) No ETHYLBENZENE (C8) An uncertainty factor of 1000 (10 for animal to human; 10 for most sensitive; and 10 for subchronic)
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was applied to the NOAEL (97.1 mg/kg/day) to obtain 0.1 mg/kg/day. STYRENE (C8) The NOAEL in this study is 200 mg/kg-day and the LOAEL is 400 mg/kg-day. The RfD of 0.2 mg/kg/day was calculated using the NOAEL of 200 mg/kg/day. An uncertainty factor of 1000 (10 for animal to human; 10 for most sensitive; and 10 for subchronic) was applied to the NOAEL (200 mg/kg/day) to obtain 0.2 mg/kg/day. XYLENES (C8) The RfD of 2 mg/kg/day was calculated using the NOAEL of 250 mg/kg, which was converted to 179 mg/kg/day based on the gavage schedule of 5 days/week. An uncertainty factor of 100 (10 for animal to human and 10 for most sensitive) was applied to the NOAEL (179 mg/kg/day) to obtain 2 mg/kg/day. ISOPROPYLBENZENE (CUMENE) The RfD of 0.04 mg/kg/day was (C9) calculated using the NOAEL of 154 mg/kg, which was converted to a 110 mg/kg/day based dosing schedule of 139 doses in 194 days. An uncertainty factor of 3000 (10 for animal to human; 10 for most sensitive; 10 for subchronic; and an additional 3 for inadequate database) was applied to the NOAEL (110 mg/kg/day) to obtain 0.04 mg/kg/day. N-NONANE(C9) NO N-PROPYLBENZENE (C9) NO
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1,3,5-TRIMETHYLBENZENE (C9) The NOEL for this study was determined at 60 mg/kg, based on increased cholesterol levels and liver weight at 150 and 600 mg/kg. A NOEL was established at 200 mg/kg based on increased phosphorous levels, liver and kidney weight reported at 600 mg/kg/day. T-BUTYLBENZENE (C10) NO N-DECANE (C10) NO DIETHYLBENZENE (C10) The NOEL for maternal toxicity was considered 20 mg/kg/day and the NOEL for fetal toxicity was considered 100 mg/kg/day. NAPHTHALENE (C10) A provisional RfD for naphthalene of 0.04 mg/kg/day was developed by the USEPA. This RfD was based on an oral subchronic NTP unpublished study (NTP, 1980). In this study, rats were administered naphthalene by gavage 5 days/week for 13 weeks. The dose levels used in this study were not published in any of the available summaries. However, the NOEL was identified to be 50 mg/kg/day. The critical effect was decreased body weight. Using the gavage schedule of 5 days/week, the 50 mg/kg/day is converted to 35.7 mg/kg/day. An uncertainty factor of 1000 (10 for animal to human; 10 for most sensitive; and 10 for subchronic) is used to calculate the RfD of 0.04 mg/kg/day.
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This provisional RfD is not on IRIS nor is it in HEAST. This value was on IRIS but was pulled pending further review. The value was also removed from HEAST due to the uncertainty in the calculation of the RfD. TETRALIN (C10) NO METHYLNAPHTHALENE (C11) The RfD of 0.06 mg/kg/day was calculated using the NOAEL of 175 mg/kg/day. An uncertainty factor of 3000 (10 for animal to human; 10 for most sensitive; 10 for subchronic; and an additional 3 for inadequate database) was applied to the NOAEL (175 mg/kg/day) to obtain 0.06 mg/kg/day. BIPHENYL (C12) The RfD of 0.05 mg/kg/day was calculated using the NOAEL of 0.1%, which was converted to 50 mg/kg/day. An uncertainty factor of 100 (10 for animal to human and 10 for most sensitive) and a modifying factor of 10 were applied to the NOAEL (50 mg/kg/day) to obtain 0.05 mg/kg/day. Neither teratogenicity nor maternal toxicity was evident at doses ranging from 125 to 500 mg/kg biphenyl FLUORENE (C13) The LOAEL is 250 mg/kg/day based on hematological effects and the NOAEL is 125 mg/kg/day. The RfD for fluorene was calculated by taking the NOAEL of 125 mg/kg/day and applying an uncertainty
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factor of 1000 (10 for animal to human; 10 for most sensitive; and 10 for subchronic) and a modifying factor of 3 for lack of adequate toxicity data in a second species and reproductive/developmental data. ANTHRACENE (C14) The RfD of 0.3 mg/kg/day was calculated using the NOAEL of 1000 mg/kg/day. An uncertainty factor of 3000 (10 for animal to human; 10 for most sensitive; 10 for subchronic; and an additional 3 for inadequate database) was applied to the NOAEL (1000 mg/kg/day) to obtain 0.3 mg/kg/day. FLUORANTHENE (C16) The RfD of 0.04 mg/kg/day was calculated using the NOAEL of 125 mg/kg/day. An uncertainty factor of 3000 (10 for animal to human; 10 for most sensitive; 10 for subchronic; and an additional 3 for inadequate database) was applied to the NOAEL (125 mg/kg/day) to obtain 0.04 mg/kg/day. PYRENE (C16) The NOAEL was determined to the LOAEL was 125 mg/kg/day be 75 mg/kg/day and for nephropathy and decreased the LOAEL was 125 mg/kg/day kidney weights. for nephropathy and decreased kidney weights. The RfD for pyrene was calculated by taking the NOAEL of 75 mg/kg/day and applying an uncertainty factor of 1000 (10 for animal to human; 10 for most sensitive; and 10 for subchronic) and a
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modifying factor of 3 for lack of adequate toxicity data in a second species and reproductive/developmental data. BENZ(A)ANTHRACENE (C18) Classified as a B2 carcinogen - use B(a)P slope factor and a potency factor. CHRYSENE (C18) Classified as a B2 carcinogen - use B(a)P slope factor and a potency factor. BENZO(B)FLUORANTHENE (C20) Classified as a B2 carcinogen - Seven PAHs (benzo(a)pyrene, killed.” use B(a)P slope factor and a benzo(b)fluoranthene, Benzo(a)pyrene, potency factor. benzo(j)fluoranthene, benzo(b)fluoranthene, benzo(k)fluoranthene, benzo(j)fluoranthene, indeno(1,2,3-cd)pyrene, benzo(k)fluoranthene cyclopentadieno(cd)pyrene, and at concentrations between coronene) 0.01% and 0.5% dissolved in acetone were applied to the clipped backs of female Swiss mice (20/dose/chemical) three times 95 per week for the lifetime of the animals (Wynder and Hoffmann, 1959). Results show that benzo(a)pyrene, benzo(b)fluoranthene, and benzo(j)fluoranthene produced high incidences of skin papillomas and carcinomas at all dose levels. Benzo(k)fluoranthene produced a limited number of papillomas only at the high dose level (0.5%). There were no control groups in the study. BENZO(K)FLUORANTHEN (C20) Classified as a B2 carcinogen - use B(a)P slope factor and a potency factor. BENZO(GHI)PERYLENE (C20) B(a)P produced tumors in 85 and 95% of the animals at
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concentrations of 0.05 and 0.1%, respectively. DIBENZ(AH)ANTHRACENE (C22) Classified as a B2 carcinogen - use B(a)P slope factor and a potency factor. BENZO(A)PYRENE (C20) Classified as a B2 carcinogen- slope factor 7.3 (mg/kg/day)-1. Aliphatic fractions Commercial Hexane Commercial hexane, contained 53% n-hexane, 16% 3- methylpentane, 14% methylcyclopentane, 12% 2-methylpentane, 3% cyclohexane, 1% 2,3- dimethylbutane, and <1% several minor compounds
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Characteristics of geological material
Table A-10 Typical values of soil porosity
Table A-11 Differences in total and effective porosity (MENZ 1999)
Table A-12 Hydraulic conductivities for different soil materials (MENZ 1999)
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Table A-13 Default Parameters for Soil Screening Values (SSVs) calculation Symbol Definition Receptor Default Reference BW Body weight (kg) Aggregate resident 51.9 Derived from equation using child and adult body weights
child 16.8 Derived from NHANES III data Adult/worker 76.1
IRo ingestion rate, oral Aggregate resident 120 Derived from equation using child (mg/day) and adult ingestion rates
child 200 USEPA (1996)
Adult/worker 50 EF exposure frequency Aggregate resident 350 USEPA (1996) (days/yr) child 350
Adult/worker 250 ED exposure duration Aggregate resident 30 USEPA (1996) (years) child 6 Adult/worker 25 SA surface area exposed Aggregate resident 4810 Derived from NHANES III data (cm2/day) child 2960 using allometric scaling Adult/worker 3500 AF adherence factor Aggregate resident 0.1 RAGS (part E), USEPA 2000 (mg/cm2) child 0.2 Supplemental Guidance for Dermal Risk Assessment – Interim Guidance Adult/worker 0.2 AT averaging time (days) 25550(70yr) RAGS (part A), USEPA 1989a (carcinogens (EPA/540/1-89/002) (AT=ED) averaging time (days) Aggregate resident 10950(30yr) (non-carcinogens) child 2190(6yr)
Adult/worker 9125(25yr)
IRi inhalation rate Aggregate resident 12.2 Exposure Factors Handbook, USEPA (m3/day) 1997 child 8.1
Adult/worker 20 DA dermal absorption ( 0.1 USEPA Region 4 Guidance unitless) (organics) dermal absorption 0.001 (unitless) (inorganics) VF volatilization factor Chemical- Soil Screening Guidance, USEPA (m3/kg) specific 1996b (EPA/540/R-95/128) (See Fig. 7) PEF particulate emission 6.672*109 Soil Screening Guidance, USEPA factor 1996b (EPA/540/R-95/128) (m3/kg) (See Fig. 6) TR target cancer risk 10-6 (unitless) THI target hazard index 1 (unitless) - Aggregate Resident: Age 1 to 31 years. - Child: Age 1 to 7 years. - The default PEF is for 0.5 acre sites with undisturbed soil. Site-specific PEFs must be calculated for sites with contaminated areas which are significantly larger in size or if warranted based on site-specific conditions.
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Appendix B
B.1 Sustainable remediation approaches and frameworks
Various international initiatives from different countries and organizations have now released a number of standards, frameworks, guidelines, authoritative reports, and road-maps with similarities and differences in the approaches to sustainable remediation. Some of the initiatives are (Common Forum, NICOLE, SuRF-UK, SuRF- Italy, SuRF-NL, ASTM, ITRC, SURF, SuRF-Brazil, SuRF-Canada, SuRF-Colombia, SuRF-Taiwan, SuRF- Australia and NewZealandICCL, ISO) (Rizzo et al. 2016). Most of them share the definition that sustainability encompasses environmental, social and economic costs, and particular considerations of sustainability used in sustainable remediation decision-making need to be drawn in a balanced procedure across the sustainability pillar (Rizzo et al. 2016). US SURF defined the concepts of sustainability as having the potential to minimize the harmful side effects produced by remediation activities to human health and the environment. The real benefit from sustainability is the criteria for remediation decision-making applied by practitioners (David E. Ellis et al. 2009, Favara et al. 2011). SuRF-UK has outlined sustainable remediation as “the practice of demonstrating, in terms of environmental, economic and social indicators, that the benefit of undertaking remediation is greater than its impact and that the optimum remediation solution is selected through the use of a balanced decision-making process.” (www.claire.co.uk/surfuk). The application of sustainable remediation should be based on sustainability assessment in order to support the decision-making of management processes (NICOLE 2010). We need to assess sustainability to know for sure that our projects are on a path of sustainable development by appropriate indicators (IISD 1999). Such representative indicators should be as small as possible, but as large as necessary (IISD 1999). SURF-UK identified guidelines for sustainable remediation approaches to balance environmental, social and economic costs. The key principles encompass the protection of human health and the environment by remediation and safe work locations. The remediation decisions should be transparent for the information of the stakeholders and should be based on sound science (Beames et al. 2014, CLARINET 2002). NICOLE recommended that sustainable remediation should be clearly reported and integrated from the early steps of risk assessment, risk management, and sustainable remediation. All stakeholders should be motivated to use risk-based management approaches and studies about risks should also be included (NICOLE 2012).
B.2 Risk-based land management framework
Contaminated sites with petroleum hydrocarbon (PHC) are found in many countries and can cause widespread problems as PHC can be easily leached into the environment. Such environmental problems may pose potential risks to human health, ecosystems, water resources, buildings and other environmental receptors (Wang et al. 2015). Managing the PHC-contaminated sites needs realizing the potential risk from the exposure to PHC. The need for developing a well-organized management framework encouraged countries to develop various approaches, such as a risk-based management system, which include some form of site investigation, risk assessment and the selection of relevant remediation technologies. Most of these approaches are based on risk- based land management concepts. Comprehensive guidelines deduced from these studies that include stages for risk assessment, remediation, spatial planning and monitoring have in general proven beneficial for the rehabilitation of contaminated sites, and thus has led to their introduction in many countries. Consequently Libya can benefit greatly by adopting best practices as now established in many countries, such as in the EU or USA after many years of experience.
B.3 Handling method of management of contaminated sites in Germany
The scheme of the German management system involves the systematic steps of the identification; risk assessment (investigating and assessing hazardous substances) and remediation of contaminated sites (Frauenstein 2009, EEA 2000). The procedure is controlled at State level while the adjusting of soil quality assessment values is controlled at a Federal level. The core of risk assessment, containing the source-pathway- receptor model, are adopted in German contaminated land regulation (Ferguson 1999). Figure D-3 shows the German management and handling method of contaminated sites. It describes the progression from identification
177 of a suspect contaminated site through historical site investigation; preliminary site characterization and risk assessment, remediation and monitoring (CityChlor 2013). The essence is based on a provided expert opinion. Within this track, different assessments are applied in a successive path to define whether a suspected site is “not contaminated”, “under suspicion of being contaminated” or “contaminated”. Site investigation and risk assessment are determined at growing levels of detail at each sequential tier so that sites with low or no risks can be excluded from the further investigation method at an early phase without bearing massive costs, and rapidly severe hazards can be specified (C. P. Nathanail et al. 2013). The site identification and investigation methods can be described in two major stages, the first stage contains a preliminary identification of sites leading to the identification of potential contamination with the objective to encompass such sites in a list of suspected contaminated sites (Verdachtsflächen). The site investigation is the second stage which aimed to find out the concentration of contaminants in soil and groundwater is compared to soil and groundwater screening values. A comparative assessment is made to setting priorities. As a result of this assessment, the relevant sites will be considered a contaminated and encompassed in the federal lists of contaminated sites (UBA 2007, EEA 2000).
B.3.1 Risk assessment in the German method
Risk assessment method in Germany means the complete process of site assessment which follows the historical investigation. The historical investigations are described as the preliminary survey which potentially contaminated sites are systematically identified then registered and evaluated at the level of municipalities (UBA 2007, EEA 2000). Risk assessment is executed for every situation alone and the decisions are decided upon the land use type, the type of contamination and the concentration, the linked receptors and the presence of pollution linkage (exposure pathways) (Ferguson et al. 1998, Ferguson 1999). Risk assessment method contains two major investigations the preliminary investigation (oriented investigation) where the hazard is assessed for the relevant pollution linkage model and a comparison between measured and estimated harmful substances is made (UBA 2007). The next is the main site investigation (detailed investigation) where the suspected hazard is either to be eliminated or becomes a contaminated site and setting of remediation criteria (UBA 2007, EEA 2000). The German framework consists of two screening values levels, the test Value (trigger value(TrV)) and the Action Value. The decision of soil investigation depends on the TrV, in other words, the exceeding of the TrV leads to additional (UBA) investigation, whilst exceeding the Action Value requires an urgent response which means the need for fast remedial action (Provoost et al. 2006). The remediation process in the German management system includes remedial investigation, implementation, and monitoring. The target of the remedial investigation is to select the proper remediation option or a group of options with respect to the economy and ecology criteria. Remediation concepts must be prepared to sustainability (UBA 2007, CityChlor 2013).
B.3.2 Land use scenarios in Germany
There are four categories according to the sensitivity of land use: playgrounds for children, residential areas, parks and recreational facilities and industrial areas (UBA 2007, C. P. Nathanail et al. 2013, Carlon 2007).
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Figure D-3 Management framework of contaminated sites in Germany (UBA 2007)
B.3.3 Features of the German method
There are many advantages of the German method (UBA 2007, C. P. Nathanail et al. 2013) Policy: A consistent and transparent management system with land use categories across all Federal States, Investment: Strong public sector in rehabilitation of contaminated sites, Research and technical capabilities: Very strong linked to contaminated land management, Treatment technologies: A large capacity in ex-situ soil, Approaches: Realistic to setting up risk management objectives, Risk assessment: Awareness of importance of such approach for determination of contamination and remediation demands, Land management: Ideas to the largest European market location, Decisions: Based on in deep hazard study; therefore decisions on remediation are done case by case.
B.4 Model procedures for the management of land contamination-UK
The Model Procedures-UK includes three parts as shown in Figure D-4. Part 1 is known by a procedure which sets out the framework of the process. Part 2 is known by Supporting Information which provides further technical detail to support the process. Part 3 is known by Information Map contains sources of further information and guidance (EA-GOV-UK 2004a). The risk management system in the model procedures-UK consists of three main parts as shown in Table D.2, risk assessment, options appraisal and implementation of the remediation strategy (EA-GOV-UK 2004a). Risk assessment - to identify if there is an unacceptable risk and, if so, what should be necessary actions needed to be possessed relevant to the site. Optional appraisal follows risk assessment process where remediation options are evaluated for the site. The third process - implementation and monitoring of the remediation technology/ies (EA- GOV-UK 2004a).
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B.4.1 Risk assessment process in the UK procedures
Risk assessment is a fundamental section in the system and supports both the part 2A EPA 1990 and the planning regime. A tiered assessment structure is adjusted and the stages are used to the circumstances of the site under consideration with an increasing level of detail required by the assessor. The three applied stages are a preliminary risk assessment, generic quantitative risk assessment, detailed quantitative risk assessment (EA- GOV-UK 2012). When the risks are assessed, then necessary action to reduce or control will be considered and the next step of the method is the options appraisal where detailed remediation options and strategy and have been identified and agreed. The next step is the practical implementation of the remediation strategy (EA-GOV- UK 2004b).
B.4.2 Land use scenarios in the UK
Most common classification of the land use in many European countries is referenced to agricultural, natural, recreational, residential and industrial land use. In the UK the distinctions can be made for the presence/absence of gardens in the residential scenario (Carlon 2007). The Environmental Agency (EA) in the UK uses a tool called by the Contaminated Land Exposure Assessment (CLEA) model to derive: (i) previously Soil Guideline Values (SGVs) through the generic land use scenarios used. The generic land use scenarios that have been used to derive SGVs are: Residential land use, Allotment land use and Commercial land use (EA-GOV-UK 2009a, b)., currently a methodology for development of Category 4 Screening Levels (C4SLs) for using four generic land-use including residential, allotments, commercial and public open space
Figure D-4 The Process of Managing Land Contamination-UK (EA-GOV-UK 2004a) B.4.3 Features of the UK procedures:
Using the Part 2A regime, therefore the model procedures, several benefits are described as (C. P. Nathanail et al. 2013): The profile of contaminated sites cases in the UK increased, the capabilities of the contaminated site's industry enhanced, the experience of the contaminated site's industry enhanced, dealing with contamination where the result has a significant impact on local residents and environment enhanced, good practice with respect to sites contamination cases within the redevelopment industry provided, developers and their advisors, planners and other regulatory staff in approving and policing the development process involved, the level of competence of those within the major consultancies employed to provide advice to some stakeholders improved the balance between cost and effect that the regime tries to maintain is generally appreciated, and the regime has been used successfully at well over 1000 sites.
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B.5 Stakeholder engagement
Decision-making processes during the management of contaminated sites require the balancing of multifaceted scientific findings and the many different perspectives and stakeholders with different priorities and opinions (Linkov et al. 2006). The stakeholder is defined as “any group or individual who can affect or is affected by the achievement of the organization’s objectives” (Hermans 2005). A stakeholder is also defined as anybody who is impacted by or can impact the development, growth, consequence or decision making of a risk assessment. Stakeholders can be organizations, communities or individuals who manage, undertake, or monitor rehabilitation actions and in addition, those who may be impacted by or who may influence and are involved in the decisions (Norrman et al. 2016, ITRC 2011d). Stakeholders may include risk assessors, project managers, tribal members, property owners, regulatory agencies, community leaders, political leaders, and business leaders, as shown in Figure 4-1 (ITRC 2015a). Stakeholder engagement is defined as the practical method of including stakeholders in the risk assessment stage. The implication of a wide range of stakeholder opinions and preferences is an important portion of understanding wider values and sustainability (Bardos et al. 2016). Stakeholder requirements, experience, overviews, and anticipations provide a high value to the growth, development, and monitoring of the risk assessment and decision-making process. Some stakeholders are involved at the core of the project decision making, and their perspectives have a controlling influence on project decisions. Other stakeholders are not as essential but their perspectives may affect or should guide project management decisions. Therefore, stakeholder engagement broadens the active process of discussions with those inside and outside of the core group. In general, perspectives are identified and evaluated early in the rehabilitation process of contaminated sites. Figure 4-2 shows how the process of stakeholder engagement can be applied by using a group of measures: a) inform, b) consult, c) involve, d) collaborate, and e) empower (Cundy et al. 2013). Perfect and active risk communication can help the engagement of stakeholders in risk assessment (ITRC 2015a, Sam et al. 2016).
Figure 0-1 Stakeholders in the contamination management process (ITRC 2015b)
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Figure 0-2 A spectrum of involvement measures for stakeholder engagement
B.6 Risk communication
An effective stakeholder engagement must understand potential risks associated with exposure to chemical release (Hazard) and the hypothesis used for the calculation of potential risks, such as the type of receptor or current and future land use. Risk communication is formal or informal communication which achieve transparent decisions for remedial action (NRC 2009) through conversations and meetings with stakeholders. Risk communication shares and exchanges data, information and results with stakeholders during the various stages of the risk management process. This results in well-informed stakeholders who are able to appreciate scientifically well-versed concepts necessary for the decision-making process(ITRC 2015a, USEPA 2007). The main elements of risk communication are: a) transparent information relayed in non-technical language; b) central issues and questions that need to be addressed and answered to understand the problem; c) significant data and information needed to deal with the questions; d) data origins and uncertainty management (Defra 2011). Risk communication will help in a) providing information on risk assessment, reduce needless worries of involved groups; b) minimize the misunderstanding of risk, minimize potential needless delays; c) establish a perfect working relationship with key stakeholders (SNIFFER’s et al. 2010). (USEPA 1991b) identified the following rules, from Seven Cardinal Rules of Risk Communication (USEPA 1988c), which should be kept in mind: 1. Accept and involve the public as a legitimate partner, 2. Plan carefully and evaluate your efforts, 3. Listen to the public’s specific concerns;, Be honest, frank, and open, 4. Coordinate and collaborate with other credible sources, 5. Meet the needs of the media, and 6. Speak clearly and with compassion Communication with all stakeholders is also important and necessary for the decision-making process to find the optimal end target of risk management and to find the appropriate procedure to realize risk reduction (Swartjes, 2011a).
B.7 Sustainable remediation management approach for the USA
In the USA, green remediation is the main approach in the management of contaminated sites as regulated by the US-EPA, under CERCLA, which considers it “as the practice of considering all environmental effects of clean- up actions and incorporating options to minimize the environmental footprints of cleanup actions” (Rizzo et al. 2016, USEPA 2008). In general, green remediation is realized as the main step in maximizing the environmental outcome of remediation of contaminated sites. Five key components of green remediation have been identified, (1) energy, (2) air & atmosphere, (3) water, (4) land & ecosystem and (5) materials & waste, as shown in Figure 4-3 (USEPA 2010).
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Figure 0-3 The key components of green remediation
The approach provides a systematic, process-based, holistic framework for the consideration, implementation, and documentation of sustainability parameters during the treatment process in a manner that complements and creates upon existing sustainable remediation guidance records. The framework is easy to use and involves each phase of a conventional remediation project: investigation, remedy option selection, remedial design, planning and construction, operation and maintenance, and project closure. Each stage is described in Figure 4-4. The application of each of the remediation project stages is illustrated in the left part of Figure 4-4. This method recommends that each project stage is a stand-alone entity and one project phase must be completed before the next stage can start. For example, the remedy selection can only commence after the investigation phase has finished. Consistent with this clear method and, sustainability parameters have been integrated into existing remediation projects in a stage-by-stage method, as shown in Figure 4-4. (Holland et al. 2011). Sustainability processes can be extended during the investigation, planning and design, construction, operation, and monitoring stages of site remediation in any of the chosen remediation technologies. As remediation technologies continue to advance and boost development, green remediation strategies offer significant potential for extending the net benefit of remediation, thus saving project costs, and protecting the environment for long- term property use or reuse alternatives without compromising remediation goals (USEPA 2008).
Figure 0-4 The phases of framework for Integrating Sustainability
(ASTM 2013) provides a six-step flowchart for Best Management Practice (BMP) selection and implementation in order to encourage users to incorporate sustainable components into remediation projects. ASTM also provides a structure that describes the relationships between the three elements of sustainability across different specific considerations: local community vitality, energy, efficiencies in clean-up cost savings, and the proposed best management practices.
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B.8 Tiered sustainable remediation management approach for the UK
SuRF-UK concluded that decisions which influence sustainability are subject to local situations and stakeholder demands, and is also influenced by firms and governmental sustainable development policies and aims. Therefore the management of sustainability could turn out to be a complex method. SuRF-UK developed a tiered framework to reduce such complexity by driving balanced decision-making method as an integral section of sustainability development part in the selection of remediation option to resort contaminated sites. The basic concepts that established by SuRF-UK to minimize such complexity are:
1. Decisions and evaluations should be structured. 2. Consistent boundaries must be used in decision making and sustainability assessment. 3. Evaluating sustainability is basically a subjective method and needs to be accepted as such.
The SuRF-UK framework characterizes two basic stages of sustainability concept, “stage A”: planning/design project and “stage B”: implementation of remediation technologies, as shown in Figure 4-5 (Bardos et al. 2011)
Figure 0-5 The management framework of sustainable remediation from SuRF-UK
B.9 Tiered sustainable remediation assessment approach for the USA
SURF-USA balances the sustainable remediation parameters throughout the remediation project life-cycle to create a harmonious process by providing remediation practitioners and regulators as stakeholders. The SURF approach is aligned with the tiered approach for Risk-Based Corrective Action (RBCA), a method authorizing decisions to be made based on the risks linked to human health and the environment (Holland et al. 2011). The tier1 sustainability assessment framework includes non-project- details, as shown in Figure 4-6. Tier 2 follows a semi-quantitative approach, depending both on project-specific and non-project-specific information. Tier 3 includes a quantitative assessment and is the most detailed and project-specific tier, , and involves a quantitative assessment. The aim of the sustainability assessment, regardless of the assessment tier selected, is to balance parameters in a way that increases the positive sustainability impacts of the remediation project while decreasing the negative sustainability impacts (Holland et al. 2011).
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Figure 0-6 Tiered sustainable remediation assessment framework SURF-USA
B. 10 Tiered sustainable remediation assessment approach for the UK
SuRF-UK defined sustainability assessment as “The process of gaining an understanding of possible outcomes across all three elements (environmental, social, and economic) of sustainable development” (www.claire.co.uk/surfuk). Figure 4-7 shows a framework of how sustainability is assessed according to the SuRF-Uk approach. The process contains three tiers of sustainability assessment, qualitative, semi-qualitative or quantitative. Figure 4-8 shows how the sustainable remediation is executed in a hierarchical system. It starts with Sustainable Management Practices (SMPs) which are aligned to the SuRF-UK sustainability indicator categories so that the same sustainability principles can underpin all aspects of land contamination management and can be applied across a full range of activities, including those that would not normally have a formal sustainability assessment. Then, the tiers of sustainability assessment follow the SMPs, which are demonstrated in a pyramid to show how a decision-making process is considered a bottom to top procedure.
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Figure 0-7 Sustainability assessment framework-SuRF-UK
Figure 0-8 Sustainability assessment pyramid SuRF-UK
Figure 4-9 shows the key steps of a sustainability assessment framework-SuRF-UK, and displays the assessment process step by step. The 1st step is preparation, and describes a decision demand, the project, and constraints. It takes into account reporting and dialogue in which the sustainability assessment method is provided in a clear specification. The 2nd step is a description of objectives, boundaries, scope, methodology and dealing with uncertainty in a clearly defined assessment method. The 3rd step is the execution of the assessment process by comparisons, aggregation, interpretation, uncertainty assessment in order to receive results.
Figure 0-9 The key steps in sustainability assessment framework-SuRF-UK
B.11 Metrics & indicators
Sustainable indicators (SI) are the key to understanding and reaching sustainability. They are a fundamental and powerful tool in the decision-making process. The term means pointing towards something. “An indicator is the
186 operational representation of an attribute (quality, characteristic, property) of a given system, by a quantitative or qualitative variable (for example numbers, graphics, colors, symbols) (or function of variables), including its value, related to a reference value.” (Waas et al. 2014). Traditionally, indicators are quantification tools. Obviously, quantitative SI and qualitative SI are important for a sustainable development. However, measuring human experiences in a quantitative manner alone does not suffice. Although it is desirable for decision-making to rely on quantified SI rather than qualitative data, we should be very cautious about interpreting and visualizing the entire system solely on quantitative terms. “The fact that people consider something ugly or beautiful, harmonious or dissonant, noble or ignoble is not to be swept away as ‘mere opinion’” (Waas et al. 2014). Indicators offer overall information about the systems forming sustainable development (IISD 1999), many requirements for finding indicators of sustainable development are identified as follows: a. Indicators of sustainable development are needed to guide policies and decisions at all levels of society: village, town, city, county, state, region, nation, continent, and the world. b. These indicators must represent all important concerns: An ad hoc collection of indicators that just seem relevant is not adequate. A more systematic approach must look at the interaction of systems and their environment. c. The number of indicators should be as small as possible, and as large as necessary. That is, the indicator set must be comprehensive and compact, covering all relevant aspects. d. The process of finding an indicator set must be participatory to ensure that the set encompasses the visions and values of the community or region for which it is developed. e. Indicators must be clearly defined, reproducible, unambiguous, understandable and practical. They must reflect the interests and views of different stakeholders. f. From a look at these indicators, it must be possible to deduce the viability and sustainability of current developments and to compare them with alternative development paths. g. A framework, process, and criteria for finding an adequate set of indicators of sustainable development are needed.
Figure 0-10 Illustration of how indicators guide the process (IISD 1999)
B.12 Life cycle assessment
Life cycle assessment is defined as “compilation and evaluation of the inputs, outputs and the potential environmental impacts of a product system throughout its life cycle” (DIN-EN-ISO-14040:2006-10 2009). LCA is a broad tool using environmental support systems for decision-making concerning the remediation of contaminated sites. LCA is used to compare the environmental effects of various remediation options. Treatment processes of contaminated sites can lead to a reduction of environmental pollution problems but increase other environmental pollution problems on the neighbor, regional and global scale. Therefore, LCA is used to assess the hidden characteristics and to compare remediation technologies with respect to their environmental effects
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(Lemming et al. 2009). (Owsianiak et al. 2013) recommend applying LCA to support decision-making processes in the management of the contaminated site to obtain cleaner environmental solutions.
Life cycle assessment often covers the analysis of the environmental impacts of a product system through all stages of its life cycle. Sometimes also called "life-cycle approach", "life cycle analysis", "cradle to grave analysis" or "Ecobalance", it has created a rapidly emerging group of tools and techniques designed to help in environmental management (Bayer and Finkel 2006) and, on the longer term, in sustainable development (Allan Astrup Jensen et al. 1998). (DIN-EN-ISO-14040:2006-10 2009) describes life cycle assessment, “LCA considers the entire life cycle of a product from raw material extraction and acquisition through energy and material production and manufacturing, to use and end of life treatment and final disposal. Through such a systematic overview and perspective, the shifting of a potential environmental burden between life cycle stages or individual processes can be identified and possibly avoided.
LCA consists of (Rebitzer et al. 2004):
1. Goal and scope definition 2. A detailed life Cycle Inventory (LCI) analysis 3. An assessment of the potential impacts 4. The interpretation of the results
The comprehensive goal of the project should be identified, for example, the comparison between two remediation options in terms of long-term environmental performance. After identifying the initial project objectives of the LCA, it is essential to establish the context in which the assessment is to be made. The ensuing stages are inventory analysis, impact assessment, and interpretation. The inventory analysis (LCI) inspects and gathers all relevant inputs and outputs (energy & materials) of processes during the life cycle of a product, activity, or service. The impact assessment (LCIA) is carried out to translate the gathered data, for example, emissions and consumptions, into environmental and/or health effects and is commonly expressed by a number of representative indicators. Lastly, the results of the inventory analysis and impact assessment are discussed during the interpretation stage in order to elicit the major sources of environmental burden and to conclude recommendations for the best product or service (Bayer and Finkel 2006).
Life cycle assessment approaches identify the total environmental impact of remediation options, from cradle to grave. LCA methods are applied in remediation projects before the remediation technology is selected and after the end of the remediation project. When applied before the selection of the remediation technology, LCA analyses evaluate environmental impacts of the alternative remediation technology, and the findings are mainly site-specific. The LCA method is also applied after the remediation project has ended, and subsequently, the applied LCA may be much more elaborate. The aim of applying LCA after the end of the remediation project is to improve and develop remediation technologies, to gain more knowledge about the environmental impacts, and to upgrade priory applied LCA frameworks in remediation (Pascal Suér et al. 2004).
The LCA procedure has been widely applied for assessing the environmental effects on a global and regional scale, such as global warming, acidification, carcinogenic (human toxicity), eutrophication, ozone depletion, and smog formation generated from the remediation projects on contaminated soil and groundwater. LCA has been used to contrast various remediation technologies for soil remediation such as bioremediation, soil washing, and soil excavation, for example, there are many study projects for remediation of contaminated groundwater. Most of the studies were conducted in order to compare a Pump-and-Treat (PT) system and a Permeable Reactive Barrier (PRB) system (Mak and Lo 2011).
A very useful descriptive Life Cycle Framework (LCF) was developed by (Miriam L. Diamond et al. 1999).I It involves descriptions of Life-Cycle Management (LCM) and the adaptation of LCA to site remediation options. LCM is a systematic approach developed in order to generalize and construct the environmental actions, upgrade the schematic design of decision making, and to constantly join economic efficiency with environmental improvement. LCF was developed to test the wider human health and environmental implications linked with the remediation of soil and groundwater, as shown in Figure 4-11 (Miriam L. Diamond et al. 1999).
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Figure 0-11 The elements of the life cycle framework for the assessment of remediation options of contaminated sites`
LCA is a particular analytical and planning tool developed to evaluate the environmental impact assessments within a general framework, while Environmental Impact Assessment (EIA) is a method used to boost decision making with regard to environmental aspects of a much wider range of activities. Therefore LCA can be adopted in EIA (Tukker 2000).
B.13 Cost-benefit analysis (CBA)
The cost-benefit assessment (CBA) method is an estimation procedure for comparing the potential costs of a project with its benefits. Such an evaluation is based on a conversion to monetary codes and is therefore characterizes as a cost-benefit analysis (Bardos et al. 2016, EA-GOV-UK 1999). By using CBA, all the benefits and costs of specific stages of the process are compared and explained. The CBA method is only implemented in order to compare the cost of potential remedial alternatives during the decision-making process of remediation projects (Harclerode et al. 2015). The main objective is to find the most efficient course of action. All benefits of alternative risk reduction options are offset against their costs in order to identify the course of action with the highest net benefit. Compared to other options, CBA offers a crucial boost for decision makers (Meyer et al. 2013). Cost and remediation time are the most significant criteria in the description of a remediation technology regarding a cost-benefit analysis. Execution is the elimination ratio, expressed as the ratio between the residual contaminant concentration in a given matrix and the initial concentration in the same matrix. Cost gives information on the overall cost per treated matrix unit (US$/t of soil matrix wet weight and US$/1,000 L of water matrix), and is strictly related to the elimination rates (Critto et al. 2006). Cost-benefit analyses facilitate well- informaed judgments by the project managers and is one of the principal analytical tools used to support environmental decision making for contaminated sitemanagement in many EU countries. Risk assessment and cost-benefit analyses are currently the major decision support approaches in the USA (Gregory A. Kiker et al. 2005). The benefits of remediation or protection can be considered as the total value of damages that would occur if the contamination were not treated, or protection measures were not applied. This should involve the applied and non- applied measures for groundwater.Economic evaluations should be designed to extend information on main factors in order to aid environmental decision-makers to select suitable remediation options (EA-GOV-UK 2002b).
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Incorporating Multi-Criteria Decision Analysis (MCDA) principles and tools with existing approaches, including the use of risk and cost-benefit analysis, will lead to more effective, efficient, and reliable decision making in environmental projects (Gregory A. Kiker et al. 2005).
B.14 Multi-criteria decision making (MCDM)
The complexity of decision-making processes in environmental projects by different stakeholders requires trade- offs between socio-political, economic and environmental effects. Multi-Criteria Decision Analysis (MCDA) is an essential methodology to face available technical information and stakeholder measures in order to boost decisions in many fields and is especially commendable in environmental decision-making processes (Linkov et al. 2005). MCDA is an application tool used to rank remediation technology options and to upgrade alternative remediation options to be offered to stakeholders (Critto et al. 2006, Gregory A. Kiker et al. 2005). Decision- making processes in environmental projects are often complicated and based upon multidisciplinary knowledge which integrates natural, physical social sciences, politics, and economics. Environmental decision makers depend on many computational models, experimental tests, and tools to assess human health risks and ecological risks associated with environmental stressors and the effect of remedial strategies on the removal of risk. However, applying such tools is becoming increasingly difficult for various reasons. Information related to the many new risks is not available. Therefore decisions are made under significant uncertainties (e.g., climate change, nanotechnology, etc.). There are different management options for many conventional stressors and cases with the same risk value. Stakeholders, who may have a vested interest in specific courses of action, are gaining increased access to all available information and, given the information uncertainty, can justify often opposing courses of action. As such, integrating the heterogeneous and uncertain information demands a systematic and understandable method in order to organize the technical information and requires expert judgment (Huang et al. 2011). MCDA is a systematic procedure to merge different inputs (e.g. natural, physical social sciences, politics, economics, many findings from experimental tests, computational models results etc.) with cost/benefit information and stakeholder opinions in order to rank project alternatives. MCDA is used to discover and quantify decision maker and stakeholder views about different (mostly) non-monetary factors in order to gain a trade-off between alternative courses of action. There are numerous methods that all fall under the MCDA approach, each including various protocols for eliciting inputs, structures to represent them, algorithms to merge them, and processes to interpret and use formal results in actual advising or decision making contexts. MCDA techniques have been applied to optimize policy selection in the remediation of contaminated sites, the removal of contaminants entering aquatic ecosystems, the optimization of water and coastal resources, and the management of other resources (Huang et al. 2011).
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Appendix C The Four administrative territories in Libya.
Figure C -1 The main territories in Libya (H.A. Zurqani et al. 2011)
Figure C-2 shows the main groundwater basins in Libya (a: Jifarah, b: Jabal Nafusah, c: Murzuq, d: Jabal al Akhdar, and e: Kufrah) (Abagandura and Park 2016).
Figure C-2 The main Groundwater basins and soil classification and land features in Libya
Table C.1 List of the most important environmental laws and legislation in Libya Law No. Subject field Brief description comments 25-1955 Petroleum Organization (Law:25 1955)
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105-1958 various issue (Ex. marine vessels collision) (Law:105 1958) 5-1969 Towns and villages organization and planning amended by 3-2002 (Law:5 1969) 142-1970 The tribal lands and wells (Law:142 1970) 8–1973 Prevention of Pollution The sea against oil (Law:8 1973) 112-1973 water well drilling (Law:112 1973) 38/39-1975 municipalities organizing environmental protection (Law:38/39 1975) actions 62-1976 marine law and Captain’s amendments (Law:62 1976) responsibility 106-1976 The health law Issuance (Law:106 1976) 2-1979 Economic crimes (Law:2 1979) 2-1982 Ionizing radiation Regulation (Law:2 1982) and the prevention of risks 3–1982 Water Resources Organization the Utilization (Law:3 1982) 5-1982 Rangelands and forests Protection (Law:5 1982) 7–1982 Environmental Protection and Improvement amended by 15-2003 (Law:7 1982) 1-1983 The agricultural inspection Creation (Law:1 1983) force 13-1984 public cleansing Executive regulation special hygiene provisions (Law:13 1984) 17-1985 Grazing Regulation (Law:17 1985) 14–1989 Marine Wealth Organization the Utilization (Law:14 1989) 15–1989 Animals and Trees Protection (Law:15 1989) 5–1992 Pastures and Forests Protection (Law:5 1992) 15–1992 Agricultural Land Protection (Law:15 1992) 3-2002 Towns and villages organization and planning (Law:3 2002) 15-2003 Environment Protection and Improvement (Law:15 2003) Decision Model Public Cleansing Regulation (Dec.No.24 1976) 24-1976 Decision Potable Water in Oil The ban 69-1980 Reservoirs Resolution Law 3 1982 Executive Regulations 190-1982 Decision water use and prevention Criteria and Rules (Dec.No.790 1982) 790-1982 of pollution Decree No. Hydrographic zones of Rules and Regulations (Dec.No.791 1982) 791-1982 Libya Resolution The General Authority for Establishment 249-1989 Water Resolution The General Authority for Establishment (Res.No.263 1999) 263-1999 the Environment
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Appendix D
Figure D-1 World map of climates in the modified Köppen classification system (A Western Paragraphic Projection developed at Western Illinois University)
(James Petersen et al. 2013)
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Figure D-2 World map of climates in the modified Köppen classification system (A Western Paragraphic Projection developed at Western Illinois University)
(James Petersen et al. 2013)
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Figure D-3 The map of Köppen-Geiger climate classification for Africa
(Peel et al. 2007)
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Figure D-4.a The map of Köppen-Geiger climate classification of the world (http://koeppen-geiger.vu- wien.ac.at/present.htm)
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Figure D-4.b The map of Köppen-Geiger climate classification of the world (http://koeppen-geiger.vu-
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wien.ac.at/present.htm)
Figure D-4.c The map of Köppen-Geiger climate classification of the world (http://koeppen-geiger.vu- wien.ac.at/present.htm)
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Figure D-5 World Map of Köppen-Geiger climate classification
(Kottek et al. 2006b)
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Figure D-6 Climatic zones in the USA
Table D-1 Q/C values by source area, city and climate zone in the USA
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Table D-2 Volatile dispersion site ranking
Table D-3 PEF calculations and site rankings
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Appendix E E.1 Contaminants
Chemical contaminants are classified in eight groups according to the Federal Remediation Technologies Roundtable (FRTR) (https://frtr.gov/) as follows: a. Nonhalogenated volatile organic compounds (VOCs); b. Halogenated volatile organic compounds; c. Nonhalogenated semivolatile organic compounds (SVOCs); d. Halogenated semivolatile organic compounds; e. Fuels; f. Inorganics; g. Radionuclides; and h. Explosives.
E.2 List of remediation technologies
The main essential strategic methods to reduce or treat most of the contaminated sites are: a. Destruction or alteration of contaminants, here the focus of work is on contaminants b. Extraction or separation of contaminants from environmental media, here the target is to cur any pathways to receptors, i.e. prevent any transport of stressors to receptors. c. Immobilization of contaminants, the strategy here is to transport contaminants.
(https://frtr.gov/) classified the remediation technologies into 14 technical groups as follows:
E.2.1 Soil, sediment, and sludge:
In situ biological treatment. In situ physical/chemical treatment. In situ thermal treatment. Ex situ biological treatment (assuming excavation). Ex situ physical/chemical treatment (assuming excavation). Ex situ thermal treatment (assuming excavation). Containment. Other treatment processes.
E.2.2 Groundwater, surface water, and leachate:
In situ biological treatment. In situ physical/chemical treatment. Ex situ biological treatment (assuming pumping). Ex situ physical/chemical treatment (assuming pumping). Containment.
E.2.3 Air emissions/off-gas treatment:
Biofiltration High energy destruction Membrane separation Oxidation Scrubbers Vapor phase carbon adsorption
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Remediation Technologies Options Table E-1 Remediation technologies used for soil, (vadose zone) (Godheja et al. 2016, FRTR 1990)
Remediation technology Method Advantages Disadvantages Features Cost Application 1.1 In-situ biological treatment 1.1.1 Bioventing feeding oxygen to existing • Very economic and • High concentrations a medium to key cost petroleum soil microorganisms easy to install can be toxic long-term drivers: hydrocarbons, • can be combined with for microorganisms technology. surface nonchlorinated other • Low soil permeability Cleanup ranges area & solvents, some technologies doesn’t from a few soil type pesticides, wood allows proper months to preservatives, and implication. several years other organic • Good for unsaturated chemicals zones of soils. 1.1.2 Enhanced indigenous or inoculated a long-term $30 to soils, sludges, and Bioremediation micro-organisms degrade technology $100 per ground water (metabolize) organic which may take cubic contaminated with contaminants existed in soil several years for meter petroleum and/or groundwater, cleanup of a hydrocarbons, modifying them to innocuous plume solvents, end products pesticides, wood preservatives, and other organic chemicals 1.1.3 Phytoremediation uses plants to eliminate, • Least environmental • Two growing seasons key cost metals, pesticides, (Vegetation-enhanced transfer, stabilize, and destroy disturbance. required drivers: solvents, bioremediation) contaminants in soil and • Solar energy driven • Limited to soils less scale of explosives, crude sediment technology. than one effort & oil, PAHs, and • Used on a large range meter from the surface density of landfill leachates. of and sampling contaminants. groundwater less than 3 • Cost-effective for large m from
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contaminated sites the surface • Contaminants may enter the food chain through animals which eat the plants used in these projects 1.2 In Situ Physical/Chemical Treatment 1.2.1 Chemical Oxidation oxidants have been able to • Target treatment group • Incomplete oxidation the site properties of the cause the rapid and complete is inorganics. may conditions is the chemical itself chemical destruction of many • Also used but less occur depending upon key to effective and its toxic organic chemicals effective the work susceptibility to for non-halogenated contaminants and oxidative VOCs and SVOCs, oxidizing degradation fuel hydrocarbons and agent used pesticides. • Not cost-effective for high contaminant concentrations. • Presence of oil and grease in the media reduces efficiency. 1.2.2 Electrokinetic implementation of a low- • Has small impact on • Efficiency reduced by $117 per heavy metals, Separation intensity direct current environment (soil alkaline cubic anions, and polar (Electrokinetics; through the soil between removal is soils. meter organics in soil, Electromigration) ceramic electrodes not required). • Requires soil mud, sledge, and • Metals are actually moisture. marine dredging removed from soil unlike stabilization, which leaves the metals
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in the soil. 1.2.3 Fracturing raise the efficiency of other in (PF: $9 to contaminant (Pneumatic Fracturing situ technologies in difficult $13 per groups with no Enhancement) soil conditions metric ton particular target Lasagna group Process: $180 to $200 per metric ton 1.2.4 Soil Flushing extraction of contaminants • Useful to all types of • Soils with low short- to key cost inorganics (Cosolvents Enhancement; from the soil with water or soil contaminants and is permeability or medium-term drivers: including Surfactant Flooding) other suitable aqueous generally used in heterogeneity are Soil radioactive solutions conjunction difficult to Permeabili contaminants with other remediation treat ty & Depth less cost-effective technologies. • Long remediation to for VOCs, • Reduces the need for times. Groundwat SVOCs, fuels, excavation, handling, or • Requires hydraulic er and pesticides transportation of control hazardous to avoid the movement substances. of contaminants off-site. 1.2.5 Soil Vapor a vacuum is implemented to • Very efficient, readily • Effectiveness medium- to key cost VOCs and some Extraction (SVE) the soil to induce the available equipments and decreases in low long-term drivers: fuels (In situ soil venting; In situ controlled flow of air and easy to install soil permeability. Economy volatilization; Enhanced eliminate VOCs and Semi- • Requires short • Useful only for the of scale & volatilization) VOCs contaminants from the treatment unsaturated soil type soil times zone. (6-48 months). 1.2.6 decrease the mobility of • Useful and established • Lack of expertise on The major inorganics Solidification/Stabilization hazardous substances and remediation technology technical factor driving (including (In Situ Vitrification) contaminants in the for guidance. the selection radionuclides) environment through both contaminated soils in • Uncertainty over the process beyond physical and chemical means many durability basic waste
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countries in the world. and rate of contaminant compatibility is release. the availability • Residual liability of suitable associated reagents with immobilized contaminants remaining on-site 1.3 In Situ Thermal Treatment 1.3.1 Thermal Treatment employs electrical • Contaminant toxicity as • Metals are not a short- to key cost SVOCs & some (Thermally Enhanced Soil resistance/electromagnetic/fib well as its concentration destroyed and end up medium-term drivers: pesticides and Vapor Extraction) er optic/radio frequency is checked by this in the flue gases or in technology soil type & fuels heating or hot-air/steam technology the ashes. depth of injection to increase the • Commercially available • Rocky soils need to top/thickne volatilization rate of semi- and widely used. be ss of volatiles and facilitate screened before use. contaminat extraction ed area 1.4 Ex Situ Biological Treatment (assuming excavation) 1.4.1 Biopiles (Heap pile excavated soils are mixed • If In-situ technology • Need to control a short-term $130 to nonhalogenated bioremediation; Bioheaps; with soil amendments and then no abiotic loss technology $260 per VOCs and fuel Biomounds; Static-pile placed on a treatment area transportation cost. • Mass transfer cubic hydrocarbons. composting) (Controlled that includes leachate problem meter Halogenated Solid-Phase collection systems and some • Bioavailability VOCs, SVOCs, Bioremediation) form of aeration limitation and pesticides
1.4.2 Composting (Solid- organic contaminants are • Cheap with rapid • Treatment time more Windrow key cost soils and lagoon phase soil treatment, Ex converted by microorganisms reaction rate. than other composting has drivers: sediments situ treatment) (under aerobic and anaerobic techniques been contamina contaminated with conditions) to innocuous, • Requires nitrogen demonstrated as nt & soil biodegradable stabilized byproducts supplementation. an effective type/total organic technology for organic compounds treatment of content
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explosives- contaminated soil 1.4.3 Landfarming (Solid incorporates liners and other • Relative simple design • Required area is high. medium- to Costs prior petroleum phase biodegradation) methods to control leaching and • Dust and vapor long-term to hydrocarbons of contaminants, which implementation generation may technologies & treatment: (gasoline, diesel requires excavation and • Short treatment times cause some air a full-scale $25,000 to fuel, No. 2 and placement of contaminated (six pollution. bioremediation $50,000 + No. 6 fuel oils, soils, sediments, or sludges months to two years technology $100,000 JP-5, oily sludge, under for pilot wood-preserving optimal conditions). tests & wastes (PCP and Cost of creosote), coke prepared wastes, and bed: Under certain pesticides $100 per cubic meter 1.4.4 Slurry Phase includes the controlled short- to using soils, sludges, and Biological Treatment treatment of excavated soil in medium-term slurry sediments (Slurry biodegradation) a bioreactor technologies reactors contaminated by range from explosives, $130 to petroleum $200 per hydrocarbons, cubic petrochemicals, meter & solvents, $160 to pesticides, wood $210 per preservatives, and cubic other organic meter chemicals (slurry- bioreactor off-gas) 1.5 Ex Situ Physical/Chemical
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Treatment (assuming excavation) 1.5.1 Chemical Extraction separating hazardous medium-term key cost sediments, (Acid Extraction) & contaminants from soils, drivers: sludges, and soils (Solvent Extraction) sludges, and sediments, Economy containing thereby reducing the volume of scale & primarily organic of the hazardous waste that moisture contaminants such must be treated content in as PCBs, VOCs, waste halogenated solvents, and petroleum wastes 1.5.2 Chemical Reduction convert hazardous short- to $190 to contaminant /Oxidation contaminants to nonhazardous medium-term $660 per group for or less toxic compounds that technology & cubic chemical redox is are more stable, less mobile, not cost- meter inorganics and/or inert effective for high contaminant concentrations 1.5.3 Dehalogenation Contaminated soil is • Target compounds are • High clay and high a short- to $220 to halogenated screened, processed with a halogenated organics, moisture medium-term $550 per SVOCs and crusher and pug mill, and halogenated SVOCs and content increases process metric ton pesticides mixed with reagents. The pesticides. treatment costs. mixture is heated in a reactor • Used for soils and • Not cost-effective for sediments contaminated large waste volumes. with chlorinated organic • Sometimes diifficult compounds, especially to capture and treat the PCBs, dioxins and residuals. furans. 1.5.4 Separation eliminating contaminated SVOCs, fuels, concentrates from soils, to and inorganics leave relatively (including uncontaminated fractions that radionuclides) can then be regarded as
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treated soil. 1.5.5 Soil Washing a water-based process for • Useful to all types of • Soils with low a short- to key cost SVOCs, fuels, scrubbing soils ex situ to soil contaminants and is permeability or medium-term & drivers: and heavy metals remove contaminants generally used in heterogeneity are a media transfer Economy conjunction difficult to treat technology of scale & with other remediation • Long remediation processor technologies. times. speed • Reduces the need for • Requires hydraulic excavation, handling, or control to avoid the transportation of movement of hazardous substances. contaminants off-site. 1.5.6 ex situ S/S contaminants are • Useful and established • Lack of expertise on a short- to key cost inorganics, Solidification/Stabilization physically bound or enclosed remediation technology technical guidance. medium-term drivers: including (Vitrification) within a stabilized mass for • Uncertainty over the technology type of radionuclides (solidification), or chemical contaminated soils in durability Most S/S waste & reactions are induced between many and rate of contaminant technologies size of the the stabilizing agent and countries in the world release. have limited mobile s/s contaminants to reduce their • Residual liability effectiveness system mobility (stabilization) associated against organics with immobilized and pesticides, contaminants except remaining on-site vitrification which destroys most organic contaminants 1.6 Ex Situ Thermal Treatment (assuming excavation) 1.6.1 Hot Gas raising the temperature of the • Waste is stockpiled • Costs of this method depending upon for process Decontamination contaminated equipment or Which is easily disposed are higher than open the size and equipment material to 260 °C (500 °F) off later. burning. geometry of the requiring for a specified period of time. • Permit reuse or disposal • Can lead to equipment or decontamination The gas effluent from the of scrap as nonhazardous explosions material to be for reuse, material is treated in an material from improperly decontaminated explosive items
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afterburner system to destroy demilitarized mines or and the all volatilized contaminants shells. temperature and • Slow rate of holding time decontamination required for the decontamination 1.6.2 Incineration High temperatures, 870 to • Used to remediate • Only one off-site short- to long- key cost soils 1,200 °C (1,400 to 2,200 °F), soils contaminated with incinerator is permitted term drivers: contaminated with are used to volatilize and explosives and hazardous to burn Type of explosives and combust (in the presence of wastes • Specific materials and waste & hazardous wastes, oxygen) halogenated and feed size required quantity particularly other refractory organics in • Bottom ash produced chlorinated hazardous wastes by heavy metals hydrocarbons, requires stabilization. PCBs, and dioxins • Volatile heavy metals, including lead, cadmium, mercury and arsenic can cause air pollution.
1.6.3 Open Burn/Open to destroy excess, obsolete, or • Very effective for many • Minimum distance to destroy excess, Detonation unserviceable (EOU) types of explosives, requirements for safety obsolete, or munitions and energetic pyrotechnics and purposes. unserviceable materials propellants • Emissions are (EOU) munitions, difficult components, to capture for treatment energetic materials, as well as, media contaminated with energetics 1.6.5 Pyrolysis chemical decomposition • Target contaminant • Specific feed size and $330 per SVOCs and induced in organic materials groups for pyrolysis materials handling metric ton pesticides by heat in the absence of are SVOCs and requirements. oxygen pesticides. • Drying of the soil
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• Can treat organic required contaminants in soils and • Highly abrasive feed oily sludges. sometimes damage the processor unit. • High moisture content increases treatment costs. 1.6.6 Thermal Desorption a physical separation process have varying key cost groups for LTTD and is not designed to destroy degrees of drivers: systems are organics. Wastes are heated to effectiveness Economy nonhalogenated volatilize water and organic against the full of scale & VOCs and fuels contaminants spectrum of moisture organic content contaminants 1.7 Containment 1.7.1 Landfill Cap (Cap; Landfill Caps can range from it is generally generally to minimize Landfill cover; Surface a one-layer system of less expensive the least generation of cover, Containment, vegetated soil to a complex than other expensive leachate until a Capping) multi-layer system of soils technologies way to better remedy is and geosynthetics and effectively manage the selected manages the human human and health and ecological risks ecological associated with risks a remediation effectively, site $175k/acre , $225k/acre 1.7.2 Landfill Cap to reduce or eliminate costs are for traditional Enhancements/Alternatives contaminant migration determined landfills, surface on a case- impoundment’s, by-case waste piles, basis sludges, and some mine tailings
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1.8 Other Treatment 1.8.1 Excavation, Contaminated material is Operation and $300 to to the complete Retrieval, Off-Site removed and transported to maintenance $510 per range of Disposal (Removal, Waste permitted off-site treatment duration lasts as metric ton contaminant Removal-Soils, Waste and/or disposal facilities long as the life groups with no Removal-Sludges, Waste of the facility particular target Removal-Non-soil Solids) group
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Table E-2 Remediation technologies used for Groundwater, (saturated zone) (Godheja et al. 2016, FRTR 1990)
Remediation technology Method Advantages Disadvantages Features Cost Application 2.1 In Situ Biological Treatment 2.1.1 Enhanced indigenous or inoculated long-term typical nonhalogenated Bioremediation micro-organisms (i.e., fungi, technologies, costs are VOCs, (Biostimulation, bacteria, and other microbes) which may take $10 to nonhalogenated bioaugmentation) degrade (metabolize) organic several years for $20 per SVOCs, and fuels contaminants found in soil plume clean-up 1,000 Pesticides also and/or ground water liters should have limited treatability 2.1.2 Monitored Natural Natural subsurface • Remediation waste is • Ethical issues remain VOCs and Attenuation (Farhad processes—such as dilution, least which has less which needs to be SVOCs and fuel Analoui et al.), (Intrinsic volatilization, biodegradation, impact act on the correctly perceived hydrocarbons Remediation; adsorption, and chemical environment; by the people. Bioattenuation; Intrinsic reactions with subsurface • Can be easily combined • Costly and complex Bioremediation) materials—are allowed to with other technologies. site characterization. reduce contaminant concentrations to acceptable levels. 2.1.3 Phytoremediation a set of processes that uses • Least environmental • Two growing seasons key cost to clean up (Vegetation-enhanced plants to clean contamination disturbance. required drivers: organic bioremediation ) in ground water and surface • Solar energy driven • Limited to soils less Scale of contaminants water technology. than one meter from effort & from surface • Used on a large range the surface and tree size water, ground of contaminants. groundwater less than 3 (maturity water, leachate, • Cost-effective for large m from the surface ) is the and municipal and contaminated sites • Contaminants may secondar industrial enter the food chain y cost wastewater. through animals which drive eat the plants used in these projects 2.2 In Situ
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Physical/Chemical Treatment 2.2.1 Air Sparging (In-situ air is injected through a • Readily available • Biochemical and a medium to long key cost VOCs and fuels air sparging, in-situ contaminated aquifer. Injected equipment; physiological duration (few drivers: aeration) air traverses horizontally and • Cost competitive; interactions are very years) Surface vertically in channels through • In situ technology complex and needs to area & the soil column, creating an be understood depth to underground stripper that • Migration of contamin removes contaminants by constituents can lead to ation volatilization toxicity elsewhere. 2.2.2 Bioslurping (Free adaptation and application of • Applied at shallolw as • Low soil permeability a cost-effective in $56/gal soils product recovery) vacuum-enhanced dewatering well as hampers situ remedial LNAPL contaminated by technologies to remediate deep sites. remediation. technology recovere petroleum hydrocarbon-contaminated • Recovers free product, • Soil moisture and d hydrocarbons & sites. thus oxygen content applicable at sites speeding remediation limits the microbial with a deep activities. ground water • Low temperatures table (>30ft.) slow remediation. 2.2.3 Chemical Oxidation converts hazardous key cost (Chemical contaminants to non- drivers: Reduction/Oxidation) hazardous or less toxic Economy compounds that are more scale & stable, less mobile, and/or contamin inert. ant conce 2.2.4 Directional Wells Drilling techniques are used to $60 to complete range of (enhancement) position wells horizontally, or $250 per contaminant (Horizontal Wells) at an angle, to reach meter & groups with no contaminants not accessible Sonic particular target by direct vertical drilling drilling group can be as much as $330 per
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meter 2.2.5 Dual Phase uses a high vacuum system to key cost VOCs and fuels Extraction (Multi-phase remove various combinations drivers: (e.g., LNAPLs) extraction; Vacuum- of contaminated ground water, Soil type enhanced extraction; Free separate-phase petroleum & depth product recovery; Liquid- product, and hydrocarbon to base Liquid Extraction) vapor from the subsurface of contamin ation 2.2.6 Thermal Treatment Steam is forced into an aquifer $100 to SVOCs and fuels (Hydrous through injection wells to $300 per pyrolysis/oxidation; In situ vaporize volatile and cubic steam extraction, (Hot semivolatile contaminants. yard water/steam flushting) Vaporized components rise to the unsaturated (vadose) zone where they are removed by vacuum extraction and then treated 2.2.7 Hydrofracturing pressurized water is injected to $1,000 to to a wide range of Enhancements increase the permeability of $1,500 contaminant consolidated material or per groups relatively impermeable fracture unconsolidated material 2.2.8 In-Well Air air is injected into a vertical halogenated Stripping (Vacuum vapor well that has been screened at VOCs, SVOCs, extraction; In-well two depths. and fuels aeration; Vacuum vaporizer well; ground water circulating wells) 2.2.9 Passive/Reactive A permeable reaction wall is long-term key cost VOCs, SVOCs, Treatment Walls installed across the flow path operation to drivers: and inorganics (Permeable reactive of a contaminant plume, control migration Economy barrier walls; In place allowing the water portion of of contaminants of scale bioreaction; In-situ the plume to passively move in ground water & choice
215 chemical filters) through the wall of suppleme ntal amendm ents & additiona l monitori ng required by regulator s 2.3 Ex Situ Biological Treatment 2.3.1Bioreactors (Rotating Bioreactors degrade • Fast degradation • Soil transport key cost SVOCs, fuel Biological Reactor; contaminants in water with • Effective use of required drivers: hydrocarbons, and Rotating Biological microorganisms through inoculants and • Expensive chemical any biodegradable Contactors (RBC)) attached or suspended surfactant oxygen organic material. biological systems demand & PH adjustme nt 2.3.2 Constructed uses natural geochemical and a long-term the have most Wetlands biological processes inherent technology capital commonly been in an artificial wetland intended to costs of used in ecosystem to accumulate and operate wetland wastewater remove metals, explosives, continously for treatment treatment for and other contaminants from years over a 10 controlling influent waters year organic matter; period nutrients, such as results in nitrogen and a cost of phosphorus; and $1.36/Kg suspended
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al; over a sediments, trace 30 years metals, and other period, toxic materials the cost is $0.45/Kg al 2.4 Ex Situ Physical/Chemical Treatment (assuming pumping) 2.4.1 Adsorption/ solutes concentrate at the Forager most organic Absorption (Liquid phase surface of a sorbent, thereby Sponge contaminants and adsorption) reducing their concentration in technolo selected inorganic the bulk liquid phase gy is contaminants estimated from liquid and at gas streams $340/100 0 gallons 2.4.2Advanced Oxidation a destruction process that $0.03 to any organic Processes (UV oxidation) oxidizes organic and explosive $3.00 per contaminant that constituents in wastewater by 1,000 is reactive with the addition of strong liters the hydroxyl oxidizers and irradiation with UV light 2.4.3 Air Stripping volatile organics are • Can achieve better than • The presence of may be tens of key cost used to separate partitioned from ground water 95% removal efficacy for solids in wastewaters years and depends drivers: VOCs from water by greatly increasing the a range of organic can foul steam strippers on the capture of Influent surface area of the compounds which and therefore it is the entire plume flow rate contaminated water exposed are insoluble or slightly generally advantageous from the ground 7 relative to air soluble in water. to remove these solids water. contamin before stripping ant volatility & off-gas
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treatment 2.4.4 Granulated ground water is pumped short-term - long- $1.20 to hydrocarbons, Activated Carbon/Liquid through one or more vessels term $6.30 per SVOCs and Phase Carbon Adsorption containing activated carbon to 1,000 explosives (Activated carbon; Carbon which dissolved organic gallons filtration) contaminants adsorb 2.4.5 Groundwater a component of many pump- for contaminated Pumping/Pump & Treat and-treat processes sites with (Waste Removal - enhanced dense, Liquids) nonaqueous-phase liquids (DNAPLs) 2.4.6 Ion Exchange removes ions from the $0.08 to dissolved metals aqueous phase by the $0.21 per and radionuclides exchange of cations or anions 1,000 from aqueous between the contaminants and liters solutions. Other the exchange medium compounds that have been treated include nitrate, ammonia nitrogen, and silicate 2.4.7 transforms dissolved key cost to convert Precipitation/Coagulation/ contaminants into an insoluble drivers: dissolved ionic Flocculation solid, facilitating the No species into solid- contaminant's subsequent sensitivit phase particulates removal from the liquid phase y t by sedimentation or filtration. analysis possible, operating costs $0.50 per 1,000 gallons of
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ground water treated 2.4.8 Separation concentrate contaminated Filtration ex situ separation waste water through physical : $0.36 to process is used and chemical means. $1.20 per mainly as a 1,000 pretreatment or liters, post-treatment freezed process to remove crystalliz contaminants ation is from waste water, estimated aqueous waste to be streams such as only ground water, $0.03 per lagoons, leachate, gallon and rinse water for a 40 gpm facility 2.4.9 Sprinkler Irrigation involves the pressurized any contaminant distribution of VOC-laden that readily water through a standard transfers from the sprinkler irrigation system. dissolved phase to simple treatment technology the vapor phase used to volatilize VOCs from (VOCs) contaminated wastewater 2.5 Containment 2.5.1 Physical Barriers used to contain contaminated $540 to contain the (Vertical cutoff walls; ground water, divert $750 ground water Hydrodynamic barriers; contaminated ground water itself, thus Slurry Trenches, Slurry from the drinking water treating no Walls, Slurry intake, divert uncontaminated particular target Walls/Underground ground water flow, and/or group of Barriers) provide a barrier for the contaminants
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ground water treatment system. 2.5.2 Deep Well Injection a liquid waste disposal VOCs, SVOCs, (Subsurface injection, technology, consists of fuels, explosives, Underground injection, concentric pipes, which extend and pesticides Class I injection wells) several thousand feet down from the surface level into highly saline, permeable injection zones that are confined vertically by impermeable strata
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Appendix F Sustainable Remediation Assessment method of Al-Wahat region, Libya
1- Assessment for contaminated soil
General view of inputs and output to produce the pilars scores
Inputs and outpus to produce the pilars scores of the 1st option
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Inputs and outpus to produce the pilars scores of the 2nd option
Inputs and outpus to produce the pilars scores of the 3rd optin
Inputs and outpus to produce the pilars scores of the 4th option
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Inputs and outpus to produce the total score of the 1st option
Inputs and outpus to produce the total score of the 2nd option
Inputs and outpus to produce the total score of the 3rd option
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Inputs and outpus to produce the total score of the 4th option
2- Assessment of contaminated groundwater
Inputs and outpus to produce the pilars scores of the 1st option
Inputs and outpus to produce the pilars scores of the 2nd option
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Inputs and outpus to produce the pilars scores of the 3rd option
Inputs and outpus to produce the pilars scores of the 4th option
Inputs and outpus to produce the pilars scores of the 5th option
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General view of inputs and output to produce the total score
Inputs and outpus to produce the total score of the 1st option
Inputs and outpus to produce the total score of the 2nd option
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Inputs and outpus to produce the total score of the 3rd option
Inputs and outpus to produce the total score of the 4th option
Inputs and outpus to produce the total score of the 5th option
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