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A materials balance analysis : petroleum products in greater Vancouver Dreher, Wilfried Hans 1975

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A M A T E R I A L S B A L A N C E A N A L Y S I S P E T R O L E U M P R O D U C T S I N G R E A T E R V A N C O U V E R hy WILFRIED HANS DREHER Eng. D i p l . Swiss Federal I n s t i t u t e of Technology 19&9 A THESIS SUBMITTED IN PARTIAL FULFILMENT OF THE REQUIREMENTS FOR THE DEGREE OF ' MASTER OF SCIENCE . In the School of Community and Regional Planning We accept t h i s thesis as conforming to the required standard THE UNIVERSITY OF BRITISH COLUMBIA A p r i l 1975 In presenting t h i s thesis i n p a r t i a l f u l f i l m e n t of the requirements f o r an advanced degree at the University of B r i t i s h Columbia, I agree that the Library s h a l l make i t f r e e l y available f o r reference and study. I further agree that permission f o r extensive copying of t h i s thesis f o r scholarly purposes may be granted by the head of my Department or by his representatives. I t i s understood that copying or publication of t h i s thesis f o r f i n a n c i a l gain s h a l l not be allowed without my written permission,, School of Community and Regional Planning, University of B r i t i s h Columbia, Vancouver 8 , Canada. May 1,1975 i i A .B S T.R A C T Identifying sources and pathways of pollutants i s one of the most d i f f i c u l t .problems to solve i n the area of water q u a l i t y management. The following three objectives focus on t h i s problem i n (1) developing the concept of the materials. balance for. i d e n t i f y i n g sources, pathways and sinks of petroleum products i n an urban environment, (2) i n v e s t i g a t i n g the effects of p o l l u t i o n due to petroleum hydrocarbons i n an urban area and (3) applying the planning technique of the materials balance i n a. case study of the Greater Vancouver Regional D i s t r i c t . The state of the present understanding of the behaviour of o i l i n water, i t s t o x i c i t y to aquatic organisms and effects on the b e n e f i c i a l uses of water i s reviewed and the essential l i t e r a t u r e on t h i s subject i s summarized. The materials balance technique, which i s a complete accounting of a l l o i l products entering i n t o , flowing through and leaving an area, has been developed because i t i s recognized that present methods f o r i d e n t i f y i n g sources and pathways of p o l l u t i o n are unsystematic and therefore do not f u l l y reveal the opportunities f o r c o n t r o l l i n g discharges of o i l y wastes. The p r i n c i p a l conclusions of the study are the following: (1) Considerable uncertainty prevails i n i n t e r p r e t i n g physiological and b i o l o g i c a l aspects of o i l p o l l u t i o n . Available evidence indicates that the greatest hazards i i i r e s u l t from large s p i l l s and toxic substances contained i n waste o i l s , predominantly heavy metals. (2) The materials balance has proven to be a useful planning technique f o r residuals management studies, i n that i t provides: a t o o l to i d e n t i f y size and sources of flows, thus i d e n t i f y i n g the c r i t i c a l waste streams, - a framework f o r making "guesstimates", which are often unavoidable due to a. lack of data and f o r testing the s e n s i t i v i t y of alternative assump-tions and - A powerful model f o r analysing alternative p o l i c y mechanisms f o r p o l l u t i o n abatement and resource conservation. (3) Applying the materials balance to the Greater Vancou-ver Regional D i s t r i c t , the following conclusions can be drawn: at present, o i l p o l l u t i o n within the Greater Vancouver Regional D i s t r i c t i s not serious, however, there are problems that require further research such as the long term effects of o i l p o l l u t i o n on the marine and estuarine environment and effects of p o l l u t i o n due to contaminated waste o i l s . I t would seem preferable to understand and control the problem before o i l p o l l u t i o n reaches serious levels due to future growth and indus-t r i a l i z a t i o n . TABLE OF CONTENTS Abstract - v /?Y. ' p a g S CHAPTER 1 Introduction 1 1.1 Scope and Objectives - 1 1.2 Concept of the Materials Balance 4 1.3 The Fraser River Water Quality:-.Management Study of the Westwater Research.Centre 6 1.4. Organization of the Study 8 1.5 Metric System 9 CHAPTER 2. O i l i n the Water Environment - A General Perspective 10 2.1. Chemical and Physical Properties of Petroleum Products 10 •2.11 Basic Chemical Structure of Hydro-carbons 10 2.12 Crude O i l s and Refined Products 12 2.13 Residuals of Burned Fuels . 13 2.14 Lubricants and I n d u s t r i a l O i l s 14 '2.2 The. Behaviour of Petroleum Hydrocarbons i n Water 16 2.21 The Physical Phases of .Oil and Water 16 2.22 Sinking '•. 18 2.23 Evaporation 19 . 2.24. Auto-oxidation 19 2.25 B a c t e r i a l Breakdown 20 2.3 . Effects of O i l P o l l u t i o n on Aquatic Ecosystems 23 2.31 Direct Effects 23 2.32 Indirect Effects 30 2.4 E f f e c t s of O i l P o l l u t i o n on the B e n e f i c i a l Uses of Water 35 •2.41 Domestic Water Supply 36 2.42- I n d u s t r i a l Water Supply . . 38 2.43 I r r i g a t i o n Water 39 2.44 Other Effects of Oily Substances 39 2.5 Remaining Uncertainties 40 V ; Page CHAPTER 3 The Materials Balance Approach - Gene-r a l Considerations 42 3.1 Theoretical Framework 42 3.2 The Sources of O i l P o l l u t i o n - A Worldwide Materials Balance 44 CHAPTER 4 Regional Materials Balance f o r Petroleum Products i n the Greater Vancouver Regional D i s t r i c t 47 4.1 Imports, Exports and Consumption 47 4.11 Province of B.C. 47 4.12 Regional Breakdown f o r the GVRD 49 4.2 Residuals- Generation 52 4.21 Fuel Consumption 52 4.22 Lubricating and I n d u s t r i a l O i l s 5i(-4.23 O i l S p i l l s and Losses 60 - 4.3 'Disposal of Residuals 61 '4.31' Waste O i l Storage and C o l l e c t i o n 62 4.32 Waste O i l Processing Industry 63 .... 4..33 Present End Uses ' ' .'. 64 4,34 A l l Petroleum Products Discharged to the Environment 69 4.4 Comparison of Total Discharges and Observed O i l P o l l u t i o n i n Greater Vancouver . 72 . 4.41 Sewers and Plant Effluents 72 4.42 Treatment Plants 7^ 4.43 Fraser-River 75 4.5 S e n s i t i v i t y Analysis 76 4.6 Overall Materials Balance 79 CHAPTER 5 Conclusions 81 5.1 Petroleum Products i n the Environment 81 5.2 O i l y Wastes i n the Vancouver Area. . 84 5.3 Waste O i l Generation and Processing 86 5.4 Assessment of the Materials Balance Approach 88 References • ' 9^  vi L i s t of Tables 1 Refinery Wastes 2 Calculation of D i l u t i o n Factor 3 Toxicity of Cadmium vs. Hardness 4 'Worldwide Materials Balance 5 Production,;. Consumption, Imports and Exports of Petroleum Products i n the Province of B.C. i n 19?2 4« 6 Regional Consumption i n f». of Province 50 7 Regional Consumption i n tons 50 8 Lubricating O i l s , Residuals Production 55 9 Waste O i l Production i n the GVRD 56 10 ' End Uses of Waste O i l . 69 11 Total Discharges to Land and Water Environment 70 12 Total Discharge to Water. Environment 71 13 Range of Values of Assumptions 77 Page 32 33 34 he L i s t of Appendices Page 1 .: Comments to Assumptions . 9 8 2 Composition of Waste O i l 109 3 Summary of To x i c i t y Tests 112 k Waste O i l Survey 115 5 Cost Comparison Fuel Use vs. Re-refining 120 L i s t of. Figures 1 Map of the GVRD 123 2 Map of the Lower Fraser River System • 124 3 C l a s s i f i c a t i o n of Hydrocarbons 125 4 Concept of Materials Balance I 126 5 Concept of Materials Balance I I 127 6••> Worldwide Materials Balance 128 7 Diagram Waste O i l Production 129 8 Materials Balance For GVRD 130 9 Maximum-Minimum Hypothesis 13! 1 CHAPTER ONE INTRODUCTION 1 . 1 Scope and Objectives The extent and seriousness of problems created by manmade p o l l u t i o n has been booming with economic growth i n the postwar period. Petroleum products have become the i n -dispensable base f o r such e s s e n t i a l basic economic ac-t i v i t i e s as transportation, energy generation and food production. The consumption of petroleum products has grown to such high l e v e l s that the generation of wastes and losses i s of a large scale even though only small percentages of the material are l o s t . The sources of p o l l u t i o n make up,,an impressive l i s t : Wrecked tankers, .tanker operations such as tank cleaning, •b a l l a s t v/ater dumping, bilge water dumping and s p i l l s during bunkering operations are the main sources at sea; f i r e s , floods, explosions, transportation on inland waterways, i n d u s t r i a l wastes, domestic sewage, o i l pro-duction operations, o i l f i e l d brines-, • r e f i n e r y wastes, natural o i l seeps, pipeline leakages, service s t a t i o n pumps, garage wastes, shore o i l terminals, o i l storage tank f a i l u r e , tank.truck accidents, o i l surfaced road-2 ways and cleaning o i l s are among the landbased sources. In t h i s l i s t , the sources of p o l l u t i o n are c l a s s i f i e d into landbased and waterbased p o l l u t i o n . The e x i s t i n g l i t e -rature on o i l p o l l u t i o n i s concerned mainly with water-borne p o l l u t i o n r e s u l t i n g from s p i l l s and ship operations. Very l i t t l e consideration has been given i n the l i t e r a t u r e on the various landbased sources i n p a r t i c u l a r those i n urban i n d u s t r i a l areas. Because of the complexity of sources, pathways and sinks i n an urban-industrial area the ad hoc approaches to the i d e n t i f i c a t i o n and control of waste discharges which have been employed i n the past are not adequate f o r i d e n t i -f y i n g the most s i g n i f i c a n t sources and opportunities f o r exerting control over such ubiquitous materials as petro-leum products. To be more s p e c i f i c , water q u a l i t y manage-ment has usually involved measuring ambient water q u a l i t y conditions, i d e n t i f y i n g the points of discharge to the waterway and measuring the quantities involved. I f water q u a l i t y conditions are to be improved then ways and means fo r c o n t r o l l i n g the i d e n t i f i e d discharges must be deter-mined and implemented. Although s i m p l i s t i c t h i s descrip-t i o n captures the essence of"the planning techniques usually employed and i l l u s t r a t e s t h e i r weaknesses. F i r s t l y i t i s d i f f i c u l t to know when a l l the sources of a p a r t i c u -3 l a r r e s i d u a l have been i d e n t i f i e d because ther i s no i n -dependent estimate of the t o t a l quantity of the material that might enter the water environment. Secondly, materials may enter the water environment by pathways which are not r e a d i l y obvious or measured, e.g. runoff. T h i r d l y , by beginning the search f o r opportunities f o r c o n t r o l l i n g waste discharges at the point where they enter the water, important opportunities f o r treatment and f o r resource recovery at some e a r l i e r stage i n the production and use of the material may go unconsidered. Fourthly, abatement of the discharge may be achieved at the expense of d i v e r t i n g the flow of the material to other parts of the water environment or to other environmental media, unless i t i s possible to assess the e f f e c t of the control on the flow of the material to that discharge source. In t h i s study i t i s hoped a planning technique can be de-veloped which w i l l overcome these l i m i t a t i o n s . The three major objectives of t h i s study are: (1) to investigate the physical, chemical and b i o l o -g i c a l e f f e c t s of petroleum products on the water envi-ronment, (2) to develop the concept.of the.materials balance; f o r i d e n t i f y i n g the sources,^.transport pathways and sinks of petroleum products i n an urban area and 4 (3) "to assess the pot e n t i a l of t h i s planning technique f o r water q u a l i t y and residuals management by a case study of waste petroleum products i n the Greater Vancou-ver area. The main thrust of the study i s therfore to develop and assess a technique that might be u t i l i z e d to generate i n -formation f o r planning i n residuals and water q u a l i t y management. The concept of a. materials- balance i s simple but i t s a p p l i c a t i o n to the flow of petroleum products i n an urban area i s complicated by the complexity of the net-work of sources, transport pathways and sinks and by the data required to develop and ca l i b r a t e the network. The development and assessment of the technique i s based on a case study of Greater Vancouver. 1.2 Concept of the Materials Balance B a s i c a l l y , the materials balance concept i s a complete accounting of a l l materials of a c e r t a i n class flowing through a system. This system can be a geographical area, a sector of an industry, a single f a c t o r y , a lake, a stream or a sewer system. Over a given period, the t o t a l -mass of the products entering a system must equal the to-t a l mass of products leaving the system plus the net addition to or depletion of the stocks. In t h i s study,, the class of materials investigated i s products manufactu-red from crude o i l except asphalt products and petroche-micals. This i s a l l the pure petroleum hydrocarbons p o t e n t i a l l y dangerous as water pollutants. As a region, the Greater Vancouver Regional D i s t r i c t was chosen, since i t i s the most developed urban i n d u s t r i a l area i n the Province of B r i t i s h Columbiaand situated beside the Fraser River estuary, the largest estuary on the West Coast of Canada, Figure 1 shows a map of the Greater Vancouver Regional D i s t r i c t . The reason f o r choosing the materials balance concept f o r t h i s study are manifold: - The materials balance has b u i l t i n checks on* the completeness of the data and analysis. Even i f l i n k s remain hidden inside the system, a balance of a l l observed outputs against a l l observed inputs provides a check that a l l sources have been i d e n t i f i e d . The p o t e n t i a l errors made i n evaluating p a r t i a l figures i s therfore l i m i t e d as the errors need not be accumulative. - The methodology of the materials balance seems par-t i c u l a r l y w e l l suited f o r i l l u s t r a t i n g the various l i n k -ages of the flow of d i f f e r e n t products through the system. • 6 The flows, can "be p a r t i t i o n e d to y i e l d good in s i g h t into how gaseous, l i q u i d and semi-liquid residuals are gene-rated by production, consumption and r e c y c l i n g of the par-t i c u l a r material involved and indicate t h e i r important i n t e r r e l a t i o n s h i p s . The increasing demand f o r the a l l o c a t i o n of resour-ces to p o l l u t i o n control makes i t c r u c i a l that available resource's are used to apply the most cos t - e f f e c t i v e con-t r o l s . The materials balance analysis provides a systema-t i c technique f o r i d e n t i f y i n g the most c r i t i c a l sources and estimating the e f f e c t of controls on the flows of petro-leum products when various degrees of control are placed oh d i f f e r e n t sources. In the event that major uncertainties ablut quanti-ties.-of discharged materials remain, which w i l l generally be the case-, the materials balance provides a framework f o r making a systematic s e n s i t i v i t y analysis of the impor-tance of the uncertainties. 1.3 The Fraser River Water Quality Management Study of the Westwater Research Centre This study i s part of a project parried out by Westwater Research Centre at the University of B r i t i s h Columbia, concerned with the management of the Lower Fraser River 7 Figure 2 between Hope and the S t r a i t of Georgia (see f i g u r e 2), The studies completed so f a r provide a basis f o r i d e n t i f y i n g the nature of the water q u a l i t y problems i n the Lower Fraser. The dissolved oxygen concentration,which i s a measure of the degree of p o l l u t i o n by biodegradable wastes, such as sewage and other organic wastes, i s close to saturation l e v e l throughout the r i v e r i n d i c a t i n g that there i s no immediate p o l l u t i o n problem from these biodegra-dable wastes. Indicator microorganisms, a measurev.of p o l l u t i o n by pathogenic organisms reach l e v e l s that, make water u n f i t f o r primary contact recreation and raw d r i n -king water supply. A t h i r d type of p o l l u t i o n i s represen-ted by the class of hazardous wastes, such as heavy me-t a l s ,polychlorinated biphenols, pesticides and petrole-um products. Average concentrations of these hazardous materials i n waters, sediments and b i o t a are s t i l l / r e l a t i -vely low, however, fluc t u a t i o n s cause occasionally high values, p a r t i c u l a r l y i n the waters around the Vancouver Area. Sources and quantities of t h i s t h i r d type of p o l l u -t i o n are s t i l l l a r g e l y uncertain. (The findings of the study are mainly described i n the f o l -lowing references: Dorcey(1974a), (1974b), H a l l (1974), Benedict (1973). and Wes.twater (1973a).) There are many po t e n t i a l sources of these hazardous was-tes i n the urban-industrial area and there i s a v a r i e t y 8 of pathways by which they might be transported to the water environment. I t i s i n providing a technique f o r iden-t i f y i n g the most s i g n i f i c a n t sources and pathways that the materials balance concept appears to o f f e r some promise. Petroleum products were chosen f o r the i n i t i a l case study because the number of products, and pathways by which they enter the Vancouver Area i s small r e l a t i v e to most other hazardous materials such, as heavy metals or polychlorinated biphenols (PCB*s). .Hopefully the technique developed i n t h i s study can be applied to other residuals. 1.4 Organization of the Study The second_chagter examines the impact of petroleum pro-ductsion the water environment. A short section i s de-voted to chemical and physical properties of petroleum products, and subsequently the ef f e c t s of o i l on aquatic ecosystems and b e n e f i c i a l uses of water are described as w e l l as the ultimate fate of petroleum products i n the land and water environment. The third_chapter outlines the concept and the t h e o r e t i c a l background of the materials balance approach. An estimate of the global use of the global use of the petroleum products i s included to i l l u s t r a t e the concept and set the • larger framework f o r the regional study i n the fourth_ 9 chapter, which develops the materials balance f o r the .•Greater Vancouver Regional D i s t r i c t . 1 ,5 Metric System Throughout t h i s study exclusive use of the metric system i s made. Where i t .is important to compare figures with s a t i s t i c a l material and other publications i n the English system, the metric system and the English-system are both used. 10 CHAPTER TWO OIL IN THE WATER ENVIRONMENT - A GENERAL PERSPECTIVE 2,1 Chemical and Physical Properties of Petroleum Products 2.11 Basic Chemical Structure of Hydrocarbons According to t h e i r name, hydrocarbons are materials whose molecules are composed of hydrogen and carbon atoms. The simplest of them, the methane molecule, consists of one Figure 3 carbon atom and four hydrogen atoms, (See Figure 3 f o r d e t a i l s ) With increasing s i z e , molecules become also increasingly complex. The C-atoms form chains, branched chains, single and multiple rings, rings with branches, etc. Furthermore, unsaturated and aromatic compounds have to be distinguished. A c l a s s i f i c a t i o n of the various groups of hydrocarbons i s given i n figure 3 . •Saturated hydrocarbons are the most abundant compounds i n natural crude o i l , they contain-the maximum number of hydrogen atoms, giving the molecule a high s t a b i l i t y . These hydrocarbons are therefore t h e : l e a s t reactive and are the main constituents of the vast majority of f u e l s , gasolines-and other refined petroleum products. The unsa-11 turated hydrocarbons (or o l e f i n s ) contain less hydrogen than saturated hydrocarbons with the same number of C-atoms. As a r e s u l t , each missing hydrogen atom i s replaced by a carbon-carbon double bond,, which i s le s s stable than the single bond. Therfore they react more e a s i l y with other elements, organic groups and with themselves. Crude o i l contains only minute quantities of o l e f i n s but large amounts are produced i n r e f i n e r i e s by d i f f e r e n t conversion pro-cesses (see figure 3 "cracking"). The t h i r d group to mention are the aromatic compounds, con-t a i n i n g one or more benzene rings i n t h e i r molecules. Theore t i c a l l y , aromatics are unsaturated hydrocarbons, but t h e i r c h a r a c t e r i s t i c s are d i f f e r e n t from unsaturated as w e l l as from saturated hydrocarbons. A large number of petro-chemicals are-based on aromatic compounds, some of them high-l y t o x i c , but the content of aromatics i n market products of pure hydrocarbons (such as f u e l s , gasolines, etc.) i s r e l a t i v e l y low. A l a s t group are the asphaltenes. These compounds con-s i s t of very large and complex molecules. Usually asphal-tenes .are contained i n crude o i l s , refined products do not contain asphaltic compounds. They are very persistent 12 and therefore often the only v i s i b l e witnesses of o i l i n the natural environment. 2.12 Crude Oi l s and Refined Products Crude o i l s are mixtures of many substances, mainly satu-rated hydrocarbons, from which the various petroleum pro-ducts such as petroleum gas, gasoline, kerosene, gas o i l , f u e l o i l s , lubricating;.oils and asphaltic bitumen-are manu-factured by means of the r e f i n i n g process. In r e f i n i n g , b a s i c a l l y two processes have to be d i s t i n g u i -shed: d i s t i l l a t i o n and cracking. The d i s t i l l a t i o n process merely separates the l i g h t e r from the heavier f r a c t i o n s of the crude o i l , whereas the cracking process reduces the size of the molecules converting heavier to l i g h t e r f r a c t i o n s . This second process i s necessary i n most countries with a r e l a t i v e l y high demand f o r gasoline. I f the demand f o r gasoline i s higher than the natural occurrence of the- gaso-l i n e f r a c t i o n i n the refined crude o i l , gasoline has to be cracked from higher b o i l i n g f r a c t i o n s . This aspect i s r e l a t i v e l y important from an environmental point of view, because cracked products contain more unsaturated hydrocar-bons which are generally more dangerous i n the natural environment. 13 The d i f f e r e n t refined products consist of a v a r i e t y of of compounds, b a s i c a l l y distinguished by a d i f f e r e n t range of molecular weight of t h e i r molecules. The following l i s t indicates the appropriate number i f C-atoms of the d i f f e r e n t products: Gases: Methane 1 Ethane 2 Propane 3 Butane 4 Liquids Gasoline 5 to 10 Kerosene 3 t o 12 Light f u e l o i l lo t o 15 Heavy f u e l o i l \h t o 22 Lubricating o i l u p t o 25 Solids Asphalts more than 3° The s p e c i f i c gravity of the l i q u i d s range from .75 to • 9 g/cm-^ . (Water 1.0 g/cm^). The weight correlates i n general p o s i t i v e l y with the number of C-atoms. (As information f o r t h i s chapter, the following references have been used: Briscoe ;(1959)i Sachanen (19^5)* Imperial O i l (195D. ) 2.13 Residuals of Burned Fuels Gasolines, kerosenes, d i e s e l fuels and f u e l o i l s are burned i n t h e i r normal use, Basically-^the end products of burned pure hydrocarbons are COg and^HgO. Chemically: CH^ + 2 0? = 2 H20 + C02 . (Methane) 14 At high temperatures, as they can occur i n i n t e r n a l com-bustion engines, nitrogen oxides are also produced by o x i d i z i n g atmospheric nitrogen.. Further end-products usually are sulphur oxides. Nearly a l l fuels, contain sulphur, how-ever, i n varying quantities. In the burning process, the sulphur i s oxidized and released to the atmosphere. A l l these end products end up i n the atmosphere as gases, thus contributing to a i r p o l l u t i o n which i s a problem by i t s e l f and not investigated further i n . t h i s study., -2.14 Lubricants and I n d u s t r i a l O i l s In t h e i r normal use, l u b r i c a t i n g o i l s and most i n d u s t r i a l process o i l s remain b a s i c a l l y unchanged chemically!. Only . small amounts.are burned or l o s t i n other ways. By f a r the largest amount of the o i l s become contaminated with various pollutants. V/hen t h i s contamination reaches a c e r t a i n l e v e l , the o i l has to be replaced and what i s l e f t over i s generally c a l l e d waste o i l . The sources of these waste o i l s are manifold and the com-po s i t i o n of these waste o i l s varies with the source. Some of the most important sources are: Automotive crank-case and transmission o i l s , hydraulic o i l s , transformer o i l s , cleaning o i l s , . t u r b i n e o i l s and a number of o i l s f o r special purposes. 15 Appendix 2 Appendix 2 shows the composition of used automotive crank-case o i l (EPS 17^). The sources of these by products are o i l additives added to the fresh o i l and materials accumu-lated during the normal use of the o i l . In the following some of the possible additives and accumulated products found i n waste l u b r i c a t i n g o i l s of i n t e r n a l combustion en-gines are l i s t e d : Additives to> O i l s : - Detergents - Dispersants - Corrosion I n h i b i t o r s - Anti-oxidants - V i s c o s i t y Index Improvers - Pour Point Depressants - Extreme Pressure Additives - Anti-Foam Additives - An t i - S t a i n Additives Additives to Fuels: - Detergents A n t i - i c i n g Additives • - Flow Improvers Pour Depressants Oxidation and Wear In h i b i t o r s - Smoke and Emission Control Aids Combustion Aids - Anti-knock Additives Biocides - Dyes - Emulsified Fuels Accumulation Products: Unburned Hydrocarbons. .. Soot and Ash - Fuel Additives. * - -Metallic abrasion Products -' - Condensed Water - • Corrosion Products - "Metallic Oxides 16 I n d u s t r i a l o i l s contain another range of additives with widely varying physical and chemical properties; i t i s not possible v/ithin the framework of t h i s study to look into d e t a i l s of the chemistry of the additives. 2.2 The Behaviour of Petroleum Hydrocarbons i n Water 2.21 The Physical Phases of O i l and Water The fundamental c h a r a c t e r i s t i c s of hydrocarbons which i n -fluence t h e i r behaviour i n water are the following: Hydrocarbons are b a s i c a l l y insoluble i n water except i n r e l a t i v e l y low concentrations. Hydrocarbons are, with very few exceptions, l i g h t e r than water. Their s p e c i f i c gravity ranges from 0.75 to 0.9 g/cm^ (Water 1.0 g/cm?).' . The d i f f e r e n t f r a c t i o n s contained i n crude o i l s and refined products have a d i f f e r e n t rate of d i s -appearance (see paragraphs 2.22 to 2.25).. Therefore the residuals of s p i l l e d petroleum vary over time, with generally l i g h t e r f r a c t i o n s disappearing f i r s t and leaving heavier and. heavier f r a c t i o n s , disappear-r i n g more and more slowly. The following describes b r i e f l y a chronological.sequence of an o i l s p i l l . When the o i l i s f i r s t introduced to the water, i t f l o a t s on top of the surface and begins to spread. The spreading of o i l on water depends on a large number 17 of variables such as s p e c i f i c g r a v i t y , v i s c o s i t y , quantity of o i l involved, the state i n which i t i s introduced into the water, distance from land, temperature, movements and depth of the water, wind i n t e n s i t y , etc. (ZoBell I963). Wind and water currents speed up the spreading and carry the o i l over long distances. The o i l of the Torrey Canyon s p i l l i n 1967> f o r example, was carried over more than 600 kilometres u n t i l i t was washed ashore i n western France, In view of a l l of these v a r i a b l e s , the extent of spreading i s extremely d i f f i c u l t to predict. A f t e r being s p i l l e d , a w a t e r - i n - o i l emulsion i s usually formed, containing up to 80 % water, which has a remarka-ble s t a b i l i t y and which makes any s p i l l cleanup procedures very d i f f i c u l t . The physical and chemical processes that, lead to' t h i s emulsion are not^.clearly understood and the effects vary widely with the p a r t i c u l a r type of mate-r i a l s p i l l e d (Dean I968). In addition to the formation of an emulsion, some lower b o i l i n g f r a c t i o n s of the crude o i l have a s l i g h t solu-b i l i t y i n water (Dean I968). These f r a c t i o n s are, however, highly volatile-and usually they are - l a r g e l y evaporated before d i s s o l v i n g i n water. D i s s o l u t i o n only plays a major role i n s p i l l s of l i g h t f u e l s or crudes which have a high proportion of lower b o i l i n g f r a c t i o n s . 18 Aft e r spreading, e m u l s i f i c a t i o n and d i s s o l u t i o n , b a c t e r i a l breakdown and auto-oxidation degrade the o i l , beginning f i r s t with the lower then the higher hydrocarbons. A f t e r a c e r t a i n time (usually on the order of 1 to 2 years), only the t a r r y residuals are l e f t f l o a t i n g on the water sur-face and p o l l u t i n g the beaches with t a r r y lumps, w e l l known to every barefooted beachcomber. The f l o a t i n g t a r lumps, which accumulate i n s h e l l f i s h and other marine animals, become heavier and f i n a l l y sink, to the bottom a f t e r a* r e l a -t i v e l y long time at the surface of the water. Due to t h i s length of time, t a r r y residuals can accumulate i n c e r t a i n areas of the oceans, as seems to be the case i n the Sar-gasso Sea of the A t l a n t i c Ocean. 2,22 Sinking O i l adsorbs to clay, s i l t , s h e l l s , s k e l e t a l remains of organisms and other p a r t i c u l a t e matter suspended i n the water (ZoBell I963). Such adsorption weights the o i l , cau-sing some of i t ' t o sink. In the case of o i l s p i l l s at sea, t h i s property has been repeatedly used to sink o i l to the. sea bottom, simply by spreading an adsorptive powder on the s p i l l e d o i l . I f waste o i l i s discharged to a s i l t y stream ( l i k e the Fraser River), a part of the o i l w i l l therefore adsorb and end up i n the bottom sediments. 19 Whether t h i s i s a b e n e f i c i a l e f f e c t or not i s d i f f i c u l t to say as i t represents simply a s h i f t of the p o l l u t i o n from the wa.ter surface to the bottom and to suspended so-l i d s . To a large extent such o i l i s withdrawn from fu r t h e r b a c t e r i a l attack because of the l i m i t e d amount of oxygen available i n bottom areas. O i l s which accumulate on the bottom may destroy bottom dwelling organisms. 2.23 ^Evaporation Light f r a c t i o n s of petroleum products have a low b o i l i n g point and evaporate quite r e a d i l y as soon as they are re-leased to the environment. These fr a c t i o n s may c o n t r i -bute therfqre to acute t o x i c i t y (see; paragraph 2 . 3 l l ) b u t they do not have any d i r e c t long term e f f e c t s . 2.24 Auto - oxidation Hydrocarbons o x i d i z e * n a t u r a l l y i f oxygen i s r e a d i l y a v a i l a b l e . The u l t r a v i o l e t rays of the sunlight speed up the o x i -dation'.process. The products of the f i r s t step of the o x i -dation are water soluble, they therefore dissolve i n the water and degrade r e l a t i v e l y rapidly, through b a c t e r i a l attack.;; According to ZoBell(I963) the'rate of auto-oxi-dation i s as l i t t l e as l/lO th that of the b a c t e r i a l break-down under s i m i l a r environmental conditions. 20 2.25 B a c t e r i a l Breakdown A large number of microorganisms have the a b i l i t y to break down hydrocarbons i n the natural environment. The break-down process takes place i n water and on land. Usually short, saturated chain molecules are the f i r s t to be bro-ken down. Unsaturated hydrocarbons have a slower rate of breakdown. The breakdown occurs f a s t e s t with dissolved hydrocarbons. Hydrocarbons, p a r t i c u l a r l y the lower, unsa-turated and aromatic ones are soluble i n water at low con-centrations. The rate of breakdown depends on a l a r g number of parameters but a lack of knowledge s t i l l e x i s t s with regard to some of these parameters. Temperature, nutrient and oxygen a v a i l a b i l i t y are probably the most important ones,. The eff e c t of temperature seems to play an important r o l e . Below 10° C nearly a l l b a c t e r i a l a c t i v i t y disappears, the optimal temperature being between 25 and 35° C. (ZoBell I963). Long term impacts are, therefore, much more serious i n cold climates than i n t r o p i c a l or moderate climates as there the breakdown occurs very slowly- or not at a l l . Nitrogen and phosphorus are required as nutrients f o r bac-t e r i a l breakdown. In most cases, nutrients are the l i m i t i n g 21 f a c t o r i n the hydrocarbon breakdown (Floodgate 1972). B a c t e r i a l breakdown has a high oxygen demand^ About three parts of oxygen are needed to break down one part of o i l (ZoBell I963). The oxygen demand i s the same i n case of auto-oxidation (paragraph 2.24). I f dispersed i n nearly saturated water of, say, 8 milligrams per l i t r e (mg/l) oxygen, the complete degradation of one l i -t r e of. o i l would deplete nearly 400 000 l i t r e s , or 400 irP of water of i t s oxygen. Different reports indicate quite varying breakdown rates. They range from 0 to 1.2 mg'per day per square metre. of water surface. (ZoBell, Floodgate 1972). 2 At an assumed rate of 0.5 mg/day/m and a breakdown time of 2 one year, an area of 2 500 square kilometres (km ) would be required to degrade an amount of 100 000 tons of o i l , approximately the quantity of o i l s p i l l e d i n the Torrey 2 Canyon accident i n 1967. 2 500 km corresponds roughly to the siz e of the Greater Vancouver Regional D i s t r i c t . Another i n t e r e s t i n g c a l c u l a t i o n shows 'the importance of land based discharges: ' • .. Assuming the same breakdown rate as i n the example above , an..average flow of the Fraser River of 2 700 m-V sec and 2 2 a constant discharge of a l l o i l y wastes of the GVRD to the Fraser River (5 300 tons/year or l7o g/sec, see paragraph 4.33), the o i l would be degraded w i t h i n 3.1 hours and the re-duction i n the dissolved oxygen would be no more than 1.9 %\ This c a l c u l a t i o n shows that the breakdown capacity of a large stream can be quite s i g n i f i c a n t . Discontinuous discharges such as o i l spills,however, are obviously ex-cluded from t h i s type, of c a l c u l a t i o n , which i s based on hypothetical assumptions which do not r e f l e c t r e a l i t y i n the proper sense. The purpose of these calculations i s to show the order of magnitude of the a b i l i t y of microorga-nisms to degrade hydrocarbons. As mentioned above, the b a c t e r i a l breakdown takes place i n water and on land. An i n t e r e s t i n g experiment has been carried out to test the breakdown a b i l i t y of microbes i n cul t i v a t e d s o i l s (EPA 1972c). Disposal of o i l y sludges by u t i l i z i n g s o i l microbes to decompose the o i l has been de-monstrated at p r e v a i l i n g soil'and c l i m a t i c conditions at Deer Park, Texas. The oil-decomposition rate was about .8 kg/m-^  (or 0.5 lbs/ft-^) of s o i l per month without f e r t i -l i z e r s and about double that amount when, f e r t i l i z e d . The amount of 16 kg/m^ corresponds to about 27 000 l i t r e s per hectare using the upper .15 cm of s o i l (or 70 bbls/acre/raonth). month) 23 The differences i n the decomposition rate and microbial species due to hydrocarbon type as present i n crude, bun-ker C and waxy r a f f i n a t e o i l s were minimal. The question of whether breakdown products are more to x i c than the o r i g i n a l hydrocarbons, i s at t h i s stage d i f f i c u l t to answer. Ultimately, hydrocarbons are t o t a l l y degraded mainly into CC>2 and H^ O and possibly other harmless com-pounds. However, a number of stages are necessary f o r the t o t a l breakdown. The l i t e r a t u r e review has not produced evidence that the intermediary products are less t o x i c than the o r i g i n a l hydrocarbons. 2.3 Effects of O i l P o l l u t i o n on Aquatic Ecosystems Two d i f f e r e n t kinds of effects have to be distinguished: the d i r e c t and the i n d i r e c t e f f e c t s . Direct effects are caused by the petroleum products themselves, whereas i n -d i r e c t effects are the r e s u l t of p o l l u t i o n by non-hydro-carbons, which, however only reach the environment due to •the use and manufacture of petroleum products. 2;31 Direct Effects In t h i s chapter, the t o x i c i t y of hydrocarbons i s more close-l y investigated. The effects of detergents are not c l e a r l y d i r e c t effects but neither are they c l e a r l y i n d i r e c t e f f e c t s . They w i l l be treated i n t h i s chapter. 2k A number of poorly understood problems remain with regard to the t o x i c i t y of. hydrocarbons. The r e s u l t s of various re- . ports often-contradict each other and are i n disagreement. However, there seems to be general agreement on the f a c t that simple saturated and unsaturated hydrocarbons have a r e l a t i v e l y low t o x i c i t y . Aromatic compounds and a number of p a r t i c u l a r unsaturated hydrocarbons form an exception to t h i s r u l e . - Neither the "Toxic Substances L i s t " of the U.S. Department of Health, Education and Welfare (U.S. DHEW 1973)1 nor the "Water Quality C r i t e r i a Data Book" of the EPA (1973) l i s t s t r a i g h t p a r a f f i n i c hydrocarbons as toxic substances. However, large amounts of o i l discharged to the water envi-ronment creates a p o t e n t i a l problem even though the t o x i c i t y of the substances involved ;is of r e l a t i v e l y low order. 2.3II Acute T o x i c i t y In appendix 3 the r e s u l t s of three d i f f e r e n t t o x i c i t y tests by Ottway (1970), Crapp (I970), and EPA (l97^b) are given. These t e s t s , as we l l as the references Carthy (I968), Cowell (1970), Holme (I969), ZoBell (1963). Mc Caull.(1969) and "SNAME (1971) have been used to summarize-the toxic effects of petroleum products. 25 Effects on Animals Tests with young 22 l}2l^i m 2D showed -mortalities of 50 % and more a f t e r being exposed during 96 hours to a test tank with a layer of crude o i l on top of the water surface, equivalent to a concentration of 35°0 ppm of o i l i n water i f the o i l were mixed homogenously. In a second series of t e s t s , the o i l was mixed with the water but s u r p r i s i n g l y no s i g n i f i c a n t differences i n m o r t a l i t i e s were obtained when compared with the f i r s t s e r i e s . Several refined products were also tested, some of them had high t o x i c i t i e s (100 ^ m o r t a l i t y a f t e r 96 hours i n a concen-t r a t i o n of 100 ppm). The mo.st frequently encountered com-pounds i n market products, l i k e gasoline, f u e l o i l s and l u -b r i c a t i n g o i l s , however, showed no s i g n i f i c a n t m o r t a l i t i e s up to a concentration of 100 ppm. The death of f i s h i s caused by a secretion of a thick f i l m of mucus over the g i l l s , which ultimately causes asphixiation. Tests with other organisms have shown that t o x i c i t i e s vary.substantially with d i f f e r e n t types of crude o i l s . Temperature has,a s i g n i f i c a n t influence on t o x i c i t y but not i n a consistent manner f o r every crude o i l tested. Some o i l s showed p o s i t i v e , others negative and yet others 26 unlinear correlations. A p o s i t i v e c o r r e l a t i o n exists between t o x i c i t y and the con-tents of sulphur, asphaltenes, aromats and low b o i l i n g f r a c t i o n s . I t i s therefore r e l a t i v e l y d i f f i c u l t , to pre= d i e t the effects of a p a r t i c u l a r crude o i l on f i s h , as i n addition to the complex composition of the crude o i l , , s y n e r g i s t i c and antagonistic e f f e c t s may occur. This i s less the case with refined products, f o r which i t should be ea-s i e r to predict the ef f e c t s on aquatic ecosystems. In the case of the p a r t i c u l a r species tested (the gastro-pod L i t t o r i n a L i t t o r a l i s ) the l i g h t gasoline and kerosene caused high mortalities,., whereas d i e s e l f u e l , l i g h t f u e l and heavy f u e l o i l s caused low m o r t a l i t i e s . F i s h that eat o i l coated,..particles are usually not adversely, affected, but- become unmarketable due to bad taste (see para-graph 2.4). Large amounts of o i l y materials that sink to the bottom (e.g. o i l s p i l l s treated with sinking agents) can coat the bottom dwelling benthic organisms and destroy them. Phytoplankton are usually not affected by o i l p o l l u t i o n , zooplankton on the other hand are affected i n the same way that algea are - they become coated by the o i l , d i e , clump 27 together and sink.to the bottom. Effe c t s on birds are usually the mos t apparent i n large o i l s p i l l s . The b i r d s 1 feathers get coated with o i l which destroys t h e i r i n s u l a t i n g capacity; the birds die from exposure, o i l ingestion and starvation. Indirectly., the breakdown of the o i l a f f e c t s a l l organisms through depletion of the oxygen concentration i n the water. In waters which are already low i n oxygen to s t a r t with, o i l p o l l u t i o n can cause serious problems. Small streams and lakes with a l i m i t e d oxygen reservoir are obviously more endange-red than large waterways which have a greater capacity to absorb biodegradable waste. The Lower Fraser can c e r t a i n l y be c l a s s i f i e d as large waterway. In f a c t , oxygen depletion does not seem to have a noticeable e f f e c t on the r i v e r (see also paragraph 2.25). A layer on top of a water surface i n h i b i t s or reduces aera-t i o n , thus amplifying the effects of a shortage i n the oxygen supply due to b i o l o g i c a l action. This e f f e c t , how-ever, occurs only i n very calm waters. Waves, wind and turbulence cause a- rupture of the f i l m , allowing the water to take up oxygen. Effe c t s on humans Toxic effects upon humans through ingestion usually i s not 28 to be feared, as food gets strong, undesirable tastes and odors before any toxic l e v e l s are reached (further com-ments i n paragraph 2.4). 2.312 Chronic Effects A considerably greater degree of uncertainty exists i n the understanding of the long term e f f e c t s as compared to the acute effects of o i l p o l l u t i o n . The substances causing long term effects are the persistent f r a c t i o n s of the crude o i l , e.g. asphaltenes, l u b r i c a n t s , heavy f u e l o i l s etc. These fractions have a r e l a t i v e l y low short term t o x i c i t y but t h e i r long term e f f e c t s could be more serious. As Blumer (I969) notes, the heavy f r a c t i o n s could b u i l d up i n organisms which are part of the aquatic food chain. Furthermore, some of the higher b o i l i n g f r a c t i o n s contain carcinogenic compounds and can therefore be dangerous to human health, even i f consumed i n small quantities. P o t e n t i a l l y one of the most dangerous aspects of long term t o x i c i t y i s the interference of o i l y f r a c t i o n s with chemical messengers which d i r e c t many b i o l o g i c a l processes and which' are important f o r the s u r v i v a l of many species, Blumer. (1969) writes: I t i s obvious that a very simple - and seemingly innocuous - interference at extremely low concentration 29 . l e v e l may have a disastrous e f f e c t on the s u r v i v a l of any marine species and on many other species to which i t i s t i e d by the marine food chain". Blumer's a r t i c l e refers to the marine environment. L i t e -rature on freshwater environments l i k e r i v e r s , streams, lakes etc. i s f a r less abundant, thus leaving a number of unanswered questions f o r t h i s study. 2.3I3 E f f e c t s of Detergents As mentioned i n chapter 2.2, the detergents cause emul-* s i f i c a t i o n Of the o i l i n water. Chemically, the detergent molecule" i s a hydrocarbon with a hydrophilic (watersoluble) group attached to i t . The hydrocarbon part of the mole-cule i s soluble i n the petroleum product and the hydro-p h i l i c part i s soluble i n water. I f a detergent i s added to a water-oil mixture, a g i t a t i o n i s needed to emulsify the o i l . This emulsion w i l l then consist of small droplets of o i l , , surrounded by molecules of the detergent, as i t i s i l l u s t r a t e d i n the f i g u r e below. O i l droplet Detergent Molecules Water Water l i p o p h i l i c part v. 30 The effects of a detergent-oil-water emulsion on a natu-r a l environment are b a s i c a l l y twofold: ( 1 ) E m u l s i f i c a t i o n speeds up the b a c t e r i a l breakdown of the o i l , as the o i l becomes more available to. the microorganisms. (2) the ne-gative aspect i s the higher t o x i c i t y of most detergents, s p e c i a l l y of those used i n o i l s p i l l cleanups, than of the o i l i t s e l f . Although the conclusions, of d i f f e r e n t authors vary, there seems to be a consensus that the negative impact of d i s -persants used f o r o i l s p i l l cleanups i s generally greater than the impact of the o i l i t s e l f . An extensive l i t e r a t u r e search by B a t t e l l e (I967) indicated that the b i o l o g i c a l e f f e c t s of a l l detergents are s i m i l a r . Canevari (I969) found concentrations ranging from 5 to'- 10 ppm or more to cause death to a variety of f i s h . A question to ask at t h i s point i s whether the required; biodegradability of detergents used in-nouseholds and indus-t r i e s have an effect on the t o x i c i t y of hydrocarbons. 2.32 Indirect E f f e c t s Indirect effects are defined here as ef f e c t s due to non- -hydrocarbon p o l l u t i o n but d i r e c t l y related to the use and manufacture ..of petroleum products. 31 The following types of p o l l u t i o n f a l l into t h i s category: - P o l l u t i o n at o i l production s i t e s ( e.g. o i l f i e l d brines) - Petroleum r e f i n e r y effluents - Discharge to the environment of a l l kinds of pe-troleum product additives. In the Vancouver Area only the l a t t e r two categories need -to be taken into consideration. The two types of p o l l u t i o n are., b r i e f l y described i n the following paragraphs to pro-vide a general overview. 2.321 Refinery Wastes The. r e f i n i n g process produces mainly three types of p o l l u -t i o n : Biochemical Oxygen Demand (BOD), sulphides and phenols Jones (1973) describes the s p e c i f i c process units of a. re-f i n e r y and t h e i r respective waste generation i n d e t a i l . Table 1 gives a summary of the•principal waste loads and waste water volumes of a r e f i n e r y of 100 000 barrels per day (or 14 000 tons/day) throughput of crude o i l . As the table shows, s i g n i f i c a n t reductions i n waste water flows and waste discharge have been achieved with more modern technology. Jones indicates that the size of the r e f i -nery has no s i g n i f i c a n t impact on the quantity of the waste loads pe-r unit of throughput, 32 Table 1 Total Refinery E f f l u e n t of a 15 0 0 0 tons/day Refinery Type of Technology Flow 1000 t/day BOD' kg/day Phenols kg/day Sulphide kg/day Older 100 28 000 1500 5Q0 Typical 40 5 0 0 0 5 0 0 150 Newer 20 2 5 0 0 2 5 0 ' 150 Oils themselves are an important component of re f i n e r y effluents but exact information on the waste loads of o i l s i s not available. Usually the e f f l u e n t passes through an oil-water separator, which removes approximately 80 % of the o i l . The remaining efflu e n t i s then passed through a p r i -mary or secondary treatment plant which removes most of the remaining wastes. . 2 . 3 2 2 Additives-and Contaminants of Waste O i l s To i l l u s t r a t e t h i s type of problem, the chemical compo-s i t i o n of waste o i l i s given as an example i n appendix 2. According to t h i s analysis of automotive crankcase o i l of a Canadian source, an impressive number of contaminants are .-found i n these o i l s . These contaminants are a r e s u l t of the numerous additives-to lubricants and of t h e i r use i n crankcase and gearboxes 33 where the o i l s accumulate metallic abrasion p a r t i c l e s , f u e l additives (lead being the most evident) and various oxidation products (see paragraph 2.14). I f such waste o i l s reach'the natural water environment i t can be speculated that the hazardous ef f e c t s w i l l mainly be caused by the by--products rather than by the o i l i t s e l f . Table 2 indicates the safe concentration f o r some of the most toxi c metals found i n waste o i l s , as w e l l as the concentrations found i n the o i l s . Fi'om these two concentrations, a d i l u t i o n f a c t o r has been calculated, i n d i c a t i n g the necessary d i l u t i o n of the o i l i n order to reach a safe l e v e l i n r e l a t i o n to spe-c i f i c metals and to the aggregate of a l l contaminants. In t h i s example, safe l e v e l has been defined as a concentra-: t i o n up to which no harmful effects occur.to marine a n i -mals. Table 2 Calculation of D i l u t i o n Factor Metal • Concentration i n waste o i l i n ppm 1) Safe Concen-t r a t i o n ppm D i l u t i o n Factor Lead. 10 0 0 0 • * 3 2 ) 77 ooo Cadmium 4 . 0 2 2 ) 200 Copper 180 .0.1 2 ) 18 000 Zinc l 5 0 0 . 0 1 2 ) 150 000 T i n 6o . 0 5 3 ) 1 200 Chromium 30 . 0 5 3 ) 6 0 0 Nickel . 2 3 ) 7 • S i l v e r 1 . 004 2.) .200 'Total . 2 4 7 0 0 0 4 ) 3 4 Footnotes to Table 2 1) Source: EPS (1974):. 2) D.O.E. (1972), Guidelines f o r Water Quality-Objectives and Standards 3) Oregon State University (1972) 4) According to D.O.E. (1972) i t i s suggested that the concentrations (or as i n t h i s example the necessary d i l u t i o n factor) f o r the d i f f e r e n t trace metals are purely a d d i t i v e , i . e . no syne r g i s t i c or antagonistic effects are considered. For the waste o i l i n t h i s example,. 247 000 times i t s own volume i s necessary to d i l u t e the w a s t e ; o i l to a safe concentration of the contaminants. Or i l l u s t r a t e d : 1 gallon of waste o i l needs appro-ximately 1 100 nP of water to d i l u t e i t . There are a number of other factors a f f e c t i n g the t o x i c i t y of the metals i n the water environment,, l i k e hardness, , ' temperature and"pH, Hardness reduces the t o x i c i t y of trace metals considerably, as the following table shows f o r the example of cadmium. -Table 3 T o x i c i t y of Cadmium vs. Hardness. Hardness (mg CaCO^/l) Incipient LC 50 mg/l* 10 .039 50 • 39 100 1.1 , 500 11.0 1000 30.5 Source: D.O.E. (1972)' * LC 50 =• Lethal Concentration 50 or concentration at which SO % of a population dies i n a c e r t a i n time. 35 Temperaturet According to an unpublished report of the Fisheries Research Board (reftD.O.E. 1972), copper and z i n c , f o r example, seem to be about three times as tox i c to salmon at 5° C as at 17° C. A further f a c t o r i s the gH of the- ambient water. Low pH (sour) or high pH (ba.sic) may increase t o x i c i t y of copper and zinc according to recent work vat- the Fisheries Research Board. As a general statement, i t can be said s a f e l y that waste o i l s have- a considerable p o t e n t i a l f o r water p o l l u t i o n . This p o t e n t i a l i s derived mainly from the various m e t a l l i c compounds contained i n the o i l and discharged with i t and, to a f a r smaller extent, from the o i l i t s e l f . 2.4 Effects of O i l P o l l u t i o n on the B e n e f i c i a l Uses of Water The uses to which water may be put .beneficially and econo-mically include: Domestic water supply I n d u s t r i a l water supply I r r i g a t i o n of crops Swimming, bathing, boating, esthetic enjoyment Navigation, and water power Stock and W i l d l i f e watering Propagation of f i s h and aquatic l i f e Production of s h e l l f i s h Maintenance of waterfowl. 1. 2. I: 5. 6. 7. 8. 9 . 36 The purpose of t h i s section i s to summarize the extent to which o i l y substances i n t e r f e r e with these uses. I t i s mainly a summary of a report of the C a l i f o r n i a State Water P o l l u t i o n Control Board (SWPCB I956). Categories 1 to 6 w i l l be discussed below; since chapter 2 . 3 covers categories 7 to 9. 2 . 4 1 Domestic Water Supply The p o t e n t i a l e f f e c t s of o i l i n domestic water supply may be grouped into the following categories: a) health hazards to consumers b) production of tastes and odors c) increased d i f f i c u l t y of water treatment d.) presence of t u r b i d i t y and f i l m s Only the f i r s t three categories are discussed, the f o u r t h ' i s u n l i k e l y to cause problems, as concentrations required to produce t u r b i d i t y or films, are s u b s t a n t i a l l y higher than the f i r s t two categories require. 2 . 4 1 1 Health Hazards, Tastes and Odors . SWPCB presents a l i s t of substances with approximate to-lerable* concentrations r e l a t i v e to t h e i r t o x i c i t y , to humans of some o i l y substances i n drinking water. Concentrations f o r pure, non-aromatic hydrocarbons range from 5000 to 1 4 000 ppm, benzene and probably other aromatics are 37 s u b s t a n t i a l l y more toxi c with a tolerable concentration of only about 560 ppm. The concentrations required to produ-ce odor and taste thresholds are s u b s t a n t i a l l y lower. SWPCB indicates threshold odor concentrations f o r hydro-carbons of 0.003 to 0.025 PPm» thus approximately 1 m i l l i o n times lower than the t o x i c thresholds. For example the odor threshold of commercial gasoline has.been indicated as low as 0.01 ppm, whereas l u b r i c a t i n g o i l i s only detectable at concentrations approximately 100 times higher than gasor-l i n e (lppm). The s i g n i f i c a n t conclusion~:is that any tolerable health concentration f o r petroleum products by f a r exceed the l i m i t s of taste and odor i n water. I t appears that human health . hazards w i l l not occur from o i l p o l l u t i o n as the water w i l l become .objectionable at concentrations f a r below chronic t o x i c i t y l e v e l s , 2.412 Effects on Water Treatment Float i n g or emulsified o i l i n raw water supplies w i l l com-: -plicate the coagulation, f l o c c u l a t i o n and sedimentation pro-cess at a treatment plant. O i l coated f l o e may not s e t t l e properly. I f free or emulsified o i l reaches sand f i l t e r s -or ion-exchangers ; i t w i l l coat the grains, decrease the-effectiveness of the f i l t r a t i o n and i n t e r f e r e . w i t h back-38 washing. O i l polluted water supply w i l l therfore r e s u l t i n increased costs of maintenance of a treatment plant. 2.42 I n d u s t r i a l Water Supply The major purposes f o r which industry uses water are the following: steam production T cooling - hydraulic transport - p r o d u c t i o n and process operations In steam_production 2 the presence of o i l i n b o i l e r water may cause foaming, priming, overheating 1 of tubes r e s u l t i n g i n b l i s t e r i n g or f a i l u r e and poor transmission of .heat from the metal to the water. Cooling waters may be used once and ..discarded, i n t h i s case o i l does not cause any major problems. I f , however, the water i s r e c i r c u l a t e d , evaporation w i l l cause impurities i n the water to concentrate. Moreover, aeration over huge surfaces favors b i o l o g i c a l a c t i o n , so that cooling waters become slimy, e s p e c i a l l y when organic pollutants and nutrient materials are present. For many 2r22enSiDS_§B^_'EE2§L125i2D_2Per^5i2B2 " t h e ^ J 0 1 * deleterious effect of o i l y substances i s the p o s s i b i l i t y of tastes and odors i n the manufactured products. This i s es-p e c i a l l y true f o r brewing, carbonated .beverages and other 39 food manufacturing. I t i s obvious that recommended thre-sholds should be below the threshold odor concentration. The major concern of industry regarding water q u a l i t y i s a v a r i a t i o n i n constituents or concentrations from day to day or hour to hour. Industry i s generally prepared to treat water and to make i t acceptable f o r a given product but such treatment processes are not adaptable to sudden changes i n the q u a l i t y of the raw water supply. Thus an occasional slug of o i l y material i n the raw.water would be more trouble-some than a steady concentration. 2 . 4 3 I r r i g a t i o n Water SWPCB indicates that i r r i g a t i o n waters polluted by o i l y materials do not have any deleterious effects on plants. E f f e c t s occur only i f concentrated hydrocarbons are used.as i n s e c t i c i d e s , f o r weed c o n t r o l , f e r t i l i z i n g and mulching. I t appears therefore that o i l y substances that may p e r s i s t i n i r r i g a t i o n waters are extremely u n l i k e l y to cause any damage to crops. 2.kh Other Effects of Oily,Substances. The effects of o i l s on w i l d l i f e and stock watering have been studied by several'investigators and summarized by • SWPCB. I t seems that s i m i l a r to domestic water supply, strong odor and disagreeable taste of water heavily p o l -luted with hydrocarbons make i t u n l i k e l y that animals w i l l drink such waters. Again, thresholds f o r t o x i c effects are much higher than the thresholds f o r odor and taste. Fur-ther negative effects of o i l p o l l u t i o n include swimming, boating, navigation, esthetic enjoyment and the handling of waste waters. L i m i t i n g threshold concentrations to pro-tect these b e n e f i c i a l uses are d i f f i c u l t to determine. . The o i l y wastes may a f f e c t these uses i n two p r i n c i p a l ways: a) f l o a t i n g o i l may f o u l boats, bathing beaches, f i s h i n g gear, p i e r s , quays, sewers and sewage treat-ment works, b) V o l a t i l e constituents may cause f i r e i n open areas or explosions i n sewers. To conclude with a statement from SWPCB: "A requirement that wastes discharged to receiving wa-te r s be free from f l o a t i n g o i l and v o l a t i l e ' c o n s t i t u -ents i s c e r t a i n l y j u s t i f i e d to protect many b e n e f i c i a l . uses. I t i s a requirement that does not impose an ex-cessive economic burden on the waste discharger. Where emulsions are involved, a case study w i l l be required to determine i f the emulsion i s l i k e l y to break i n the sewers or receiving waters, or i f i t w i l l i n t e r f e r e with any b e n e f i c i a l use", 2 . 5 Remaining.Uncertainties • v If t h i s chapter has demonstrated one thing with absolute c e r t a i n t y , i t i s the fa c t that none of the phy s i o l o g i c a l and b i o l o g i c a l aspects of o i l p o l l u t i o n , are completely under-4 1 stood. The effects of o i l p o l l u t i o n depend on the prevai-l i n g combination of p a r t i c u l a r environmental conditions and the types and rates of discharge of petroleum products i n -volved. Environmental conditions are made up of the type of the receiving water, the cl i m a t i c conditions, the type of the ecosystem, the season, etc. Possible pollutants are a large number of d i f f e r e n t crude o i l s or refined products. I t is-, obvious, that there e x i s t s a gigantic number of pos-s i b l e combinations of these f a c t o r s , making any systematic research on long and short term t o x i c i t y of petroleum pro-ducts and t h e i r -possible breakdown by-products, on'-break-down rates, effects of detergents and contaminants of waste o i l s ; extremely d i f f i c u l t . -~ The available r e s u l t s of e x i s t i n g research provide therefore only a general guideline and most r e s u l t s are not compara-ble to one another, In l i g h t of these uncertainties, i t would be adviseable, to include a-security f a c t o r i n consi-dering discharges of o i l y wastes to the environment. Some resu l t s of t h i s chapter suggest, that the detrimental ef-fects of o i l i n the environment have often been ov e r e s t i -mated,as i s often the case with environmental issues that a are debated with a great deal, of emotion. However, caution has to be exercised not to f a l l into the other extreme by l i g h t l y permitting any kind and.amount of petroleum dischar-ges. C H A P T E R T H R E E THE MATERIALS BALANCE APPROACH - GENERAL CONSIDERATIONS 3.1 Theoretical Framework As suggested i n the introduction, the materials balance concept seems to be best suited f o r . f u l f i l l i n g the objec-t i v e s of t h i s study. According to Kneese (et a l . 1970), the idea of a.pplying materials balance concepts to waste dispo-s a l problems was f i r s t expressed by F.A. Smith (I967). E a r l i e r applications,, based on the materials balance approach however, e x i s t i n various f i e l d s , of study, to mention only the following: biogeochemical cycles, energy balances etc. The concept therfore i s not.new, i t has only been recently considered f o r a new f i e l d . In recent times, a number of studies using the materials balance approach f o r waste disposal problems have appeared. Three balances on a nationwide basis have been carried out at the Oak Ridge National Laboratory i n the U.S. f o r the tox i c substances' mercury, polychlorinated biphenols (PGB's) and Cadmium (NTIS 1971,1972 and 1973). A more general discussion of the concept i s found i n Kneese (et a l I97O). 4 3 Besides these studies there e x i s t a number of materials .balances f o r petroleum products. The EPA report "Waste O i l Recycling and Disposal" (EPA 1974a), contains a com-plete balance f o r a l l petroleum products i n the United Sta-tes. For some materials, .some rough; estimates are made i n the report? f o r some others, r e l a t i v e l y detailed and r e l i a -ble figures were av a i l a b l e . In spite of t h i s d i f f i c u l t y , t h i s EPA study i s r e l a t i v e l y w e l l suited f o r f i l l i n g i n gaps that remain'in the materials balance f o r the Vancouver Area i n chapter 4 . Environment Canada has carri e d out a survey on waste l u b r i -cating o i l s including a materials balance f o r t h i s material f o r Canada. No p r o v i n c i a l or regional breakdown of the f i -gures i s available (EPS 1974). A further c o l l e c t i o n of data on volumes of waste o i l s i s found i n EPA( l974d) . In the state of Maryland, an exten-sive survey has been carried out on waste o i l s . This study contains an analysis of al t e r n a t i v e disposal systems, i n -cluding cost analyses. Outside North America the study by the Ba t t e l l e Institute-on the waste o i l s i t u a t i o n i n the German Federal.Republic i probably the .most i n t e r e s t i n g one (B a t t e l l e 1971). As t h i s l i s t shows, a l l but one. of these studies e s t a b l i -shed materials balances on a national l e v e l f o r r e l a t i v e l y 44 l a r g e c o u n t r i e s . The u s e f u l n e s s o f t h e s e b a l a n c e s , a t l e a s t • f r o m the p o i n t o f v i e w o f p o l l u t i o n c o n t r o l , i s l i m i t e d . I n a v e r y l a r g e c o u n t r y l i k e Canada, where most o f the economic a c t i v i t i e s a r e c o n c e n t r a t e d i n a . r e l a t i v e l y s m a l l a r e a , na-t i o n w i d e t o t a l s do n o t r e v e a l any p o l l u t i o n problems. The a p p r o a c h g a i n s i m p o r t a n c e o n l y when a p p l i e d t6 a r e l a t i -v e l y s m a l l r e g i o n , f o r example th e G r e a t e r Vancouver Re-g i o n a l D i s t r i c t . 3 . 2 The S o u r c e s o f O i l P o l l u t i o n - A Worldwide M a t e r i a l s B a l a n c e . F i g u r e 6 I n f i g u r e 6 a n a.ttempt - i s made t o p r e s e n t a w o r l d w i d e m a t e r i -a l s b a l a n c e . As a s o u r c e o f d a t a , t h e a v a i l a b l e r e p o r t s were used and e x t r a p o l a t e d t o a . w o r l d w i d e - l e v e l . The. ob-j e c t i v e o f t h i s b a l a n c e i s t o show the m a t e r i a l i m p o r t a n c e o f t h e d i f f e r e n t pathways o f p e t r o l e u m p r o d u c t s t o t h e en-v i r o n m e n t and t o p r o v i d e a b a s i s f o r c o m p a r i s o n w i t h o t h e r F i g u r e 6 s t u d i e s . F i g u r e 6 shows t h a t more t h a n 98 % o f t h e crude o i l p r o d u c t i o n i s burned as l i q u i d f u e l s , 1 fo i s l u b r i -c a t i n g o i l s a l e s , t h e r e s t i s marine and t e r r e s t r i a l o i l s p i l l s and l o s s e s . Two t h i r d s o f t h e waste o i l s and s p i l l s a r e burned ( r e c o v e r e d w a s t e - l u b r i c a t i n g o i l s and s p i l l s ) ; t h e o t h e r t h i r d i s d i s p o s e d o f t o t h e l a n d and w a t e r e n v i -. ronment. ' . ^5 There i s a major d i f f i c u l t y i n estimating the amount of o i l s p i l l e d . An extrapolation of data from the e x i s t i n g re-ports probably r e s u l t s i n an underestimation of the marine s p i l l s , as the only balance which include marine s p i l l s (EPA 1974a) i s l i m i t e d to coastal waters. Furthermore, the amount of o i l s p i l l e d i n the high seas i s very i r r e -gular due to a small number of large s p i l l s . I t i s , there-fore, l i k e l y that marine s p i l l s are larger than indicated i n f i gure 6. A notable feature of these figures i s the very high use of waste o i l as f u e l (10 m i l l i o n tons p.a.) as compared to the amount re-refined (830 000 tons). Also i t i s s u r p r i -sing that 45 °?o of the material treated by waste o i l pro-cessors come from o i l s p i l l cleanups (according to EPA 1974a). The t o t a l of 6.25 m i l l i o n tons. of', o i l y discharges • to the water environment compares with 2.1 m i l l i o n tons reported i n a former study by SCEP ( I 9 7 0 ) . The study by SCEP only accounts f o r the o i l i n f l u x to the oceans and disregards the p o s s i b i l i t y of breakdown i n freshwater before entering the sea. As shown i n paragraph 2 . 2 5 , t h i s amount i s l i k e l y to be substantial. Table 4 (page 46) shows a. s i m p l i f i e d version of figure 6 46 Table 4 Worldwide Materials Balance Figures i n 1 0 0 0 tons per year Crude O i l 2 322 000 Lubricants 22 100 O i l S p i l l s . marine 2 100 . t e r r e s t r i a l 11 8 0 0 - Total 36 0 0 0 Fuels 2 286 0 0 0 Consumed as lubricants 11 3 7 0 V Fuel Use 10 66oj To Environment 10 7 4 0 To Roads 3 2 3 0 Total 36 pop To Environment Land 9 340 Water 6 2 5 0 Roads 3 8 0 Total 15 9 7 0 To A i r -2 306 0 0 0 Figure 4 Figure 4 shows a conceptual network f o r i n v e s t i g a t i n g the flow of petroleum products i n the GVRD. Figure-5 Figure 5 shows the same, but the flows are grouped into the d i f f e r e n t classes of products. 47 C H A P T E R F O U R REGIONAL MATERIALS BALANCE FOR PETROLEUM PRODUCTS IN THE GREATER VANCOUVER REGIONAL DISTRICT 4,1 Imports, Exports and Consumption 4.11 Province of B r i t i s h Columbia; This section summarizes the available data of s t a t i s t i c s Canada f o r the Province of B r i t i s h Columbia. In the next paragraph anattempt -is made to break these figures down to the regional l e v e l of the GVRD; The various petroleum products are grouped into the following categories: Gasoline . - ' - Aviation Fuels - Diesel Fuels - Fuel O i l s - Lubricating oils.and I n d u s t r i a l O i l s In a few cases, the f i r s t four groups are treated as one class of products, namenly l i q u i d f u e l s . These two cate-gories are allocated to the following sectors: ^ Transportation Gasoline and service s t a t i o n sales Government sales and other transportation Construction Industry } Forest Industry - f Industry Other Industry J Residential, Appartment and Farm Use . Domestic 48 The p r o d u c t i o n , s a l e s , i m p o r t s and e x p o r t s o f the p r o v i n c e f o r t h e s e groups o f p e t r o l e u m p r o d u c t s a r e shown i n t a b l e 5 T a b l e 5 P r o d u c t i o n , Consumption, Imports and E x p o r t s o f P e t r o l e u m • P r o d u c t s i n the P r o v i n c e o f B.C. i n 1 9 7 2 , i n 1000 m e t r i c t o n s . P r o d u c t S i 1 "0 "0 ]. V R e f i n e r y P r o d u c t i o n 1 import 2 Total • 3 G a s o l i n e 2558 I486 4046 A v i a t i o n 245 68 313 D i e s e l 1101 868 : - 1969 F u e l O i l s 2041 1045 3086 L u b r i c a n t s 101 101 . T o t a l 59^5 }'-*-::\ ' 3570 ;.. , 9515 P r o d u c t C ; 0 n s j \ j. m '.p t. i. ;o n Transp. I n d u s t . Domest .T o t a l ' I Export,; T o t a l II-; 4 - 5 ' 6 , • 7 ' -8 • . 0 G a s o l i n e " , 2531 , .12Q - 2660 1352 ' 4() 12 A v i a t i o n 280 ' - 280 . 31 3 U D i e s e l 895 427 1322 625 1947 F u e l O i l s 128 1245 1098 2471 560 303I L u b r i c a n t s 57 .9 34 .1 • - 92 ' 10 l o 2 T o t a l 3892 . 1835 1098 6 8 2 5 : • 2 5 7 8 . 9403 S o u r c e : S t a t i s t i c s Canada, " R e f i n e d P e t r o l e u m P r o d u c t s " P u b l i c a t i o n No. 4.5-208 The t o t a l s o f columns 3 and 9 show the - t o t a l s u p p l y and the t o t a l demand ( e x p o r t and consumption) r e s p e c t i v e l y . 49 Total I represents the t o t a l amount consumed wi t h i n the province, t o t a l I I the t o t a l amount flowing through the province. 4.12 Regional Breakdown f o r the GVRD In t h i s section, an attempt i s made to break down the pro-v i n c i a l figures to a regional l e v e l . A simple breakdown per capita or per job does not produce useful r e s u l t s , as the regional d i s p a r i t i e s within the province are substan-t i a l . D i s p a r i t i e s such as climate which af f e c t s the per ca-p i t a heating f u e l consumption, population density which af-fects use of cars and length of t r i p s , concentration of • >- :.V.' many industries not proportional to population or jobs a f f e c t i n g the use of many i n d u s t r i a l o i l s and fuels are just a few examples. Therefore, other ways have to be found to calculate the figures f o r the GVRD. Table 6 shows the percentages of GVRD consumption of the province f or the d i f f e r e n t classes of products. The num-Appendix 1 bers i n brackets () r e f e r to appendix 1 which describes the methods "used i n deriving the figures. Table 7 shows the r e s u l t of the breakdown f o r the d i f f e -rent classes of products. Table 6 Regional Consumption i n f> of the t o t a l f o r the Province Sector* ' • ' Product Trans po r t a t i on Industry Domestic Total Motor Gasoline (1) 36.3 34.0 36. 1 A v i a t i o n Fuels (2) 85 - - 85 Diesel Fuels (3) 36 21 - 30 Fuel O i l s 50 (4) 30 (5) 44 (6) . 37.4 Lubricants (7) 40 26.4 - 34.3 Total 39.8 28.1 44 37.4 Table 7 Regional Consumption i n 1000 tons (1972) B.C. G V R D Product Trspt Indus Dom. Total Trspt Indus Dom. Total I Expt. Total I I fo * Gasoline A v i a t i o n Diesel Fuel O i l 2531 • 280 895 • 128 129 42? 1245 1098 2660 280 1322 2471 918 240 304 64 44 90 375 485 962 240 394 924 1075 30 487 500 2037 270 881 1424 36 85 ' 30 37.^ Total Fuels 3834 1801 . 1098 6733 1526 509 485 2520 2092 4612 37.4 Lubricants 57.9 34.1 - 92 23.6 8 31.6 10 41 . 6 34.3 Total 3892 1835 1098 6825 1550 517 485 2552 2102 4654 37.5 * Total I of GVRD i n f> of Total of B.C. o 51 The:breakdown of the available figures to the regional l e v e l from s t a t i s t i c s Canada data i s based on many assumptions, as the description i n appendix makes quite clear. However, i n -the case of the l i ^ u i d ^ f u e l s , a f i r m figure i s available f o r gasoline which accounts f o r more than 60 % of the t o t a l l i q u i d fuels sold to the transportation sector. An error i n the other figures w i l l a f f e c t only 40 % of the t o t a l and i s therefore, of lesser significance than might appear. Data f o r the i n d u s t r i a l and domestic sector are somewhat less s o l i d . However, as stated i n appendix 1, the estimate of the l i q u i d fuels i s only of secondary importance. The transportation sector consumes approximately 75 % of the lubricants. The f i r m data f o r gasoline, therefore, provides a good basis f o r estimating the use of t h i s commodity. The figure f o r the i n d u s t r i a l "sector has' been divided into three subsectors (construction, f o r e s t and other industry), of which the forest industry makes up approximately two thirds of the t o t a l , The estimate.for t h i s sector i s based on information by a representative of McMillan Bloedel and i t can be expected that t h i s estimate i s reasonably good. For these reasons, the o v e r a l l figure f o r the regional breakdown can be considered .as f a i r l y s o l i d . 52 4.2 Residuals Generation This section i s divided into three parts according to the three basic ways residuals are generated from petroleum products: Residuals production (1) through l i q u i d f u e l marketing and use, (2) through waste o i l disposal: and (3) through o i l s p i l l s and losses (crude o i l or f u e l s ) . 4.21 •• Fuel Consumption .,v The normal burning of f u e l does not produce any residuals that could be hazardous as water p o l l u t a n t s , except possi-bly some o u t f a l l of nitrogen and sulphur oxids which are more serious as a i r pollutants. A c e r t a i n portion of the f u e l s , however, are discharged un-bumed to the a i r environment through evaporation and exhaust emissions of unburned hydrocarbons. These can reach the water environment through f a l l o u t i n rainwater. A study by B.C. research, summarized i n GVRD (1973)» estimates that the following amounts of hydrocarbons are discharged to the a i r i n the GVRD: (Figures f o r I969) - Losses i n O i l Refining 4 520 tons/year [13] - Gasoline marketing 15 890 - Transport .2-700 - Automobile emissions 86 120 Non automobile emissions 2 194 Total Hydrocarbon Emissions: 111 424 tons/year [.4J Figures i n brackets [-] r e f e r to fi g u r e 8 i t 53 These losses represent approximately 4.4 % of the t o t a l amount of fuels sold (2 5*0 000 tons). The amount of burned f u e l i s therefore about 2 400 000 tons [32]. These 2.4 m i l l i o n tons of f u e l require approximately 8.2 m i l l i o n tons of oxygen and produce a t o t a l of 10.5 m i l l i o n tons of gas-eous emissions (water and carbon dioxide). A ce r t a i n amount of the evaporated hydrocarbons c e r t a i n l y reach the water environment with rainwater. Any attempt to estimate the amount of hydrocarbons entering the water t h i s way i s very u n l i k e l y to produce accurate r e s u l t s . Further-more, i t seems u n l i k e l y that these hydrocarbons create any s i g n i f i c a n t p o l l u t i o n problem. An analysis of a great num-ber of samples throughout the German Federal Republic has shown that the hydrocarbons present i n rainwater originate to a large extent from natural sources, i . e . they are not petroleum hydrocarbons. I t was concluded by the Germans, that auto-oxidation and microbial degradation are r e l a t i v e l y rapid f o r evaporated hydrocarbons. Furthermore, even i f these hydrocarbons reach the water, they are r e a d i l y broken down by b a c t e r i a l attack as these hydrocarbons are (1) dissolved i n water and (2) composed of l i g h t f r a c t i o n s . Both factors favor microbial breakdown.^ (Personal com-munication of Dr. H. Hellmann, Federal I n s t i t u t e of Hydro-logy, Koblenz, Germany). 54 In l i g h t of these statements i t seems safe to say that the f a l l o u t from the atmosphere i s u n l i k e l y to be an important source f o r water p o l l u t i o n . 4.22 Lubricating and I n d u s t r i a l O i l s 4.221 Residuals Production Diagram .1 below shows the model used to determine: ( 1 ) the amount of waste o i l generated (2) the amount of o i l s l o s t by burning or chemical decomposition ( i . e . non-hydrocarbon wastes) (3 ) the recovered waste o i l s \ (4) the non recovered, but p o t e n t i a l l y recoverable waste o i l s and (5) the non-recoverable waste o i l s Total O i l Sales Waste O i l Recovered Waste O i l s 1 Consumed, non-KC losses I Non recovered Waste O i l recoverable 1 Non-recoverable Waste O i l s 55 Comments on Diagram 1 T o t a l O i l s o l d ; R e p r e s e n t s consumption i n the GVRD (see (7) i n a p p e n d i x 1) Consumed O i l : L u b r i c a n t s b u r n e d . d u r i n g t h e i r normal use by blowby and decomposed by o t h e r p r o c e s s e s . Recovered Waste O i l s : A l l o i l s p r e s e n t l y r e c o v e r e d by o r -g a n i z e d waste o i l p r o c e s s o r s o r r e c y c l e d by the o i l u s i n g i n d u s t r i e s t h e m s e l v e s . R e c o v e r a b l e Waste O i l : A l l o i l s p r e s e n t l y n ot r e c o v e r e d b u t p o t e n t i a l l y r e c o v e r a b l e ( e . g . do i t y o u r s e l f o i l change mar-k e t , many i n d u s t r i a l o i l s ) Non R e c o v e r a b l e Waste O i l s : . O i l s t h a t a r e l o s t i n a manner t h a t t h e y cannot be r e c o v e r e d a t a r e a s o n a b l e c o s t ( l i k e s m a l l l e a k s , s m a l l s p i l l s , s m a l l m a c h i n e r y e t c . . ) T a ble 8 L u b r i c a t i n g o i l s r e s i d u a l s p r o d u c t i o n as--% o f t o t a l s a l e s f .Consumed Waste Recove- Recove- Non-reco-: o i l . o i l r e d o i l r a b l e . 0 . v e r a b l e T r a n s p o r t a t i o n • -S e r v i c e S t a t i o n s 30 70 65 65 5 (8) D o - i t - y o u r s e l f m. 30 70 5 65 5 (9) Other t r a n s p o r t 70 30 13 27 3 (10) I n d u s t r y 10 90 2.3 55 35 (11) • * F i g u r e s i n () r e f e r t o a p p e n d i x 1 f o r e x p l a n a t i o n o f the a s s u m p t i o n s . TABLE 3 Waste O i l Production i n the GVRD tons per year (base year 1972) Sector Sales Waste O i l Consumed O i l Recovered O i l Non recovered recoverable Non recove-rable Automotive Service Stations 9'200 [26] 6'440 [33] 2'760 [30] ' 5'980 460 "bo i t yourself marke t 3'400 [25] 2'380 [34] 1'020 [29] 170 2'040 170 Other Transport ll'OOO [24] •3'300 [35] 7'700 [28] 1'430 1'540 330 Industries 8'000 [2] 7'200 [36] 800 &] 1'840 2»560 2 1800 Total .y, • 31'6.00 19'320 12'280 9'420 [3] 6*140 [38] 3'760 [39] Total i n 1 100 61.1 38.9 29.8 19.4 11.9 Figures i n brackets [J refer to figure 7 57 '4.222 Waste O i l Surveys As i t was recognized that l u b r i c a t i n g and i n d u s t r i a l o i l s play an important role i n water p o l l u t i o n , further atten-t i o n must be given to these materials. In order to back up the estimates, based on several studies, mentioned i n appendix 1, a questionnaire survey was carried out i n August 1974. Two types of questionnaires were used, one f o r auto-motive crankcase o i l and the other f o r i n d u s t r i a l o i l s . The f i r s t was sent out to a l l gas st a t i o n s , automobile garages, car dealers, bus and truck services i n the GVRD. The other was sent out to manufacturing industries of a se l e c t i o n of 55 sectors which are suspected of using o i l s i n t h e i r manu-facturing processes. In order to i d e n t i f y the i n d i v i d u a l firms, the B.C. Trade Directory ( I 9 7 I ) of the Department of I n d u s t r i a l Development, Trade and Commerce was used. Appendix 4 The two questionnaires are given i n appendix 4. A t o t a l of 731 questionnaires was sent out f o r the crank-case o i l survey; 208 or 28 .5 % of the questionnaires were returned which i s a -reasonably good response considering the type of questions involved. In the i n d u s t r i a l waste o i l survey, 652 questionnaires were sent out and 101 or 15.5 f° were returned. The lower return i n the i n d u s t r i a l -survey can at least p a r t l y be explained by the fact that questionnaires were sent out to firms which probably do not involve any o i l s i n t h e i r processes. 58 Appendix k shows the accumulated figures f o r both questionnai res, i . e . the o i l sales and the waste o i l production of the replying firms. The figures have been converted to tons/ year f o r purposes of comparison with other figures i n t h i s study (1 year = 12 x 1 month) a) Waste Crankcase..Oil Survey According to table 7 ( P. 5 ° ) i 23 600 tons o f . l u b r i c a t i n g oi-ls are sold annually to the- transportation sector i n the GVRD. The t o t a l of the questionnaires; sums up to 1578 tons or approximately 7 fo of the t o t a l . Despite the r e l a t i v e l y high return rate of the questionnaires of 28 fo, i t seems th that a number of large firms did not return t h e i r question-naire. In addition, the survey i s not t o t a l l y complete; i n the e x i s t i n g time constraints i t was not possible to i d e n t i -f y the following establishments and to send questionnaires to them: some bus and truck service operations (the 50 . • questionnaires required by B.C. Hydro have not been returned yet, they are not included i n the 731 . questionnaires sent out. - Private companies running and s e r v i c i n g t h e i r own truck and automobile f l e e t s , - Do-it-yourself-market, i . e . o i l s sold by e s t a b l i s h -ments other than gas-stations (super markets, auto accessory'stores, etc.) This market, has been e s t i -59 mated to account f o r 27 % of the t o t a l automotive ' l u b r i c a t i n g o i l sales (EPS 1 9 7 4 ) . ' Among the large sectors which did not reply to the ques-tionnaires are the ra i l r o a d s and the a i r l i n e s . Railroads use 6 5 7 0 tons of l u b r i c a t i n g o i l s throughout B.C. I f i t were assumed that 3° i° of t h i s amount was used i n the GVRD (about the share of the other transportation sectors) t h i s would amount to 1 9 7 0 tons. Yet, the ques-tionnaires returned by establishments i n d i c a t i n g to be ac-t i v e i n r a i l r o a d s e r v i c i n g sum up to only 10 tons per year The a i r p o r t i s l i k e l y to' use mostly synthetic l u b r i c a n t s , as these lubricants are used i n modern jet turbines. However, a quite large amount of smaller planes are ser- ' viced i n Vancouver, using petroleum based lubricants. . No.replies at a l l were obtained by a i r l i n e s or airplane service operators. b) I n d u s t r i a l Waste O i l Survey The i n d u s t r i a l waste o i l survey was more d i f f i c u l t to ana-lyze due to the wide v a r i e t y of applications of the o i l s used and the vari e t y of industries. As i n the crarikcase survey, the t o t a l s as reported i n appendix 4 represent less . o i l than the proportionate amount of returned ques-tionnaires. The 8 I 7 tons per year represent 1 0 . 2 fa of the 60 estimated figures according to table 7, whereas 15 % of the questionnaires were sent back. This suggests that e i t h e r not a l l o i l using industries received questionnaires, or that some large firms did not return the questionnaire. Despite these l i m i t a t i o n s , the questionnaire survey was i n several respects a. useful backup f o r the e x i s t i n g es-timates made i n other studies and used as ba.se i n t h i s study. Points (.8) and (11) of appendix 1 give more d e t a i l s about where i n t h i s study the questionnaire was. used f o r the nu-merous estimates. In most cases, the questionnaire con-firmed the former estimates w i t h i n a reasonable range. The estimates i n table 9 can therefore be regarded as r e l a -t i v e l y safe. 4.23 O i l S p i l l s and Losses The most d i f f i c u l t figure to estimate i s the amount of pe-troleum products s p i l l e d . Environment Canada keeps a record of o i l s p i l l s i n a computerized data bank. Three problems arise i n attempting to estimate the t o t a l amount l o s t to the environment: (1) In spite of the requirement to report a l l major o i l s p i l l s , there w i l l l i k e l y remain a number of unreported s p i l l s , .(2) f o r a large' number of reported s p i l l s , the sour-ce, cause and amount of s p i l l e d o i l i s unknown. 61 (3) The amount of s p i l l s vary greatly from year to year. Even i f a good estimate i s a v a i l a b l e f o r one year, another year can produce a considerably higher or lower figure. For these reasons, no attempt i s made to generate data f o r the Vancouver Area and the estimate of the EPA (1974a) has been adopted f o r t h i s study. EPA .assumes that 0 . 5 % of the t o t a l amount of l i q u i d s handled are l o s t or s p i l l e d i n t h e i r d i s t r i b u t i o n from the point of production to the point of consumption. This figure i n c l u d e s ' s p i l l s and losses*on land and losses from processing., .Appendix 1 (12) describes how the t o t a l amount of 14 900 tons of s p i l l e d m a t e r i a l " i n the GVRD i s calculated. Assuming the same rate of recovery as EPA indicates, 39 fo or 5 800 tons [54] are cleaned up and handled by waste o i l processors ( 13) . Of the remaining:. 61 f».or 9lQi0 tons ^55} • 20 fo or 1820 tons [ l l ] are s p i l l e d i n water and 80 % or 7280 tons [56] are s p i l l e d on land (14). 4 . 3 Disposal of Residuals This paragraph deals with the present s i t u a t i o n of the waste petroleum products i n the Vancouver Area. I t i s ba-sed on the questionnaire survey, as. w e l l as on the study by Environment Canada EPS (1974) on used l u b r i c a t i n g o i l s i n Canada. 62 4.31 Waste O i l Storage and C o l l e c t i o n According to the survey, nearly a l l of the waste o i l i s picked up but i t i s possible that a number of less respon-s i b l e gas s t a t i o n operators-idid not f i l l out the questionnai res at a l l or f a i l e d to f i l l i t out appropriately.-Through the questionnaires i t was possible to i d e n t i f y 10 d i f f e r e n t pickup services in'the Vancouver Area. The questionnaire indicates further that two of them c o l l e c t more than 87 of a l l the .waste o i l s . The service stations usually pay f o r the pickup service, with prices ranging from 1 to 7 cents per gallon. The d i f -ference i n charge i s rather due to the q u a l i t y and unifor-mity of the o i l rather than of the quantity. The largest operator, f o r example, c o l l e c t s o i l free of charge i f the service s t a t i o n guarantees a c e r t a i n standard f o r the pro-duct. The size of the storage f a c i l i t i e s of service sta- : tions vary greatly. Some service stations have simply a . 45 gallon drum; others.have 500 to 1000 gallon underground storage tanks. The railway companies have t h e i r own storage and c o l -l e c t i o n system. Canadian P a c i f i c has a c o l l e c t i o n system which allows i t to recover approximately 20 % of i t s con- -sumption i n the form of re-refined o i l . (EPS 1974). The o i l of the P a c i f i c region i s shipped to Edmonton, where i t i s re-refined. 63 Canadian National Railway has only recently begun to re--refine i t s locomotive crankcase o i l and up to t h i s time has disposed of i t i n "other ways". No information was av a i l a b l e , however', either on what "other ways", r e a l l y means, or on the s p e c i f i c s i t u a t i o n i n the Vancouver Area. -.4.32 Waste O i l Processing Industry As mentioned above, only two major firms c o l l e c t and process waste o i l s . One.of them operates a small r e - r e f i n i n g plant with a capacity of approximately 2000 gallons per day or roughly 2500 tons per year [23] .(Information from f i r m ) . This r e - r e f i n i n g f i r m i s the l a s t one of a number of re-re f i n e r s that existed several years ago. Adverse economic conditions forced most of them out of business and the l a s t e x i s t i n g operator.is l i k e l y to,close down i n the near future The f i r m i s too small and operates with too obsolete equip-ment to be able to produce a r e l i a b l e p r o f i t . Furthermore, the plant i s located i n an area of r e l a t i v e l y dense commer-c i a l . i n d u s t r i a l and r e s i d e n t i a l land use and has no adjacent land available f o r further expansion, modernization and increased storage ?space. The only s o l u t i o n i t has would be to b u i l d an e n t i r e l y new plant, which"-would require a-large . i n i t i a l investment that a small f i r m i s unable to provide, 64 The other large collector/processor i s a paving and road o i l i n g firm which has approximately 60 % of the market share.' This f i r m uses o i l f o r spraying unpaved roads as well as i n producing an inexpensive road topping from a mixture of used o i l , medium cured asphalt and coarse aggre-gate. Furthermore, a part of the o i l i s used as f u e l i n the asphalt plant. At present, e f f o r t s are being made to r a i s e funds f o r a new r e - r e f i n e r y i n the Vancouver Area by two i n -dependent organizations. No concrete r e s u l t s have been re-ported so f a r and i t w i l l probably take more time before the s i t u a t i o n of r e - r e f i n i n g i n the Vancouver Area impro-ves. I t i s l i k e l y , that economic conditions f o r r e - r e f i -ning w i l l improve as prices f o r petroleum products i n -crease. This, however, does not preclude the f a c t a sub-, s t a n t i a l amount of c a p i t a l i s required to b u i l d a new re-r e f i n i n g plant, • -4.33 Present End Uses . If current methods of c o l l e c t i o n and storage of waste o i l can be shown as inadequate and l a r g e l y unregulated, more serious r e s u l t s stem from most of the e x i s t i n g end uses of waste o i l . Most methods, besides being wasteful and i n e f f e c t i v e , pose.health and environmental hazards. The following paragraph examines the d i f f e r e n t categories of end uses and estimates the amounts of o i l s involved.. 65 • 4.331 Road O i l i n g For the waste o i l processor, road o i l i n g appears to be at present the most economically a t t r a c t i v e use, since muni-c i p a l i t i e s pay between 18 and 20 cents a gallon:for o i l spread on the road. However, t h i s method of disposal has disadvantages. A study by the EPA (1972a) on a p a r t i c u l a r road found that only 1 % of the o i l stays on the road, 70 to 75 f° leaves the road by dust transportation and runoff, 25 to 3° f° i s l o s t by v o l a t i l i z a t i o n . This study also shows that the vegetation i n the adjacent f i e l d s contained large amounts of metallic compounds that come from the waste o i l s . These statements, however, seem to contradict several t e s t r e s u l t s of the German Federal I n s t i t u t e of Hydrology. These researchers found that the o i l stays, f o r a r e l a t i v e l y long period i n the ground and has only l i m i t e d a b i l i t y to spread. At the same time, the contaminants contained i n the waste o i l s are l i k e l y to be washed out and reach the water environment. Also i t i s l i k e l y that i f tod much o i l i s spread i n one a p p l i c a t i o n , a r e l a t i v e l y high runoff rate must be expected. Appendix 2 shows the composition of a t y p i c a l automotive waste o i l . The use of waste o i l as a dust p a l l i a t i v e i s i n several respects an unsatisfactory method f o r the f o l l o -wing reasons: 66 (1) i t i s questionable whether the method as such i s w e l l suited f o r keeping dust down, however, no consensus exists' between d i f f e r e n t research groups. (2 ) Road O i l i n g represents a loss of a r e l a t i v e l y valuable non-renewable natural resource which could be recycled; and (3 ) At least a part of the o i l and i t s contaminants (heavy metals, polynuclear aromatics) are entering the a i r , land and water environment, thus causing a substantial p o l l u -t i o n hazard. Presently i n the GVRD, about 3 800 tons [42]. of o i l s are sprayed on unpaved highways. This i s about'-. 25 fo of the c o l -lected waste o i l s (15). I t i s assumed that 40 fo (16) of t h i s amount leaves the road by runoff, which result s i n 1520 tons [43] of o i l going into the water environment. 4.332 Fuel Use This section summarizes some important points of the EPS study (EPS 1974, pp 34 to 50). I f the excess heat can be used i n a b e n e f i c i a l way, burning the waste o i l s seem to be a natural, simple and economic disposal process. However, there are a-number of problems involved i n burning waste o i l s : (1) Burning waste o i l s re-presents a net loss to the o v e r a l l economy as the t o t a l cost of producing v i r g i n l u b r i c a t i n g o i l i s higher than the cost } 67 of r e - r e f i n i n g the same quantity of waste o i l even i f the waste o i l i s priced as f u e l , (see appendix 5 f o r d e t a i l s ) . (2) Due to the contaminants, possible deposits i n the b o i l e r tubes and f i r e box, wear on the burner and a i r emissions can occur with the use of normal f u e l burners. PACE (1973) suggests that the waste o i l . should therefore be blended with f u e l o i l and that the waste o i l content should not exceed 2 % of the t o t a l mixture. (3) The major problem r e s u l t s from the emissions to the a i r by burning the highly contaminated o i l s . A p a r t i c u l a r pro-blem i s the high content of lead as w e l l as polynuclear aro-matics,. Both elements are not destroyed i n the burning process and are emitted to the a i r . This problem, however, could become less severe i n the future as the lead con-tent i n motor gasoline, which i s the source of the l u b r i -cant contamination, can be expected to decrease. EPA (1972a projects that by 1982 nearly a l l vehicles would be able to use low lead or no-lead f u e l s . (4) I f waste o i l i s to be used as f u e l , pre-use t r e a t -ment of the o i l ( s e t t l i n g , centrifugation, solvent extrac-t i o n or s i m i l a r treatment) i s es s e n t i a l to prevent the emis-sion of toxic substances. The cost of t h i s treatment would make burning even less a t t r a c t i v e economically i n comparison with r e - r e f i n i n g . 68 In the Vancouver Area, approximately 7900 tons [4l] or 58 fo of waste o i l s are burned (Personal communication (17)). 4 . 333 Re-refining Re-refining i s undoubtedly the most a t t r a c t i v e means of s o l -ving the problem of used l u b r i c a t i n g o i l . Unfortunately, d i f f i c u l t i e s such as the varying composition of waste o i l s , present tax structures ..which do not favor're-refined o i l , problems with the disposal of the process residues and high gasoline content of the waste o i l , causing f i r e hazards, prevent r e - r e f i n i n g from being a simple and easy answer that i t would otherwise appear to be. In recent years, the i n t e r v a l s between changes of automobile crankcase o i l has increased , . the o i l capacity i n the en-gine decreased and the o i l pan temperatures have increased. These changes have only been possible with the a p p l i c a t i o n of more sophisticated additives. Unfortunately., the increa-sed effectiveness of the additives i n the o i l i s matched by the increased d i f f i c u l t y i n removing them in-the re-r e f i n i n g process. In addition to these d i f f i c u l t i e s , pre-sent storage methods emphasize the problem. Heavy;oils, l u b r i c a t i n g oils,,, l i g h t b o i l i n g hydrocarbons f o r cleaning-and degreasing are mixed and simply l a b e l l e d "waste o i l " ; these o i l s cannot be re-refined. 69 These reasons, along with the economic problems mentioned i n the paragraph above, have had the r e s u l t that only 16.% of the collected o i l or only 12 % of the recoverable o i l i s re-refined. Considering the t o t a l sales of l u b r i c a t i n g o i l s , only about 8 % are re-refined • (18). Table 10 End Uses of Waste O i l s (Summary of chapter 4.33) Use tons/year % of t o t a l Road O i l i n g 3 800 . [42] (15)* 25 . . . Burning 7 920 [4l[ (17) 52 Re-refining 2 500 [23] (18) 16.4 Process Wastes 1 000 [45+46] (19); 6.6 Total 15 220 [40] 100 Figures i n [ ] re f e r to figure. 8 ,, Figures i n () re f e r to appendix 1 4.34 A l l Petroleum Products Discharged to the Water Environment This paragraph summarizes the paragraphs 4.2 and 4.31 to 4.33, i n which the t o t a l amount of o i l s discharged to the environment (land and water) has been estimated. Further-more, an attempt i s made to estimate the amount ending up i n the water environment. ' ?o ' Table 11 Total discharges to land and water environment Method of Disposal tons/ye ar S p i l l s and losses 9 100 55 Road O i l i n g 3 800 42 Automotive losses 46o * Do-it-yourself market 2 210 * Other Transportation losses 1 .870 * I n d u s t r i a l losses i - • 5 360 * Process-Residuals 1 000 45 + 46 Total,;. . 23 800 * see figure 6 , sum of "non recovered" + "non-recoverable" Discharge Rates to Water Environment No det a i l e d data are a v a i l a b l e i n the l i t e r a t u r e on the amount of the discharges entering the water.environment. The f i r s t unknown i s the amount discharged d i s r c t l y to the water environment and the second i s the amount of the o i l discharged on land which reaches the water through runoff. In table 12, t h i s amount i s estimated, the assumptions on the percentages are discussed i n appendix 1 71 Table 12 Method of Disposal • Total; to fo to Total to Land+Water Water Water S p i l l s i n Water ... 1 8 2 0 . [ i i ] 100 1 8 2 0 [ill S p i l l s on Land 7 2 8 0 [56] 30 ( 2 0 ) 2 180 [57] . Road O i l i n g 3 8 0 0 1^ 2] 40 (16) 1 5 2 0 L4 3 ] Automotive Losses 4 6 0 ; 50 ( 2 1 ) 230 Do-it-yourself market . 2 2 1 0 " 30 ( 2 2 ) 6 6 0 Other Transportation 1 8 7 0 5°1 940 I n d u s t r i a l Losses ' 5 -36o . 5 0 - ( 2 3 ) 2 6 8 0 Process Residuals . 1 0 0 0 [45+46] 5 0 . • • 5 0 0 [45] Total 23 8 0 0 , . . . \"; 39.4 10 5 3 0 ' Figures i n t . ] see figure 8 Figures i n () see appendix 1 An estimated t o t a l of approximately 10 000 tons of waste petro-leum products i s , therefore, annually discharged to the waters of the Vancouver Area. These, pollutants enter the natural waters either through sanitary sewers, storm sewers or they enter the natural waters (Fraser River and Burrard'-Inlet) d i r e c t l y through natural runoff. Diagram 2 (p.72) shows a quantitative estimate.of the petroleum product i n f l u x to the water environment. According to these assumptions, a t o t a l of 8 8 6 0 tons [ 8 J of petroleum hydrocarbons enter the waters of the Vancouver Area. Approximately 60 fo. of t h i s amount, can be expected to enter the • Fraser River (approxi-mately 5 300 tons) and 40 f> the Burrard Inlet (approximately ,3 500 tons) see .appendix . 1 , ( 2 7 ) . Diagram 2 Petroleum Product Influx to the Water Environment. " : (Tons / year) _ S p i l l s on Water 1*820 [ l j S p i l l s on Land - 2' 180 [5?J Waste O i l s 6'530 [5l3 1530 (30) Runoff, Storm Sewers 4*180 [63] (31) 3880 Sanitary Sewers 4'530 [59] Treatment Plants 2*790 [65] To Natural Water Environment 8860 L66I Degraded ; 1670 [12} Figures i n ( ) r e f e r to appendix 1. 4 , 4 Comparison of Total Discharges and Observed O i l : P o l l u t i o n i n Greater Vancouver 4 . 4 1 Sewers and Plant Effluents ' , In July 1974 water samples were taken by Westwater i n Vancouver Sewers at several locations. Measured concentrations of hydro-carbons range from 15 to 60 mg/l with a-mean value of 27 mg/l. I f the 3 ^80 tons [59] of. o i l would be continuously discharged through the sanitary sewers, one would expect the following 73 concentration i n the sewer: Total annual flow i n Vancouver sanitary sewers:. 500 000 mVday * or 1.82.x 1 0 8 m^/year (Dorcey 1974b) 3 480 ; to9 mg = 1 9 > 1 mR/l (or 7lf» of 27 mg/l). 1.82 . 1 0 - 1 1 ' These estimates suggest therefore that roughly 70 fo of the hydro-carbons found i n sanitary sewers are of petroleum o r i g i n , the other 30 fo would be made up of detergents, PCB's, pe s t i c i d e s , various petrochemicals and natural hydrocarbons and edible o i l s and f a t s . The-; f r a c t i o n of 70 fo of petroleum hydrocarbons appears to be r e l a t i v e l y high considering the research of the German Federal I n s t i t u t e of Hydrology. A large number of water samples of c i t y sewers, rainwater, road runoff and water of the Rhine River i n Germany have shown r e l a t i v e l y low percentages of petroleum hydro-carbons compared with the t o t a l content of hydrocarbons ( H e l l -mann 1974a,b). The explanation of t h i s phenomenon i s given by Hellmann (1974b). Translated from the German the quote reads: "The major part of the measurable hydrocarbons are not of petroleum o r i g i n , but are biogenous products which are, and have always been formed i n large quantities i n the biosphere through processes which are s t i l l p a r t l y unknown. Our petroleum reserves would not have been formed without these processes i n e a r l i e r times". For the Germans, these r e s u l t s were s u r p r i s i n g , they r e a l i z e that there i s a large gap between the t o t a l mass of l o s t petro-leum products and the small mass of petroleum products found i n *The 500 000 m^/day i s a dry season flow. In wet periods,- storm water runoff has to be added to t h i s f i g u r e , thus reducing- the concentration. 74 sewers, runoff and r i v e r s . Up to the present time the , Germans have only hypothetical explanations f o r t h i s phe-nomenon, the most l i k e l y i s the p o s s i b i l i t y that o i l s p i l l e d or spread on land i s kept back i n the underground and never reaches the water. I f the assumption of a. continuous discharge seems reasonable f o r sanitary sewers, t h i s i s c e r t a i n l y not the case f o r storm-sewers. I t must be expected that o i l s can accumulate i n sewers and o i l separators during dry periods and be flushed out i n rainy periods, thus creating large var i a t i o n s i n the waste load. Furthermore, as Diagram 2 suggests, most of the discharges i n strom sewers originate from s p i l l s , therefore increasing:the fl u c t u a t i o n s of the waste load even more. With the presently a v a i l a b l e information i t i s impossible to a r r i v e at any detailed estimates of waste loads i n storm sev/ers and runoff. 4 . 4 2 Treatment Plants' According to 'Dorcey (1974b) a primary treatment plant can o f f e r an abatement e f f i c i e n c y f o r o i l s of approximately 50 to 60 f>, whereas a b i o l o g i c a l secondary treatment plant could go as high as 90 f>. In Diagram .2' an average of 60 fo 75 was used, considering the fa c t that a l l Vancouver sewage treatment plants have primary treatment only. According to SWPCB (1956) and personal communications with o f f i c i a l s of the Greater Vancouver Sewerage and Drainage D i s t r i c t , the e x i s t i n g l e v e l of o i l p o l l u t i o n i n Vancouver sewers are fa r below a l e v e l at which the o i l . could cause major prob-lems i n sev/ers and treatment plants. 4 . 4 3 Fraser River-• An estimated 53°° tons per year i s discharged to the Fraser River from the Vancouver Metropolitan Area. As the short c a l c u l a t i o n i n paragraph 2.25 shows, t h i s t o t a l amount would be no serious problem i f the o i l were discharged continu-ously. However, as i t was stated i n paragraph 4.41, t h i s i s not the case at l e a s t f o r storm sev/ers and runoff. O i l w i l l therefore reach the r i v e r i n lumps of various sizes. These lumps eith e r occur d i r e c t l y as a r e s u l t of an o i l i n , s p i l l , or/the i n i t i a l phase of a storm a f t e r a dry period,. Again, i t i s impossible, to. compare the t o t a l load with the concentrations i n the r i v e r . The t o t a l flow of the r i v e r i s of a size that a very elaborate sample c o l l e c t i n g scheme would have- to be used to get an accurate picture of the t o t a l waste load and the average concentration. A further d i f f i c u l t y i s that o i l s are not .dispersed .uniformly 76 i n water, i t . f l o a t s on the surface and adsorbs to s i l t and i s therefore d i f f i c u l t to measure. The available information hov/ever, suggests that concentrations of petroleum hydrocarbons are no major problem i n the Fraser River to date and probably w i l l not be i n the near future. This however, i s not true f o r o i l s p i l l s , which are a problem' no matter where they occur and they have to be prevented wh wherever possible. 4 . 5 S e n s i t i v i t y Analysis Due to the fact that a considerable number of estimates had to be made which lack s u f f i c i e n t backup,, i t is/appropriate 1 to indicate a range of values i n the form of,a maximum-mini-mum hypothesis rather than i n d i c a t i n g only average values. Following the materials flow through the system, several estimates follow one another, each of them with a c e r t a i n error. In t h i s process the figures containing t h i s error are m u l t i p l i e d with one another. I f i t i s assumed that-the maximum-minimum assumptions represent the standard error of the mean value.of the estimate'according to s t a t i s t i c a l theory, the product of two; standard.errors i s calculated -as follows.: 77 The standard error of the sum.of two values as follows: Where: Xj_ = Mean value of estimate 1 X2 = Mean-value of estimate 2 G*xi = Standard error of C>X2 = Standard error of X2 G*xi • X2= : Standard error of product X^ -Gxi + X2= Standard error of sum X^ + X 2 The calculations of the maximum and minimum values as repre-sented i n figure 9 are based on these formulae. I t i s , how-ever, not possible to indicate a p r o b a b i l i t y at which the true value can be expected to l i e between the two indicated f i g u r e s ; the objective of the c a l c u l a t i o n i s rather to show the s e n s i t i v i t y of the t o t a l discharge i n r e l a t i o n to the various assumptions,-Table 1 3 Range of values used f o r the f i n a l materials balance Estimate Runoff S p i l l s i n Water 100 % n S p i l l s on Land 30 ± 40 + 11 Road O i l i n g 11 Automotive Losses 50 t II.- •• Do i t yourself market. 30 ± 11 Other Transportation 50,+ •1 I n d u s t r i a l O i l s 50 + 50 + i t Process Residuals S p i l l s on land / t o t a l s p i l l s 80 Jt S p i l l s on Water/total s p i l l s 20 5800 Recovered S p i l l s (20) (16) (21) (22) (23) (14) _ 10 fo (14) 5800 + 2000 tons (13) 78 As a r e s u l t of these c a l c u l a t i o n s , the amount of oily-wastes ending up i n the water environment i s 886.0'* I900 tons, which corresponds to-an error of approximately t 20 %. The maximum value amounts therefore to 10 750 tons, the mini-mum value to 6970 tons. The discharge to the Fraser River, using the same method as i n the previous paragraph (p. 7.4). i s calculated to 5300 + 1140 tons, a maximum of 6440 and a minimum of 4160 -tons. Calculating the concentrations i n the sewers i n the Van-couver sewerage system, according to paragraph 4.41, these would be the following: - maximum 23.9 mg/l or 19.1 * 4.8 mg/l - minimum 14. 3 mg/l The measured "concentrations range between 15 and 65 mg/l, therefore a f r a c t i o n of 0 to 5° mg/l are hydrocarbons of other than petroleum o r i g i n . These figures seem to be i n a reasonable range, however, some further monitoring of .sewer water through, dry and wet periods would be desirable i n order<to back up these c a l -culations based on.many "guesstimates". > Despite these uncertainties, however, i t can be saf e l y 79 said that the uncertainties i n i n t e r p r e t i n g the b i o l o g i c a l and physiological effects of o i l p o l l u t i o n are larger than the uncertainties associated with the r e s u l t s of the materials balance. 4 . 6 Overall Materials Balance Fig. 8 + 9 See figures 3 and 9 Figure 8 shows the t o t a l flow of petroleum products within the Vancouver Area. The most important figures can be summarized as follows': The t o t a l flow of petroleum products i n the Greater Vancouver Area amounts to 4 670 900 tons per year (base year 1972). Except f o r l u b r i c a t i n g o i l s , a l l products are manufactured i n the four l o c a l re-f i n e r i e s . 2 102-000 tons of petroleum products are exported out of the region, mainly to other parts of the Pro-vince of B.C., leaving 2 568 000 tons of"products a c t u a l l y consumed i n the Vancouver Area. Approximately 1.1 % of the t o t a l flow are l u b r i c a t i n g o i l s ; the remaining 98.9 % l i q u i d f u e l s . (Asphalts and petrochemical feedstocks are not included i n these f i g u r e s ) . - Of the l i q u i d f u e l s , rotighly 4 % or 111 000 tons [4] evaporate to the atmosphere, approximately 0.5 f° or 14 900 tons [I7J are l o s t as s p i l l s and other ope-r a t i o n a l losses before consumption. 80 2 4-33 700 tons of products or 94.7 % of the t o t a l are burned Approximately'- 62 % of a l l wastes discharged to land and water environment are used l u b r i c a t i n g o i l s and i n d u s t r i a l process o i l s , the other 38 •?<> are s p i l l e d l i q u i d s (fuels or crude o i l s ) . Of a t o t a l of 23 800 tons of o i l s discharged to the environment 92.4 fo or 21 980 tons are land based, of. those 40 fo or 87IO tons end up i n the water environment through runoff, 7 f° or I670 tons are degraded i n treatment plants. A further unknown element that would have to be i n v e s t i -gated i s the f a l l o u t of hydrocarbons from the evaporative losses. Even though these losses are quite substantial i n t h e i r amount, t h i s source seems to be n e g l i g i b l e , as-explained i n paragraph 4.21, p 53. 81 C H A P T E R F I V E CONCLUSIONS The conclusions of t h i s study are divided into three parts •• according to the three objectives mentioned i n the beginning. Af t e r summarizing the effects of petroleum products i n the environment the major findings of the case study of applying the materials balance to the Greater Vancouver Re-gional D i s t r i c t are summarized and the materials balance as a'technique i s assessed. 5.1 Petroleum Products i n the Environment • ' . Despite a seemingly abundant l i t e r a t u r e on environmental ef-fects of petroleum products, there s t i l l remains conside-rable uncertainty i n i n t e r p r e t i n g the r e s u l t s of many ex-periments and studies on t h i s matter. The major d i f f i c u l t y i n i n t e r p r e t i n g the fragmentary evidence i n the l i t e r a -ture stems from the f a c t that environmental effects w i l l vary tremendously with d i f f e r e n t petroleum products, d i f f e r e n t organisms and d i f f e r e n t environmental conditions. Neverthe-l e s s , some general•conclusions can be drawn about the ef f e c t s 82 of petroleum products i n the environment and the nature of the uncertainties about these. The t o x i c i t y of the petroleum products i s r e l a t i v e l y low compared with other toxic substances, however, t h i s low t o x i c i t y can be more than o f f s e t by huge quantities of material released to the environment. Crude o i l s are com-posed of a v a r i e t y of compounds, ranging from l i g h t hydrocar-bon' gases and gasolines to heavy asphalts. Each crude o i l has a d i f f e r e n t composition and therefore d i f f e r e n t e f f e c t s i f they are l o s t to the natural environment. In general, l i g h t f r a c t i o n s and unsaturated hydrocarbons as found i n re-fined products are more toxic to most organisms than heavier fractions*and saturated hydrocarbons. Short term and long term t o x i c i t y have to be distinguished. The former being an e f f e c t of the l i g h t hydrocarbons, the l a t t e r of the heavier f r a c t i o n s . Furthermore there exists a positive corre-l a t i o n between'toxicity and the content of c e r t a i n elements, the ..most important perhaps being sulphur. The t o x i c i t y to organisms manifests i t s e l f i n various ways. Some smaller or-ganisms are affected through coating and asphixiation, f i s h get coated g i l l s and die through a s p h i x i a t i o n or death i s caused by.an unbalanced blood-ion concentration. Birds die through exposure when t h e i r feathers get coated with o i l , which' causes the loss of' the feathers' water repellent and e heat i n s u l a t i n g c a p a b i l i t y . Variations' i n environmental 83 conditions such as temperature and s i l t content of water w i l l a l t e r these t o x i c i t y e f f e c t s . Ultimately most hydro-carbons disappear through auto-oxidation and microbial brekdown i n the environment. However, t h i s breakdov/n can be very slow, e s p e c i a l l y i n a r c t i c areas with low tempera-tures. Furthermore, a v a i l a b i l i t y of oxygen-and nutrients i s a cru-c i a l factor . v for the breakdown of o i l s , breakdown p r a c t i c a l l y stops i n anaerobic conditions. An accumulation of o i l i n water therefore only occurs where the discharge exceeds the breakdown capacity of the natural ecosystem. On a world-wide scale t h i s i s seemingly the case with the asphalt f r a c t i o n of the crude o i l . These molecules have a very long breakdov/n time and accumulate i n c e r t a i n areas of the world's oceans. Any i n v e s t i g a t i o n of effects of o i l p o l l u t i o n i s incomplete without considering the i n d i r e c t e f f e c t s . Refinery wastes and petroleum product additives f a l l into t h i s category. The r e f i n e r y wastes contain predominantly phenols, and s u l -phides and have a high BOD, whereas waste o i l s ( i n d u s t r i a l and automotive lubricants) contain high concentrations of heavy metals due to additives to the o i l and to the fuels.-The presence .of detergents i s a further important f a c t o r a f f e c t i n g t o x i c i t y i n the water environment. A higher 84 t o x i c i t y i s caused by the e m u l s i f i c a t i o n of the o i l and t h i s process i s f a c i l i t a t e d by turbulence. I t i s concei-vable that these contaminants can be more dangerous than the o i l i t s e l f , however, further research has to provide more evidence on the t o x i c i t y of these wastes. 5.2 O i l y Wastes i n the Vancouver Area As-figure 9 shows, a /total of 18 000 to 26 000 tons of o i l y wastes are discharged annually to the environment i n the Greater Vancouver Regional D i s t r i c t . Of t h i s amount 11 000 to 15 000 tons stay i n the land environment and 7000 to 11 000 tons are discharged to the water environment. Of t h i s l a t t e r f i g u r e , today about' 60 f> i s discharged to the Fraser River. This percentage' w i l l increase once the Annacis Island treament plant and i t s related sewer system comes into operation. It i s quite d i f f i c u l t to determine the e f f e c t s t h i s o i l has on the Fraser River, the r e c e i v i n g waters of Georgia S t r a i t and the Burrard Inlet, If a continuous discharge of these wastes were assumed as^discussed i n paragraph 4.4.1 and the o i l would be dispersed i n the r i v e r , a concentra-ti o n of 0.0.1/to 0.5 mg/lof o i l would have to be expected 85 i n the Fraser River. However, due to discontinuous d i s -charges, t h i s concentration w i l l vary and probably substan-t i a l l y . These concentrations are. f a r below what have been suggested as dangerous l e v e l s for. humans or water organisms on a short term t o x i c i t y basis. However, major uncertainties remain i n explaining the long term e f f e c t s of o i l p o l l u t i o n from the Vancouver Area on the marine and-estuarine environment. Despite the seemingly low concentrations of o i l s detected i n the waters of the Vancouver Area i n a number of areas of the Georgia S t r a i t the harvesting of seafood had to be r e s t r i c t e d due t c hydrocarbon p o l l u t i o n . To what extent t h i s was due to marine.oil s p i l l s , and to what extent to land based o i l p o l -l u t i o n cannot be e a s i l y answered. Further unanswered questions remain with respect to the heavy metals associated with waste o i l s . I t would require a study by i t s e l f to determine to what extent the heavy me-t a l s found i n the watersheds of the Vancouver Area are due to waste o i l discharges. Apart from the above mentioned three possible negative e f f e c t s (short term e f f e c t s of o i l s p . i l l s , long term ef f e c t s and heavy metal pollution) there are economic reasons f o r a more c a r e f u l and e f f e c t i v e handling of petroleum products and t h e i r residuals. These reasons are summarized i n the following paragraph. 86 5 . 3 Waste O i l Generation and Processing The o i l s p o t e n t i a l l y dangerous as pollutants originate from three major sources: s p i l l e d o i l s , waste l u b r i c a t i n g and i n d u s t r i a l o i l s and waste o i l processing residues. These three categories are summed up i n table 11 (p. 72). O i l s p i l l s contribute 38 %, waste l u b r i c a t i n g and i n d u s t r i a l o i l 42 % and process residues 20 fo to the t o t a l o i l y waste d i s -charges to the environment (23 800 tons).. In the; f o l l o -wing i s summed up how much,of these discharges are poten-t i a l l y recoverable, thus i n d i c a t i n g the po t e n t i a l e f f e c t s of any p a r t i c u l a r p o l i c y mechanisms aimed at the control of one of these categories. O i l S p i l l s : Major uncertainties about sources and quan-t i t i e s of s p i l l e d o i l makes i t d i f f i c u l t to indicate- ways and means of c o n t r o l l i n g these s p i l l s and how much of them are avoidable and recoverable. The data bank of the emer-gency service of Environment Canada can serve as basis f o r fu r t h e r investigations. Looking at the t o t a l of s p i l l e d o i l i t can be expected that a p o l i c y of preventing or reducing s p i l l s has a large p o t e n t i a l of reducing o v e r a l l o i l ' l p o l l u -t i o n . Waste Lubricating and I n d u s t r i a l O i l s : It has been .e s t i -mated/that '62 fo of these wastes are recoverable (see f i g . 7 ) . A t o t a l recovery of a l l p o t e n t i a l l y recoverable o i l s ' would 87 therefore reduce the t o t a l o i l discharge to the environ-ment by 26 f0. In order to achieve t h i s recovery, a closer i n v e s t i g a t i o n of the three contributing sectors, the-; do-it-yourself mar-ket, other transportation and the i n d u s t r i a l sector would be needed. Each of those has d i f f e r e n t c h a r a c t e r i s t i c s and involves d i f f e r e n t materials. Process Residuals: Road o i l i n g and o i l y sludges from re-r e f i n i n g of waste o i l s belong to t h i s category. These d i s -charges are deliberate and can therefore be completely pre-vented, thus reducing the t o t a l i n f l u x of o i l to the environ-ment by 20 %. The End Uses of the collected o i l s i n the Vancouver Area are mainly use of waste o i l - a s f u e l , road o i l i n g and re-re-f i n i n g , i n th i s order of importance. Each of these and possible other end uses would have to be evaluated regar-ding t h e i r costs and benefits such as c o l l e c t i o n , storage., d i s t r i b u t i o n and processing costs, environmental impacts and opportunity costs i n considering the al t e r n a t i v e uses of the waste o i l . Appendix 5 shows a comparison of costs, of f u e l use versus ^  r e - r e f i n i n g , however, environmental e f f e c t s , differences i n c o l l e c t i o n and storage costs are not included, 88 'According to t h i s c a l c u l a t i o n , r e - r e f i n i n g i s economically . preferrable and possible costs which are not included i n the comparison are u n l i k e l y to change t h i s . Considering that r e - r e f i n e r s seem to be disappearing i n the Vancouver Area, increased e f f o r t s seem to be necessary to revive t h i s dying economic sector. 5 . 4 Assessment of the Materials Balance Approach The materials balance approach, as developed i n t h i s study and applied i n a case study of the Greater Vancouver Regio-nal D i s t r i c t has proven to be a very useful method f o r iden-t i f y i n g sources and discharges and the opportunities f o r c o n t r o l l i n g these discharges. The strengths of the technique can be summarized as follows: What enters a system must leave i t somewhere. An over-a l l control c a l c u l a t i o n i s therefore possible which w i l l indicate whether any s p e c i f i c sources have been omitted. The complete balance permits the i d e n t i f i c a t i o n of the important waste streams and the magnitude of the problem at any point inside the system. 89 Once the general structure of the materials balance i s established, i t can serve a wide v a r i e t y of purposes. Each of them, of course, may require d i f f e r e n t degrees of d e t a i l . Subsystems can be i s o l a t e d or combined according to p a r t i c u l a r needs, s t i l l maintaining an overview of the system as a whole. The balance, as developed here f o r petroleum products, can be understood as a subsystem of a larger system. The materials balance f o r petroleum products i n the GVRD i s a subsystem of the balance f o r the Lower Mainland or the Province of B.C. and i s also a subsystem of the materials balance f o r hazardous wastes i n the GVRD. The materials balance can be used f o r other classes of materials. The e f f o r t involved i n carrying out a materials balance f o r other m a t e r i a l s i s , however, d i f f i c u l t to judge. More complex networks of sources and pathways and a greater lack of s t a t i s t i c a l data might make the materials balance more d i f f i c u l t . However, t h i s i s p r e c i s e l y the reason f o r u t i l i z i n g the materials balance,, as i n those cases, where information i s t h i s , i t i s imperative to organize and analy-ze t h i s data as e f f e c t i v e l y as possible. The materials balance i s p a r t i c u l a r l y useful when major uncertainties remain due to these unavoidable guesses, 9 o b e c a u s e f i r s t l y the e s t i m a t e o r guess i s made w i t h i n a f r a m e w o r k w h i c h u s u a l l y i n d i c a t e s a c e r t a i n order o f mag-n i t u d e of the' f i g u r e t o be e s t i m a t e d of g u e s s e d a n d s e c o n d l y t h e f l o w c h a r t of t h e m a t e r i a l s b a l a n c e c a n be u s e d a s a b a s i s f o r a c o m p u t e r s i m u l a t i o n t o t e s t t h e e f f e c t o f c h a n g i n g a s s u m p t i o n s made a b o u t p r o d u c t i o n a n d c o n s u m p t i o n c o e f f i c i e n t s ( i . e . a s e n s i t i v i t y a n a l y s i s ) . Such a n a n a l y -s i s i s u s e f u l t o d e t e r m i n e p r i o r i t i e s i r . a l l o c a t i n g e f f o r t to f u r t h e r r e s e a r c h a n d d a t a c o l l e c t i o n . A c o m p u t e r i z e d m a t e r i a l s b a l a n c e c a n be p a r t i c u l a r l y w e l l s u i t e d a s a m o d e l f o r d e v e l o p i n g p o l i c i e s f o r c o n t -r o l l i n g w a s t e d i s p o s a l a n d m a t e r i a l s r e c o v e r y . Such a m o d e l can f a c i l i t a t e t h e d e v e l o p m e n t o f a n i n f o r m a t i o n s y s t e m v / h i c h w i l l i m p r o v e t h e e f f i c i e n c y o f f u r t h e r r e s e a r c h , a v o i d gaps i n i n f o r m a t i o n a n d o v e r l a p p i n g r e s e a r c h due t o a l a c k • o f c o m m u n i c a t i o n among r e s e a r c h e r s . The p r o b l e m s e n c o u n t e r e d i n t h i s s t u d y c a n be s u m m a r i z e d as f o l l o w s : The major p r o b l e m s e n c o u n t e r e d i n c a r r y i n g o u t the ma-t e r i a l s b a l a n c e - a r e r e l a t e d to d a t a - c o l l e c t i o n . I t w o u l d f a c i l i t a t e t h e e s t a b l i s h m e n t o f a m a t e r i a l s b a l a n c e s u b s t a n * t i a l l y , i f (1) o f f i c i a l C a n a d i a n s t a t i s t i c s w e r e d i s a g g r e -g a t e d t o r e g i o n a l f i g u r e s a s . r e s i d u a l s a n d w a t e r q u a l i t y Ql management problems are l a r g e l y regional i n character-and the balance therefore has to be at a regional l e v e l and (2) not o n l y sales and consumption figures were accumulated' but also a better accounting f o r quantities of waste pro-ducts and t h e i r end-uses were carr i e d through. Another problem i s the evaluation of materials flows which have l i t t l e s ignificance f o r the objective of the study and yet have, to be quantified f o r the sake of completeness of the materials balance. I f data i s hard to generate i n these cases, reasonable "guesstimates" are•appropriate, however, the s e n s i t i v i t y of a possible error has to be made clear . In t h i s study, t h i s problem has been encountered i n evaluating the regional figures f o r the l i q u i d f u e l s . In the p a r t i c u l a r problem of petroleum products, a very-large flow of products (fuels) with a r e l a t i v e l y small po-t e n t i a l f o r water p o l l u t i o n as w e l l as a r e l a t i v e l y small flow of products (lubricants and i n d u s t r i a l o i l s ) with a re-l a t i v e l y high p o t e n t i a l f o r water p o l l u t i o n are both elements of the same balance. This l i m i t s therefore the p o t e n t i a l of .the o v e r a l l balance i n determining amounts of waste gene-rated. This phenomenon can be called.the problem of the difference of two large figures of the same order of mag-, nitude not accurately known .(.Explanation see (28)). 92 A problem of a rather general nature i s that private enterprises ( i n t h i s case o i l companies) are p r i n c i p a l l y reluctant to release trade figures. Therefore the simplest route of getting data i s often. made impossible. Balancing the advantages against the disadvantages, t h i s case study has shown that the materials balance approach can serve as a valuable t o o l i n i n v e s t i g a t i n g residuals disposal problems. Despite the s c a r c i t y of hard data, valuable insights into the network of sources and pathways of o i l y wastes were possible which would not have been pos-s i b l e by using any method that does not provide information about the system as a whole. The materials balance approach made i t possible to i d e n t i f y the most important waste, flows. These include o i l s p i l l s , , runoff rate from landbased o i l s p i l l s and. voluntary d i s -charges and the r a t i o of waste flow to sewers versus d i r e c t runoff to natural waterways. The most s i g n i f i c a n t r e s u l t , however, of the balance i s the f a c t that l u b r i c a t i n g o i l s play at le a s t as important a role i n the oily, discharges to the water environment as the more spectacular s p i l l s . F i n a l l y , the analysis has lead to the insi g h t that federal and p r o v i n c i a l regulations i n Canada, governing storage, c o l l e c t i o n and disposal of'" o i l y v/astes are very ineompre-hensive and that there i s an urgent need f o r developing 93 p o l i c y m e c h a n i s m s f o r c o n t r o l l i n g a w a s t e f u l a n d i n e f f i -c i e n t d i s p o s a l o f o i l y w a s t e s , 94 R E F E R E N C E S B a t t e l l e I n s t i t u t e 1 9 6 7 . O i l S p i l l a g e Study. Report AD 666 289 1967, U.S. Dept o f Commerce B a t t e l l e I n s t i t u t e 1971. "Untersuchung tiber Umfang, • Ursache, H e r k u n f t und V e r b l e i b m i n e r a l o e l h a l t i g e r A b f a e l l e i n d e r B u n d e s r e p u b l i k DeutschlandV. ( I n v e s t i g a t i o n o f the c a u s e s , e x t e n t , o r i g i n and u l t i m a t e f a t e o f waste m i n e r a l o i l s i n the German F e d e r a l R e p u b l i c . ) Bund-estagsdrucksache Nr. Vl/3312 B e n e d i c t , A.H., H a l l K . J , Koch F.A. 1973. A p r e l i m i n a r y Water Q u a l i t y . S u r v e y o f th e Lower F r a s e r R i v e r System. Westwater, t e c h n i c a l r e n o r t No. 2 , A p r i l 1973 Blumer M. ' . I969. O i l P o l l u t i o n o f the Sea .  I n : H o u l t , I 9 6 9 . •-Briscoe-H. T. 1959. A S h o r t Course i n O r g a n i c C h e m i s t r y Houghton M i f f l i n Co.mp. B o s t o n 1959. •. Canada, Department o f the Environment 1972. • G u i d e l i n e s f o r Water Q u a l i t y O b j e c t i v e s and S t a n d a r d s P r e l i m i n a r y r e p o r t , I n l a n d Waters Branch. Canada, E n v i r o n m e n t a l P r o t e c t i o n S e r v i c e 1974. P r e l i m i n a r y Review o f Used L u b r i c a t i n g O i l s i n Canada. Report EPS 3-WP-74-4 ;• Canevar 1 , G. P. 196'9. TheRole o f C h e m i c a l D i s p e r s a n t s i n O i l - C l e a n u p . I n : H o u l t I 9 6 9 C a r t h y . J . D , A r t h u r D.R. I968/ The B i o l o g i c a l E f f e c t s o f O i l P o l l u t i o n on L i t t o r a l Communities P r o c e e d , o f Symp. a t O r i e l t o n F i e l d C e n t r e , Pembroke., Wales Feb. I968. . Cowe11 E.3..1971. The. E c o l o g i c a l E f f e c t s . o f O i l P o l l u t i o n on L i t t o r a l Communities. I n s t i t u t e o f P e t r o l e u m , London 1971. v Crapp G.B. I 9 7 I . The E c o l o g i c a l E f f e c t s o f S t r a n d e d O i l I n : Cov/e.l.l I 9 7 I . 95 Dean R.A. I968; The Chemistry of Crude O i l i n Relation to Their Spillage on the Sea. In: Carthy I968. Dorcey A.H.J. H ^ l l K.J, 1Q?4 a. Water Quality Management i n a Metropolitan Area. Paper f o r AWWA, FACE Conference, A p r i l 1974. Dorcey, A-. H.J. I9?4b. Water Quality Management i n an Ur-ban I n d u s t r i a l Region: The Fraser Estuary and Greater Vancouver. Paper presented at the Conference on Economic In-centives f o r A i r and Water P o l l u t i o n Control, V i c t o r i a , June 1974. Floodgate P.P. 1972. Biodegradation of Hydrocarbons . i n the Sea. ' In: Mi t c h e l l R. 1972 GVRD 1973. Environmental Quality i n Greater Vancouver. Pamphlet, .August 1 9 7 3 , 39 p. "Hall K.J. Koch,F.A. Yesaki I. I 9 7 4 . Further Investigations into Water Quality i n the Lower Fraser River System. Westwater, tech n i c a l report A p r i l 1974. .Hellmann H. 1974a, Kohlenwasserstoffe i n Quellgewassern -Oelverschmutzung oder Naturstoffe? (Hydrocarbons i n Springwater - O i l P o l l u t i o n or ^  Natural Products '?) • • i n : Tenside Determents, 11, Heft 4 1974. •Hellmann H,1974b. Nachweis und<derzeitiger Umfang von Mineraloelverschmutzungen i n unseren. Oberflae-chengewaessern, (Detection and Present Extent of Mineral.. O i l P o l l u t i o n i n our Surface Waters) • .In: Wasserv'irtschaft 64, Heft 7/8, I974 Hepple P. 1971. V/ater P o l l u t i o n by O i l . In s t i t u t e of Petroleum, London 1971 . 393 P. Holme N. A. I 9 6 9 . E f f e c t s of the Torrey Canyon P o l l u -t i o n on Marine L i f e In: Hoult I 9 6 9 . Hoult, P.P. 1969. O i l on the Sea. Dept. of Mechanical Engineering, MIT. Plenum Press; Proceed, of Symposium on the S c i e n t i f i c Aspects of O i l P o l l u t i o n of the Sea at Woods Hole. 96 Imperial O i l Ltd. 1951. O i l - Processes and Products. Jones H. R. 1973. P o l l u t i o n Control i n the Petroleum Industry. Noyes Data Corporation, 1973. Kneese A.V. Ayres R.U. D'Arge R.C.- 1970. Economics and the Environment: A Materials Balance Approach. Johns Hopkins Press 1970. Mc Caull J. 1969. The Black Tide. In: Environment. Vol 11, No. 9 , Nov. I969.. Matthews, W.G. 19?4. Recommended Dis p o s i t i o n of Used Lub-r i c a t i n g O i l s Prom an Energy'' Conservation Standpoint. Unpublished paper, Dept, of Energy, Mines and Re-sources, Ottawa, 1974. M i t c h e l l R. 1972. Water P o l l u t i o n Microbiology. Wiley, Interscience. NTIS 1972. Mercury i n the Environment - the Human Element. ' (National Technical Information Service) by: R.A. "Wallace et. a l . Oak Ridge National Lab. NTIS 1972. PCB*s and the Environment NTIS 1973. Cadmium, the Dissipated Element.. Oregon State University 19?2. Water Resources Research I n s t i t u t e : . Heavy Metals i n the Environment. Ottway S. 1970. The Comparative T o x i c i t i e s of Crude O i l s . • In: Cowe11, 1970 PACE 1973. Report on the Disposal of Used Automotive O i l From Service Stations. Petroleum Association f o r Conservation of the Canadian Environment. S.achanen, A.N. 194.5, • The Chemical Constituents of Pe-troleum. • Reinhold Publishing Corp. N.Y. 1945. SCEP 19?0. Man's Impact on the Global Environment. Report of theStudy of Critical-Environmental Problems (SCEP). MIT Press 1.970. Russell C. S. -.1.973. Residuals Management i n Industry -A Case Study of Petroleum Refining Resources f o r the Future, Johns Hopkins Univ. Press. Baltimore 1973. 97 Smith F.A. 1967. The Economic Theory .of I n d u s t r i a l Waste Production and D i s p o s a l . D o c t o r a l D i s s e r t a t i o n , Northwestern 1 9 & 7 . SNA ME 1971. Tankers and the Ecology. SNAME- Transactions 1971 , pp. I69 - 179. 'SWPCB I 9 5 6 . O i l y Substances and t h e i r E f f e c t s on the Bene-f i c i a l Uses of Water. ..State Water P o l l u t i o n C o n t r o l Board, C a l i f o r n i a 1956.. U.S. PHEW 1973. Toxic Substances L i s t , 1973- E d i t i o n . U.S. Dept.- of Heal t h , Education and Welfare. 1 0 0 1 p. U.S.: EPA 1972' a. Waste O i l 'Recovery P r a c t i c e s , State of the A r t . State of Maryland Environmental S e r v i -ce. C o n t r a c t o r : Environmental Q u a l i t y Systems Icn. 1.972b. Runoff of O i l s from Rural ..Roads Treated to Suppress Dust. EPA R 2 - 7 2 - 0 5 4 . 1972c. O i l y Waste D i s p o s a l by S o i l C u l t i v a t i o n Process. EPA R 2 - 7 2 - 1 1 0 . l 9 ? 4 a . Waste O i l . R e c y c l i n g and D i s p o s a l . EPA 6 7 0/2 - 7 4 - 0 5 2 ._. 1974b. E f f e c t s of Crude O i l and some of i t s • Components on Young Coho Salmon and.Sockeye Salmon. EPA 6 6 0 / 3 - ? 3 - 0 1 8 I9 ' ?4c. Used O i l Law i n the United States and Europe. EPA 6 o o / 5 - ? 4 - 0 2 5 ( i n c l u d e s Canada) _ I9_7_4d. State of Maryland V/aste O i l Recovery . . and Reuse Program. EPA. 6 7 0 / 2 - 7 4 - 0 1 3 . ' ' Westwater 1973. Annual Report. A p r i l 1 ,1972 to Aug. 3 1 , 1973. Westwater Research Centre, U n i v e r s i t y of B r i t i s h Columbia. Working Group "Water and Petroleum". 1970. E v a l u a t i o n and Treatment, of O i l S p i l l A ccidents on Land w i t h a View to the P r o t e c t i o n of'Water Resources,. . , German Federal I n s t i t u t e of Hydrology 1970. Z.oBell C.E. I 9 6 3 . The Occurrence, E f f e c t s and Fate of O i l P o l l u t i n g the Sea. . I n : • i n t l . Journal, of Air.and Water P o l l u t i o n , V o l . 7 1 9 6 3 , pp. 173 - 198. '• ! ~ 98 A ' P P E N D I C E S 99 A P P E N D I X 1 Comments to Assumptions 100 ( 1 ) - (6) l i q u i d Fuels The exact breakdown of a l l l i q u i d fuels to the GVRD l e v e l i s of secondary importance i f the objective of the. study i s to investigate the water p o l l u t i o n p o t e n t i a l o;f the petro-leum products, These products have a p o l l u t i o n p o t e n t i a l only through s p i l l s which, according to ( 1 2 ) represent 0 . 5 % of the t o t a l of the fu e l s . An error i n estimating 'the'regional breakdown has therefore only a very l i m i t e d impact on the t o t a l discharges to the environment. ( 1 ) Gasoline, Regional Breakdown (p. 5 0 , table 6 ) S t a t i s t i c s Canada indicates t h i s figure d i r e c t l y (Sta-t i s t i c s Canada, 5 7 0 0 2 , Vol 8 No. 46). ( 2 ) Aviation Fuels A i r p o r t s t a t i s t i c s indicate that Vancouver Air p o r t handles 9 3 % of a l l i n t e r n a t i o n a l t r a f f i c and 63 $ of a l l domestic a i r t r a f f i c of the Province. As a re s u l t of t h i s , weighing the f l i g h t s according to t h e i r f u e l consumption, Vancouver Airp o r t consumes approximately 8 5 % of the a v i a t i o n fuels of the province. This method does not necessarily produce an accurate r e s u l t , however, as the figure i s of secon-dary importance, no further research was put into t h i s e s t i -mate. ( 3 ) Diesel Fuel The share of the GVRD i n the transportation sector i s assu-med the same as f o r gasoline ( i . e . 36 f°). This seems to be a•legitimate assumption inasmuch as a representative of Imperial O i l estimated that the sales of d i e s e l f u e l i n the i n t e r i o r of the province are about the same as i n the Vancouver Area compared with the sales of gasoline. 101 The construction sector i s calculated to be 5 0 % of the pro-v i n c i a l t o t a l on the basis of a simple breakdown per capita. Forestry and mining, b a s i c a l l y non-urban a c t i v i t i e s , have obviously a smaller share of the province's sales. Ten and f i f t e e n fo respectively have been assumed a r b i t r a r i l y (fores-t r y s l i g h t l y higher, as a number of wood and paper indus-t r i e s e x i s t i n the GVRD). Fuel O i l , Transportation Sector In the transportation sector, f u e l o i l s are mainly used by marine operators ( bunker f u e l f o r ships). This sector has a l a r g e r share of i t s B.C. t o t a l than other transporta-t i o n sectors according to a personal communication of an o f f i c i a l of the Ministry of Transport i n d i c a t i n g that a "large" part of fuels used f o r marine purposes are sold i n Vancouver. The assumption of 5 0 f i s therefore r e l a t i v e l y a r b i t r a r y . Fuel O i l , I n d u s t r i a l Sector In the i n d u s t r i a l sector the breakdown was c a r r i e d out according to the number of jobs i n the manufacturing indus-t r y , i . e . 30 f> of the. province. Again, t h i s assumption i s rough, but the figure i s of secondary importance. Fuel O i l s , Domestic Sector • I t can be assumed that colder winters i n the i n t e r i o r of the province cause a higher neating f u e l consumption per household. As the population i n the i n t e r i o r i s r e l a t i v e l y .small, a s l i g h t error does not- affect, the balance very much. I t i s a r b i t r a r i l y assumed that heating a housing unit i n the coastal zone of B.C. requires 7 5 fo i f the energy nee-ded to heat the same housing unit i n the i n t e r i o r . Taking into account that 76 f of B.C.'s population l i v e s i n coastal areas, the f u e l consumption i n the domestic sector i n the GVRD i s calculated to be 4 8 5 0 0 0 tons/year or 4 4 fo of the-102 p r o v i n c i a l t o t a l . I f instead of 75 f a v a r i a t i o n of 50 to 10.0 fo would be assumed, the t o t a l f u e l consumption i n the GVRD would vary between 415 000 and 516 000 tons which a f f e c t s the s p i l l s (14 900 tons U7] ) by 3 .3 f only. (7) Lubricating O i l s (p.50, table 6) The following.table summarizes the assumptions. Comments on the p a r t i c u l a r figures are given below, (tons/year) Sector Consumption i n B.C. f> i n . GVRD Consumption i n GVRD. R e t a i l pumps Gvts + other Trsp. Total Transportation. 27 015 30 897 57 912 34 (a) : 46 (b) 40 9 200 14 400 23 600 1.22] Construction Forest Industry Other Industry «X6tal -Industry 2 978 20 404 . 7 016 30 398 50 (c) 26 (d) 17 (e) 26.4 1 500 5 300 1 220 8 020 [2 l ] Farms • 3 740 0 0 • • Total 92 052 34. 3. 31 620 121+22] > No o f f i c i a l data i s available f o r the breakdown of these fig u r e s . As the use of l u b r i c a t i n g o i l s i n the transpor-t a t i o n sector i s c l o s e l y related to the use of gasoline, i t i s assumed that the t o t a l share used i n Vancouver i s the same f o r l u b r i c a t i n g o i l s as f o r gasoline, i . e . 34 f (a). The estimate f o r the other sectors have to be "reasonable guesses", they have been made a f t e r discussions with -knowledgeable people i n the p a r t i c u l a r subject (Mr. K a l l e r of P u r o i l Refineries f o r (b) and (e), Mr. Hamm of McMillan Bloedel f o r (djj (c) i s assumed to be proportional to the population). 103 (8) Waste O i l Generation, Service Stations (p 55* Table 8) The o i l consumed by automobiles has been estimated i n several reports (EPA 1974a, EPS 1974). They indicate that approximately 35 f> of the t o t a l l u b r i c a t i n g o i l sold i s consumed. This fig u r e was reaffirmed through the ques-tionnaire survey. Most of t h i s consumed o i l i s burned (30 fo) according to several discussions with people from the automobile main-tenance industry. The other 5. f° i s leaked or l o s t i n other ways. This means that 65 f> of a l l sales are actu-a l l y recoverable o i l s . As the questionnaire indicates, a l l of t h i s category of recoverable o i l i s recovered i n the Vancouver Area. (9) Waste O i l Generation, Do-it-yourself Market (p. 5 5 . table 8) Waste o i l production i s i d e n t i c a l to (8) since the same vehicles are involved. Only small amounts of these sales are recovered (EPS 1974) but no. estimates are a v a i l a b l e i n the l i t e r a t u r e . A recovery rate of 5 f° i s a r b i t r a r i l y assu-med. (10) Other Transportation (p. 55, table 8) >Railroads, marine sector and government sales. EPS (1974) indicates a recoverable amount of JO f f o r r a i l -roads and 22 f> f o r the marine sector. BC Hydro indicates a recoverable amount of approximately 40 fo f o r i t s bus-operations (personal communication). ' .Based on t h i s i n f o r -mation, a recoverable share of 27 f i s assumed, of the remaining 73 %>$ 70 f> i s consumed by burning i n the d i e s e l engines of the locomotives,, buses and .Ships and 3 f° i s l o s t 104 i n form of unburned o i l . Based on EPA (l ° 7 4 d ) i t i s assumed that half of the 27 f- recoverable o i l i s a c t u a l l y recovered (I3 f). (11) I n d u s t r i a l Waste O i l Generation I t was not possible to obtain meaningful data on the con-sumption rate of the i n d u s t r i a l o i l s . As "waste o i l " i s defined i n t h i s study, i t i s reasonable to expect that a c t u a l l y l i t t l e o i l is- burned or otherwise decomposed. The figure of 10 f> f o r consumed o i l s i s calculated according to B a t t e l l e ( I 9 7 I ) , assuming that o i l s are burned only i n combustion,engines. About 40 fo of the i n d u s t r i a l o i l s are motor o i l s and 30 % of t h i s o i l i s burndd. (see ( 8 ) ) , which equals approximately 1-0 f o v e r a l l losses. A l l other o i l s are used f o r a wide v a r i e t y of purposes and i t i s d i f f i c u l t to get an o v e r a l l recovery fi g u r e . The B a t t e l l e study indicates 17 d i f f e r e n t groups of i n d u s t r i a l o i l s . According to t h i s study 55 f° of the o i l i s recoverable and 35 f° i s non-recoverable o i l s ; 10 fo are burning losses. . According to the- i n d u s t r i a l , waste, o i l survey i n the Vancouver Area, approximately 23 f> of the. t o t a l i n d u s t r i a l o i l s are recovered. (12) Total O i l S p i l l s (p. 61) As mentioned i n the text, the estimate of the EPA (1974a). has been adopted f o r t h i s estimate. The 0.5 f of the ma-te-rial .losses occur between the point of production and the point of consumption. A ce r t a i n amount of these losses occur therefore outside the GVRD which i s the point of consumption. 'To be on the safe side, however, i t i s assumed that a l l the, 0 , 5 f.of the products consumed i n the GVRD (2 550 000 tons) are l o s t i n the GVRD, i . e . 12 760 tons. To t h i s figure,'.the s p i l l s due to the materials 105 • shipped through the GVRD have to he added. It i s a r b i t r a -r i l y . assumed that these s p i l l s amount to 0.1 f of the t o t a l (2 100 000 tons), i . e . 2100 tons. The t o t a l o i l s s p i l l e d in. the. GVRD amount therefore to 12 ?6o .+ 2100 = 14 900 tons (13) Recovery Rate of S p i l l s (p 61, 77) Based on an estimate of the EPA (1974a) report. Due to a major uncertainty i n t h i s f i g u r e , a v a r i a t i o n of t 2000 tons i s assumed (see chapter 4 . 5 ) . (14) S p i l l s on Land vs. S p i l l s on Water Again, EPA (1974a) has been used f o r t h i s estimate. A v a r i a t i o n of t 10 f of the discharge r a t i o has been assu-med. (15) Road O i l i n g (pp. 6 5 , 1 6 9 ) According to a personal communication with the manager of the lar g e s t waste o i l processing f i r m i n Vancouver (Imperial Paving), approximately 25 f° of the colle c t e d o i l s i n the Vancouver Area are used f o r road, o i l i n g . (38OO tons [42]). (16) Runoff from Oiled Roads EPA (1974a) indicates that "dust transportation and runoff" amounts to 70 to 75 f° of the o i l spread on roads. For t h i s study, i t i s a r b i t r a r i l y assumed that runoff accounts f o r 40 f0, the other 30 f> to 35 .fo being l o s t by dust trans-portation. This part of the o i l i s not included i n the waste discharged to the environment. The information on.the o i l l o s t from o i l e d roads are"quite controversial. The research by the German Federal I n s t i t u t e of Hydrology seems to contradict the EPA-figures. Due to th i s uncer-tainty,, a v a r i a t i o n of 1 25 f has been adopted f o r t h i s 106 f i g u r e which means that a t o t a l runoff from o i l e d roads ranging from 15 to 65 f> ha;s to be expected. (17) Amount of Waste O i l Burning (p. 68) According to information by Imperial Paving (18) Amount of Re-refining (p. 69) According to information by W i l l s O i l Re-refining, the only r e - r e f i n e r i n Vancouver (Mr. Nye) (19) Process Residuals (p. 69) Source: EPA(l974a) (20) to (23) Runoff of Landbased Wastes, to Water (p. 71, table 12) These figures are a r b i t r a r y assumptions and are therefore subject to the s e n s i t i v i t y analysis i n paragraph 4 . 5 . Some rationales f o r the p a r t i c u l a r assumptions are given i n the following. (20) S p i l l s on Land A r e l a t i v e l y low runoff rate has to be expected according to Dr. He 11 ma.nn of the German Federal I n s t i t u t e of Hydrology due to a l i m i t e d spreading of the o i l i n the underground and due to a r e l a t i v e l y large number of small s p i l l s . Assumed i s 30 f + 10 fo. (21) Automotive Losses (non-recoverable) These o i l s * a r e mostly discharged to road surfaces, which are d i r e c t l y drained to. sewers and have therefore a higher runoff.rate. (50: fo t 10 f> i s assumed). (22) D o - i t - y o u r s e l f Market The v e h i c l e o p e r a t o r s who change t h e i r own o i l a r e r e l a -t i v e l y u n l i k e l y t o d i s c h a r g e the o i l d i r e c t l y i n t o t h e sev/ers. I n s t e a d , t h e waste o i l i s s p r e a d on b a c k a l l e y s o r p u t i n t o garbage cans w h i c h end up a t garbage dumps. I t i s t h e r e f o r e assumed t h a t t h i s r u n o f f r a t e i s the same as f o r s p i l l s (30 ± 10 fo) (23) O t h e r T r a n s p o r t a t i o n , I n d u s t r i a l O i l s and Waste O i l Pro c e s s i ng Re s 1 d us. 1 s ; A r e l a t i v e l y h i g h r u n o f f r a t e i s assumed. I n t r a n s p o r -t a t i o n . , t h e marine s e c t o r i s l i k e l y t o have a h i g h e r d i s c h a r g e t o the w a t e r t h r o u g h dumping of waste o i l , t h e i n d u s t r i a l s e c t o r o p e r a t e s w i t h a number o f c l a s s e s o f o i l s l o s t i n the m a n u f a c t u r i n g p r o c e s s i n p l a n t s w h i c h end up d i r e c t l y i n sewers (some i n d u s t r i e s i n d i c a t e d t h i s i n the q u e s t i o n n a i r e s o f the i n d u s t r i a l waste o i l s u r v e y ) . Assumed v a l u e : 50 t 10 fo. (24) t o (26) Sewer Runoff v s . N a t u r a l R u n o f f (p. ? 2 , diagram 2) A g a i n , no h a r d d a t a a r e a v a i l a b l e f o r e s t i m a t i n g t h e s e f i -g u r e s . They'are t h e r e f o r e s u b j e c t t o the s e n s i t i v i t y ana-l y s i s . (24) S p i l l s on Land A l a r g e number o f s p i l l s o c c u r a t p l a c e s where t h e y cannot e n t e r sev/ers, e x c e p t i n t h e ' c a s e o f t a n k t r u c k a c c i d e n t s , o t h e r s p i l l s on r o a d s and s p i l l s i n the immediate e n v i r o n -ment o f a sewer. Most o f the o i l t h a t r e a c h e s the v/ater c a n be e x p e c t e d t o do so t h r o u g h n a t u r a l r u n o f f . The p a r t e n t e r i n g sewers i s t h e r f o r e assumed t o be r e l a t i v e l y s m a l l a t 30 f'. 100 (25) Waste O i l s The numerous waste o i l s are more l i k e l y to enter sewers through road surface runoff and through Various i n d u s t r i a l operations. Assumption: 50 ±' 10 fa enters the sewers. (26) Treatment Plants Presently, the Iona Island Treatment Plant, the plants i n Richmond and on the North Shore, a l l of which are primary treatment plants, serve approximately 60 fo of the population of the GVRD. The r e s t of the sewage i s discharged d i -r e c t l y to the Fraser River without treatment. (27) ' Discharge to Fraser River vs.. Burrard Inlet Presently, about 90 f of the domestic sewage i s discharged to the Frasere River, about 5° f> of the area i s drained to the Fraser River through natural runoff. According to an o f f i c i a l of Environment Canada, approximately 80' f of the s p i l l s - on water are i n the Burrard I n l e t , most of i t i n the harbor area and i n the coastal zones of the Georgia S t r a i t . The other 29 f° occur i n the Fraser River. (28) An example i l l u s t r a t e s the problem Figure 1: 1000 ±20 Figure 2: 1030 ± 50 The difference of Figure 2 minus figure 1 y i e l d s the r e s u l t of 30! 40 which has no p r a c t i c a l s i g n i f i c a n c e , as the error i s i n the same order of magnitude as the r e a l value i t s e l f . For t h i s reason., differences i n s t a t i s t i c a l accountings . (like'--table 5,. p. -48 have-to be investigated very care-f u l l y . ' . 109 A P P E N D I X 2 C o m p o s i t i o n o f W a s t e O i l 1 1 0 RANGE OF PROPERTIES OF USED LUBRICATING OILS Value Property Min. Max. Gravity, API at 60°F 20.7 27.9 Specific Gravity 0.887 0.934 Density . lb/US gal 7.40 7.78 lb/Can gal 8.90 9.35 Viscosity, SUS at 100°F 87 837 centistokes 17.3 180.6 Pour Point °F <-40 -30 Flash Point °F 175 415 Heating Value BTU/lb 13,571 19,300 BTU/US gal 105,555 143,360 BTU/Can gal 126,560 171,890 Neutralization Number mg KOH/g 4.0 14.3 B S $ W %v/v 0.1 22.0 Sulphur % w/w 0.21 0.65 Ash % w/w 0.03 3.78 Silicon ppm 10 875 Calcium ppm 700 3,000 Sodium ppm 16 300 Iron ppm 50 2,000 Magnesium ppm 10 1,108 Lead ppm 800 21,700 Vanadium ppm 3 39 Copper ppm 5 348 Barium ppm 10 2,000 Zinc ppm 300 3,000 Phosphorus ppm 500 2,000 Tin ppm 5 112 Chromium ppm 8 50 Nickel ppm 3 30 Beryllium ppm 6 Magnesium ppm 5 10 - 88 -RANGE OF PROPERTIES OF USED LUBRICATING OILS Value Property Min. Max Cadmium ppm 4 Silver ppm 1 Strontium ppm 10 30 Aluminum ppm 10 800 Boron ppm 3 20 Molybdenum ppm 2 3 Titanium ppm 5 30 NOTE: ppm - parts per million by weight. - 89 -112 A P P E N D I X 3 S u m m a r y o f T o x i c i t y T e s t s 113 1. T o x i c i t y o f C rude O i l t o L i t t o r i n a L i t t o r a l i s R e s u l t s o f t e s t s d e s c r i b e d i n O t t w a y ( 197°) T o x i c i t y t e s t s were c a r r i e d o u t w i t h 20 d i f f e r e n t c r u d e o i l s . The s p e c i e s was e x p o s e d t o t h e o i l f o r one h o u r , t e s t s were c a r r i e d o u t a t v a r i o u s t e m p e r a t u r e s ( 3 ° , 16° and 26° C . ) . The c o n c e n t r a t i o n o f t h e o i l s t o w h i c h t h e a n i m a l s were e x p o s e d i s n o t m e n t i o n n e d The f o l l o w i n g g e n e r a l c o n c l u s i o n s a r e drawn f r o m t h e t e s t s 1. The d i f f e r e n t c r u d e o i l s v a r y w i d e l y i n t h e i r t o x i c i t y t o t h e t e s t a n i m a l s 2 . The t o x i c i t i e s v a r y s u b s t a n t i a l l y w i t h t h e t e m p e r a t u r e , bmt no c o n s i s t e n t p a t t e r n i s d e m o n s t r a t e d , i . e . no c l e a r c o r r e l a t i o n s o f t o x i c i t y w i t h c h e m i c a l c o m p o s i t i o n d a t a and t e m p e r a t u r e i s imme-d i a t e l y a p p a r e n t , a l t h o u g h c e r t a i n t e n d e n c i e s a r e i n d i c a t e d . E . g . o i l s w i t h h i g h e r s u l p h u r and a s p h a l t e n e c o n t e n t t e n d t o be more t o x i c a t l o w e r t e m p e r a t u r e s , a l s o t h e o r d e r o f t o x i c i t i e s o f c r u d e o i l s a t l 6 ° C i s f a i r l y c o n s i s t e n t w i t h t h a t o f t h e p r o p o r -t i o n o f a r o m a t i c s and l o w b o i l i n g f r a c t i o n s . T h i s c o r r e l a t i o n i s n o t a p p a r e n t a t 3° and 26°C. 3. Low b o i l i n g f r a c t i o n s c o n f e r a c o n s i d e r a b l e d e g r e e o f t o x i -c i t y a l t h o u g h o t h e r t o x i c e l e m e n t s ( p a r t i c u l a r l y s u l p h u r ) h a v e r e s i d u a l t o x i c i t i e s . ^ 2 . T o x i c i t y o f R e f i n e d P r o d u c t s t o t h e Same S p e c i e s Type o f O i l M o r t a l i t y R a t e in ' - % a f t e r e x p o s e d t o o i l l e n g t h o f t i m e ' P r o d u c t 6 M i n 30 M i n . 1 H r . 3 H r s 6 H r s G a s o l i n e 7 8 80 76 78 70 K e r o s e n e 10 14 20 50 68 D i e s e l O i l 0 o 0 0 0 F u e l O i l 2 0 0 o 2 2 3500 F u e l O i l 0 o 0 0 0 K u w a i t C r u d e 12 10 28 48 62 114 3» T o x i c i t y o f P e t r o l e u m H y d r o c a r b o n s t o Sa lmon R e f e r e n c e : EPA ( l974b) M o r t a l i t y R a t e s a f t e r 96 h o u r s : S u b s t a n c e c o n c e n t r a t i o n % m o r t a l i t y a f t e r 96 ppm h o u r s Crude O i l 3*500 55 1»3 c y c l o h e x a d i e n e 50 33 Benzene . 10 3 50 60 100 100 E t h y l b e n z e n e 10 13 50 100 X y l e n e 1 23 10 30 100 100 T o l u e n e 1 10 10 50 100 P e n t a n e , h e x a n e , h e p t a n e , o c t a n e , c y c l o p e n t a n e , e t h y l c y c l o p e n t a n e , c y c l o h e x a n e , e t h y l c y c l o h e x a n e , c y c l o p e n t e n e and c y c l o h e x e n e showed no s i g n i f i c a n t m o r t a l i t i e s up t o 100 ppm. 115 A P P E N D I X 4 W A S T E O I L S U R V E Y WASTE CRANKCASE OIL SURVEY 116 Your Postal Code M M M M 1. Please indicate which of the following types.of facilities describes best the operation of your firm, (check appropriate box) • Gasoline Service Station Q Non Highway Vehicle, Construction Equipment Service 1 I Auto Dealer/Repair Q Other, Please describe I I Fleet Service/Repair — — I [ Truck or Bus Service/Repair _ . — 2. How many oil changes do you perform per month on the average? 3. What average amount of oil do you sell per month (including transmission, hydraulic oils etc.)? Total gallons per month Gallons per month resulting from oil changes 4. How much waste oil do you accumulate per month on the average? Gallons per month How do you dispose of the waste oil at present? I j Picked up by collector I I Burned I I Other, Please describe Gallons per pickup Pickups per year Gallons per month 6. Do you have holding (storage) tank facilities for waste oil? • • Yes No Gallons capacity 7. If your waste oil is picked up by collector, please give name and address of collector. Cost of Pickup or If collector pays you Cents per Gallon Dollars per pickup Cents per Gallon 8. Any additional comments you might have are invited. Please return to: Westwater Research Centre 2075 Wesbrook Place University of B.C. Vancouver, B.C. V6T 1W5 117 1 . Waste Crankcase O i l Survey Accumulated Figures (Tons per year) Service Stations Truck and Bus Services Other Total Total Sales 1339 156 8 8 . 3 1578 Sales for O i l Changes 9 4 4 1 4 1 4 6 1131 Waste O i l Generation 886 131 47 1046 Returned Questionnaires 182 14 10 206 Total questionnaires sent outs 731 Total questionnaires returned: 208 118 INDUSTRIAL WASTE OIL SURVEY Your Postal Code Please indicate which of the following types of facilities best describes the operation of your f i rm, (check appropriate box). | | marine | | aeromotive [ | railroad equipment & service | | pulp & paper, wood products | j metalworking | | construction, non nighway vehicles | | food processing other, please describe '. What is your average monthly oil consumption? (check appropriate box and estimate usage rate [ | gear & transmission [ | hydraulic oils | [ water soluble cutting oils | | straight cutting oils f^ ] turbine oils [ | other, please describe gallons per month gallons per month gallons per month gallons per month gallons per month What is your average monthly generation of waste oil? | | gear & transmission | | hydraulic oils Q water soluble cuttings oils | \ straight cutting oils [ | turbine oils | | other, please describe gallons per month gallons per month gallons per month gallons per month gallons per month Do you refine or purify waste oils for own reuse? | | gear & transmission | | hydraulic oils [ | water soluble cutting oils I | straight cutting oils • turbine oils I I other, please describe gallons per month gallons per month gallons per month gallons per month gallons per month (over) 1 1 9 2 . I n d u s t r i a l Waste O i l S u r v e y A c c u m u l a t e d F igures - . (Tons p e r y e a r ) 1 . * T r a n s m i s s . H y d r a u l i c C u t t i n g O t h e r \ 8 T o t a l j + C r a n k c a s e O i l s O i l s O i l s 8 M a r i n e 6 4 . 5 11.0 " 3 . 8 79 .3 l 4 . 8 2.9 3 . 1 - 21.0 Pulp+ P a p e r 122.5 362 ' . 8 8 . 8 494 3 0 . 3 293 -•' •7 M e t a l w o r k i n g 21.9 14 .4 55*1 5.1 9 6 . 6 9 .0 5 . 6 43.9 2 .2 60.8 C o n s t r u c t i o n 9.8 21.6 . 2 39.0 7 0 . 7 g 6.3 16 .4 . 1 2.1 25.9 j O t h e r 72.3 3.0 .3 - 75.7 1 W : , .17.9 •'• 2.4 ... - 2 0 . 4 1 vToJbal 291.2 412.4 6 0 . 4 53.0 817 . 1 7 8 . 5 321.4 4 7 . 3 5.1 452.3 1 Upper f i g u r e : O i l c o n s u m p t i o n Lower f i g u r e : Waste O i l G e n e r a t i o n T o t a l q u e s t i o n n a i r e s s e n t o u t : 652 T o t a l q u e s t i o n n a i r e s r e t u r n e d : 102 (=15.6 % ) . 120 A P P E N D I X 5 C o s t C o m p a r i s o n F u e l U s e R e - r e f i n i n g 121 C o s t C o m p a r i s o n F u e l Use - R e - r e f i n i n g ( C o s t s 1972) 1. R e - c r e f i n i n g a ) C o s t o f R e - r e f i n i n g , s m a l l r e f i n e r y Of 500'000 g a l l o n s / y e a r g / g a l l o n 0.145 b) C o s t o f p r o d u c t i o n o f f u e l o i l f o r amount o f w a s t e o i l T o t a l ^ / g a l l o n 0.10 ^ / g a l l o n 0 .245 1) 2) 2. B u r n i n g C o s t o f p r o d u c i n g v i r g i n l u b r i c a t i n g o i l ^ / g a l l o n 0 .433 3) R e - r e f i n i n g c h e a p e r t h a n b u r n i n g : .433 - .254 = 1 8 . 8 ^ / g a l l o n S o u r c e s : 1) EPA 1972a ( p . l 4 4 ) 2) R u s s e l l (1972) p . 9 9 f f . 3) EPA 1974a ( p . l 4 ) 122 F I G U R E S U N I V E R S I T Y O F B R I T I S H C O L U M B I A S C H O O L O F C O M M U N I T Y A N D R E G I O N A L P L A N N I N G ©SEATiR VANCOUVER REGIONAL DISTRICT A M A T E R I A L S B A L A N C E A N A L Y S I S P E T R O L E U M P R O D U C T S I N C R E A T E S V A N C O U V E R 2 UN1VSRS8TY O? BRITISH COLUMBIA SCHOOL OF COMMUNITY AND REGIONAL PLANNING ! ' • . . i . ; I i • A MATERIALS BALANCE ANALYSIS : PETROLEUM PRODUCTS SN GREATER VANCOUVER .Ag.B_l.JL 19? 5 M e t h a n e i . « • • ' -c ~C -C-C °C - C S i m p l e C h a i n P a r a f f i n ( n - h e x a n e ) B r a n c h e d C h a i n A r o m a t i c s ( B e n z e n e ) C r a c k i n g : » » H C 5 H 1 2 U (t M - C - C - C - 4 M H M K » • » c w-c-c-c - " » I I C 2 H 4 + C3 H8 R i n g ( C y c l o h e x a n e ) 1 c a r b o n - c a r b o n d o u b l e bond i s f o r -med w i t h e a c h s p l i t t i n g o f t h e m o l e c u l e R i n g w i t h b r a n c h e s U n s a t u r a t e d H y d r o c a r b o n ( P r o p e n e ) UN1VEKS8TY OF BRITISH COLUJVIB8A SCHOOL OF COMMUNITY AND REGIONAL PLANNING A M A T E R I A L S B A L A N C E A N A L Y S S S P E T R O L E U M P R O D U C T S I N G R E A T E R V A ^ C O U V E K X UNIVERSITY OF BRITISH COLUMBIA S C H O O L O F C O M M U N I REGIONAL PLANNING m A MATERIALS BALANCE ANALYSIS PETROLEUM PRODUCTS IN GREATER MMJLJLiZ5_ UNIVERSITY'OF BRITISH COLUMBIA SCHOOL O F COMA1 UNITY AND REGIONAL PLANNING M A T E ! i Q A A PETRQLE VANCOUVER S BALANCE PRODUCTS ANALYSIS IN GREATS! A P R I L 1975 UNIVERSITY OF BRITISH COLUMBIA S C H O O L O F C O M M U N I T Y A N D R E G I O N A L P L A N N I N G Morldwici< 1 0 0 0 METRIC TONS A MATERIALS BALANCE ANALYSIS PETROLEUM PRODUCTS IH GREATER VANCOUVER S*/es S'2oO S&/<as 3<foo S'ooo 7'2oo Recovered rsoo Do-//'-yours e// /W^r/ce/1 Consumed /'O2o I 1 Ice cove /-G.CH Non -2o4o - l7o /nc/us/r/d/ 0//s Consumed So a EESB33S Non-recovered 2 sco hfesre Of/ 3'3oo ZE Recovery W3o 9zoo 3 too I/'ooo ff'ooo M&s/e. Of/ 6«4o 233o 7'2oo 3'3oo /2320 Recovered 5-S8o /&4o 9<tZo 0//?er frdnsporfehon I Non-Recovered Recover^f>/e 33o kfa/er Seo Tbfdl' Lt/frricd/1//?*? d/?c/ hc/usfr/d/ O/'/s UNIVERSITY OF BRITISH COLUMBIA SCHOOL O F COMMUN REGIONAL PLANNING pa E H E R U m e t r i c A MATERIALS BALANCE Af*4AlYSE PETROLEUM PRODUCTS m GREATS. VANCOUVER UNIVERSITY OF BRITISH COLUMBIA •' Reft. 7 '-osses 4'SOO C'3l t-ijoi'c/ file. f% 4''6/2 '^6o El/3f>or j / < V e Losses /iftoo C<fJ /2-eeo [31] lO'Soo'ooo © '0 IHWMWWaaBBSB Bur r?t 7-92o SCHOOL OF COMMUNITY AND REGIONAL PLANNING kETRIC T O N S PiEK 1972 A M A T E R I A L S B A L A N C E A N A PETROLEUM PRODUCTS I N GRE VANCOUVER APg lL 1 9 7 5 '31 Cv6.Z> tZe-fi'neri'es 4 63/'800 OJ t-i'yt/ic/ Kiefs •OH SO rnf 4'6/2 'Uoo £t€.J /o'ooo £-ti&>/-,'caA'iet o./s. 47'Goo C20J 0 .0 $1 Bv*po/-*/,'ve L o s s e s ///'too C<f] /2'ZSo fj/J -tew ? V e / Cany &o>^>^' Or) 2'<*33'7*o /SJ to 'SoO'OOO IS! -»»( 4 Co//cc/eJ 9-<f2o flof-'••ahlc i. £3S7 UNIVERSITY OF BRITISH COLUMBIA SCHOOL OF COMMUNITY AND' REGIONAL PLANNING ™ i i i If Hfc: METRIC TONS A MATERIALS BALANCE ANALYSIS: PETROLEUM PRODUCTS IN GREATER VANCOUVER 

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