EPA-600/8-82-010 June 1982 MANUAL OF PRACTICE CHEMICAL TREATING AGENTS IN OIL SPILL CONTROL by Robert W. Castle, Carl R. Foget, and Eric Schrier Woodward-Clyde Consultants Three Embarcadero Center, Suite 700 San Francisco, California 94111 Contract No. 68-03-2621 Project Officer Leo T. McCarthy, Jr. Solid and Hazardous Waste Research Division Oil and Hazardous Materials Spill Branch Municipal Environmental Research Laboratory (Cincinnati) Edison, New Jersey 08837 MUNICIPAL ENVIRONMENTAL RESEARCH LABORATORY OFFICE OF RESEARCH AND DEVELOPMENT U.S. ENVIRONMENTAL PROTECTION AGENCY CINCINNATI, OHIO 45268 ------- DISCLAIMER This report has been reviewed by the Municipal Environmental Research Laboratory - Cincinnati, U.S. Environmental Protection Agency, and approved for publication. Approval does not signify that the contents necessarily reflect the views and policies of the U.S. Environmental Protection Agency, nor does mention of trade names or commercial products constitute endorsement or recommendation for use. 11 ------- FOREWORD The U.S. Environmental Protection Agency was created because of increasing public and government concern about the dangers of pollution to the health and welfare of the American people. Noxious air, foul water, and spoiled land are tragic testimonies to the deterioration of our natural environment. The complexity of that environment and the interplay of its components require a concentrated and integrated attack on the problem. Research and development is that necessary first step in problem solution; it involves defining the problem, measuring its impact, and searching for solutions. The Municipal Environmental Research Labora- tory develops new and improved technology and systems to prevent, treat, and manage wastewater and solid and hazardous waste pollutant discharges from municipal and community sources, to preserve and treat public drink- ing water supplies, and to minimize the adverse economic, social, health, and aesthetic effects of pollution. This publication is one of the prod- ucts of that research and provides a most vital communications link between the researcher and the user community. The purpose of this manual is to provide the On-Scene Coordinator (OSC) with a systematic methodology consistent with national policy that can be used to assess the case-by-case acceptability of oil spill treat- ment using chemicals, and to determine appropriate application procedures. Francis T. Mayo, Director Municipal Environmental Research Laboratory 111 ------- ABSTRACT The purpose of this manual is to provide the On-Scene Coordinator (OSC) with a systematic methodology consistent with national policy that can be used to assess the case-by-case acceptability of oil spill treatment using chemicals, and to determine appropriate application procedures. It contains guidelines for evaluating spill safety, determination of relevant spill characteristics, prediction of treated and nontreated spill movement, and criteria for comparison of probable impacts with and without treatment. Dispersion of oil at sea, dispersion on the shoreline, and the use of surface collecting agents are considered. The manual additionally describes general chemical agent application procedures and dosage regulation. This manual is submitted as partial fulfillment of Contract No. 68-03- 2621 by Woodward-Clyde Consultants under the sponsorship of the U.S. Environmental Protection Agency. IV ------- CONTENTS Abstract Contents Figures Tables x Acknowledgment x^i 100 Introduction 100-1 101 Purpose 100-1 102 The National Contingency Plan 100-2 103 Use of Manual 100-3 200 Information Checklist 200-1 300 Spill Characteristics and Movements 300-1 301 Oil Classification 300-1 302 Slick Movement 300-5 303 Fire/Explosion Hazard 300-12 400 Criteria for Dispersion of Oil at Sea 400-1 401 Decision Rationale 400-1 402 Identification of Threatened Areas 400-3 403 Conventional Control and Recovery Potential 400-7 404 Oil Dispersibility 400-13 405 Selection of Application Technique, Dispersant and Dosage 400-15 406 Movement of Dispersed Oil 400-23 407 Impact Comparison 400-41 500 Criteria for Dispersion of Oil on Shorelines 500-1 501 Decision Rationale 500-1 502 Conventional Protection and Cleanup Potential 500-3 503 Natural Cleaning Potential 500-4 504 Selection of Application Technique, Dispersant, and Dosage 500-9 505 Ecologic Criteria 500-16 600 Criteria for Use of Surface Collecting Agents * 600-1 601 General 600-1 602 Environmental Criteria Controlling Use 600-2 603 Selection of Application Method and Dosage 600-6 ------- Appendices A. Annex X A-l B. Techniques for Dispersion at Sea B-l C. Techniques for Dispersion on Shorelines C-1 D. Techniques for Use of Surface Collecting Agents D-l VI ------- FIGURES Number Page 103-1 Chemical treatment of oil spills - decision process 100-4 301-1 Field identification of oil types 300-4 302-1 Volume, film thickness, appearance, and area covered by oil spill 300-6 302-2 Vector addition for 10 km/hr NW wind and 0.3 km/hr north current 300-8 302-3 Maximum oil spill radius versus time 300-9 302-4 Typical evolution of slick surface 300-10 303-1 Decision guide - fire hazard and response 300-13 401-1 Decision guide - dispersion of floating oil 400-2 403-1 Assessment guide for mechanical control and recovery 400-8 403-2 Windwaves at sea 400-9 403-3 Recovery rates of skimmers for different sweep widths and vessel speeds 400-12 405-1 Product selection procedure 400-18 405-2 Product selection worksheet 400-19 405-3 Dispersant requirements at manufacturer's recommended application ratios 400-21 406-1 Dispersed oil movement worksheet 400-24 406-2 Concentration of dispersed oil at 25 percent dispersion effectiveness 400-27 406-3 Concentration of dispersed oil at 50 percent dispersion effectiveness 400-28 vii ------- Number Page 406-4 Concentration of dispersed oil at 75 percent dispersion effectiveness 400-29 406-5 Concentration of dispersed oil at 100 percent dispersion effectiveness 400-30 406-6 Dispersant concentration 400-31 406-7 Concentrations of dispersants in upper meter 400-32 406-8 Concentrations of dispersants in 3 meters 400-33 406-9 Concentrations of dispersants in 10 meters 400-34 406-10 Concentrations of dispersants in 30 meters 400-35 406-11 Maximum plume centerline concentration 400-38 407-1 Impact comparison matrix 400-42 407-2 Impact severity chart 400-46 407-3 Hypothetical spill event 400-52 407-4 Hypothetical spill event impact comparison matrix 400-53 501-1 Sequence for consideration of dispersant use on shorelines 500-2 503-1 Shoreline energy levels 500-5 503-2 Natural cleaning potential for sediment shorelines 500-7 503-3 Natural cleaning potential for non-sediment type shorelines 500-8 504-1 Decision guide - dispersant beach cleaning techniques for sediment beaches 500-14 504-2 Decision guide - dispersant beach cleaning techniques for non-sediment beaches 500-15 603-1 Collecting agent application 600-7 B-l Schematic of low pressure vessel spraying system - full strength application B-4 B-2 Schematic for vessel spraying system - diluted application B-5 Vlll ------- Number Page B-3 Schematic for high pressure vessel spraying system using eductors to introduce dispersant B-6 B-4 Schematic for high pressure jet spray system B-7 B-5 U.S.C.G. foam eductor system B-9 B-6 Eductor rate versus dispersant discharged B-10 B-7 Vessel speed - dosage rate graph B-12 B-8 On-board helicopter spray system B-15 B-9 Bucket-type helicopter spray system ... B-17 B-10 Light agricultural aircraft spray system: wind driven pump B-18 B-ll Light agricultural aircraft spray system: hydraulic pump B-19 B-12 Pump output calculation nomogram B-22 D-l Surface collecting agent application speed guide D-3 ------- TABLES Number Page 200-1 General Spill Information 200-2 200-2 Environmental Data 200-3 301-1 Spill Response Oil Classification 300-2 303-1 Flash Points and Flammability Limits of Refined Petroleum Products 300-14 402-1 Special Features, Resources, and Uses 400-4 403-1 Checklist for Logistics of Containment and Recovery Operations 400-10 404-1 Oil Type: Dispersant Compatability 400-14 405-1 Application System: Dispersant Type Compatability 400-16 405-2 Advantages and Disadvantages of Major Dispersant Application Systems 400-17 405-3 Product Screening Criteria 400-20 406-1 Estimated Initial Mixing Depths 400-25 406-2 Typical Evaporation - Dissolution Loss 400-40 407-1 Criteria for "Severe" Impact Rating 400-43 407-2 Grades of Toxicity 400-45 407-3 Summary of Toxicity Data 400-50 504-1 Dispersant Type versus Substrate Type 500-10 504-2 Equipment and Application Methods for Different Dispersant Types 500-11 504-3 Dispersant Beach Cleaning Techniques 500-13 ------- Number Page 602-1 Conditions Under Which Surface Collecting Agents Are Effective and Are Not Effective 600-3 602-2 Checklist for Determining Feasibility of Using Surface Collective Agents for Oil Containment and Shoreline Protection 600-4 603-1 Application Techniques for Surface Collecting Agents 600-8 B-l Basic Vessel Application Systems B-2 B-2 Representative Aircraft Specifications B-14 C-l Water Base Dispersant Application Methods C-2 XI ------- ACKNOWLEDGMENT The authors wish to express their appreciation to Mr. James D. Sartor, Mr. Martin Cramer, and Dr. David Liu of Woodward-Clyde Consultants, Environ- mental Systems Division for their invaluable assistance and guidance in the preparation of this manual. We also gratefully acknowledge technical advice supplied by Dr. John Frasier, Shell Oil Company; Mr. Gordon Lindbloom, Exxon Chemical Company; Mr. D.E. Fitzgerald, Atlantic Richfield Company; Mr. Eric Cowell, British Petro- leum Company; Mr. Sol Schwartz, EPA Region IX Technical Assistance Team; and Dr. Royal Nadeau, EPA Emergency Response Team, for their review of the draft report and helpful comments. Special thanks is given to Mr. Leo T. McCarthy, Jr. who served as Project Officer for the Environmental Protection Agency. XII ------- SECTION 100 INTRODUCTION 101 PURPOSE The major types of oil spill response actions include physical contain- ment, mechanical recovery, and chemical treatment. Those actions resulting in the actual recovery of the spilled material are preferred. However, such actions are operationally limited to relatively calm conditions, localized areas, and cases where there is minimal risk of fire or explosion. The use of chemical treating agents (dispersants and surface collectors) expands the range of operating conditions under which mitigating actions can be conduct- ed, permits treatment of large areas, and reduces fire and explosion hazard. This manual of practice is designed to provide a systematic methodology for determining the acceptability of using chemical agents in the treatment of oil spills. The methodology allows assessment of the threat or extent of sensitive area contamination, evaluation of the relative impacts associated with various response alternatives, and selection of appropriate application methods. 100-1 ------- 102 THE NATIONAL OIL AND HAZARDOUS SUBSTANCES POLLUTION CONTINGENCY PLAN Developed pursuant to Public Law 92-500 (The Federal Water Pollution Control Act), the National Oil and Hazardous Substances Pollution Contingency Plan (NCP) provides a basis for ensuring efficient, coordinated, and effec- tive action to minimize damage from oil and hazardous substance discharge, including containment, dispersal, and removal. While advocating physical control and removal of spilled oil, the NCP (Part 1510, Chapter V, Title 40, The Code of Federal Regulations) provides a schedule for case-by-case utili- zation of chemical treating agents and other additives. Known as Annex X, this schedule is reproduced in Appendix A. Annex X permits case-by-case consideration of chemical dispersion in the following circumstances: • In any case when, in the judgment of the federal On-Scene Coordinator (OSC), its use will prevent or substantially reduce hazard to human life or limb or substantially reduce explosion or fire hazard to property. • For major or medium discharges when, in the judgment of the on-scene Environmental Protection Agency representative, its use will prevent or reduce substantial hazard to a major segment of the population(s) of vulnerable species of waterfowl. • For major and medium discharges when, in the judgment of the Environmental Protection Agency response team member in consultation with appropriate state and federal agencies, its use will result in the least overall environmental damage, or interference with desig- nated water uses. Annex X also permits case-by-case consideration of surface collecting agent use under the following conditions: • For all size discharges when its use will result in the least over- all environmental damage or interference with designated water uses. • For all size discharges when its use will provide a key element in the most effective system for removing oil from the water environ- ment . Annex X requires submission of certain product and laboratory test data prior to consideration of a product for field use. Data so submitted are intended to provide information for case-by-case decision-making by on-scene federal personnel. The NCP further provides for certain technical, logistical, and scien- tific support. This manual is designed to incorporate and utilize these pro- visions and resources. As such, it is essential that the user of this manual be familiar with the provisions, procedures, and restrictions of the NCP in general and Annex X in particular. 100-2 ------- 103 USE OF MANUAL This manual provides the user with guidelines which enable case-by-case assessment of the feasibility and acceptability of chemical agent use in the control of oil spills in the marine environment. Figure 103-1 presents a flow diagram illustrating the decision-making sequence and general organiza- tion of the manual. Each decision point indicated represents one or more subsections of the manual, which provide instructions on how to conduct a specific evaluation or make a decision. Section 200 contains field checklists which assemble information neces- sary to access chemical treatment feasibility and application criteria, and to compare impacts resulting from the available options. Section 300 uses portions of this material to develop assessments regarding spill characteristics and movement. It also provides criteria to assess fire and explosion hazards. Use of chemical agents is acceptable to the degree necessary to mitigate risk to human life, limb, or property with- out further qualification. Section 400, Criteria for the Dispersion of Oil at Sea, deals with situations where shoreline contamination will not occur immediately. In evaluating the acceptibility of chemical treatment, it provides criteria for identification of threatened features or areas; assessment of control and recovery potential using conventional techniques; evaluation of oil disper- sibility; application techniques, dispersants, and dosage; prediction of oil movement and characteristics; and comparison of the impacts associated with dispersion versus those associated with conventional or no treatment. Section 500 discusses the use of dispersants in treating shorelines where oiling is imminent or has already occurred. It provides guidelines for assessment of the probable adequacy of conventional protection and cleanup; evaluation of probable natural cleaning processes; guidelines for the selec- tion of agent, application technique, and dosage; and assessment of ecologic factors. Section 600 discusses the applications of surface collecting agents; environmental factors which control their successful use; and the selection of appropriate application methods, dosage, and supporting equipment. A series of appendices is included to provide support information. These appendices include: Appendix A Annex X Appendix B Techniques for Dispersion at Sea Appendix C Techniques for Dispersion on Shorelines Appendix D Techniques for Use of Surface Collecting Agents 100-3 ------- Spill information ^v (200) ) K Environ mental information (200) f Determine oil characteristics^ I and classification I v" (301) y C c Predict slick movements (302) Evaluate fire and explosion hazard (303) Does spill present a threat to human life or limb, or explosion/fire hazard to property' O O Floating slick (401) Identify threatened areas (402) Assess conventional control and recovery capability (403) ^Surface collecting ^ -4 agents )- \(600) (Appendix D)/ Chemical dispersion acceptable as necessary to control hazard (404, 405, Appendix B) Slick grounded or grounding imminent (501) Identify primary or secondary threatened areas (402) Assess conventional control and recovi capability (502) -\ 'ery 1 Will control and recovery actions be adequate' IMPLEMENT Can environmentally acceptable control and recovery actions be taken' ------- (Evaluate dispersibility ^ of oil 1 (404) I c Assess natural cleaning potential (603) O o I Ln Is chemical dispersion feasible? Prepare to treat on shore (501) Allow to clean naturally Is natural cleaning acceptable? Select dispersant, application, technique and dosage ' (405) 'Predict movement and X characteristics of ' dispersant and dispersed oil; (406) J ^ ^ / Select dispersant, ( application, technique I and dosage V '«*) Evaluate impacts of chemical dispersion vs other treatment (505) ^^^^^^^^^^^^^^^^^^^^^^ Compare impact of chemical dispersion vs no treatment (407) Chemical dispersion less environmentally damaging Is chemical dispersion less environmentally damaging' Prepare to treat on shore (501) Chemical dispersion acceptable (Appendix C) Chemical dispersion acceptable (Appendix B) Figure 103-1. Chemical treatment of oil spills - decision process. ------- SECTION 200 INFORMATION CHECKLIST Evaluation of the acceptability of chemical agent use involves numerous assessments requiring a variety of information. While many types of informa- tion can be assembled for a geographic area prior to actual need, every spill has its own combination of unique characteristics which can only be deter- mined during the incident. Tables 200-1 and 200-2 are checklists designed to facilitate collection of appropriate data. Table 200-1 lists general information including time, location, volume, and characteristics of the oil which can be used in estimating the extent of the spill and its treatability. Meteorologic and oceanographic data are also included to help predict spill movement and conventional cleanup potential. Table 200-2 guides the collection of general ecologic data which are necessary to identify possible threats and evaluation of impacts. Normally, state and local officials and experts are available to contribute this type of information. Their input may be particularly valuable in the identifica- tion of local conditions, problems, and attitudes. 200-1 ------- TABLE 200-1. GENERAL SPILL INFORMATION INCIDENT DATA Apparent source: Time and date: _ Location: Is spill continuing? Yes No Volume of discharge: Known (barrels) Estimated (barrels) Loss rate if continuing: (barrels/day) Size and location of slick: (plot on chart) Observed rate and direction of slick movement: Oil type: A B C D (section 301) Slick type: Continuous Windrows Other (specify) Estimated average thickness: Emulsification: METEOROLOGIC DATA Air temperature: Wind: Speed Direction Precipitation: Visibility: Forecast: OCEANOGRAPHIC DATA Water temperature: Currents: Type Speed . Direction. Sea state: 1 2 3 4 5 Average wave height (crest to trough): (m) HYDROLOGIC DATA (near shore) Wave height: (m) irrents: Tidal (ebb): Velocity Tidal (flood): Velocity Rlwk w/atpr- Direction Direction Duration Duration (min) Longshore currents: Velocity Direction Tidal range: Rising Falling Turbidity: ADDITIONAL INFORMATION 200-2 ------- TABLE 200-2. ENVIRONMENTAL DATA OFFSHORE AREAS Sensitive Marine Resources Waterfowl: Present Species Number Marine mammals: Present Species Number. Other (specify): Commercial Use Industrial (specify type, location): Finfish (specify type, location): — Shellfish (specify type, location):- Other (specify type, location): Recreational/Navigational use: Other special features: NEARSHORE/ONSHORE AREAS Sensitive Marine Resources Waterfowl: Present Species Number Nesting Area. Marine mammals: Present Species Number Estuaries: Wetlands: Coral reefs: Rare, endangered, unique species/ associations (specify species/type): Other (specify): Commercial Use Industrial (specify) Finfishery: Shellfishery: Other: Recreational Use Harbors: Recreational beaches/parks: Boating: Tourism: Other (specify):. 200-3 ------- SECTION 300 SPILL CHARACTERISTICS AND MOVEMENT 301 OIL CLASSIFICATION Petroleum can differ widely in its physical and chemical properties and reactions when spilled in the environment or subjected to various types of control actions. Weathering, emulsification, and other processes can further alter the nature of the material with time. An understanding of the oil and its probable reactions is necessary in predicting impacts and designing an effective spill response. The spilled material must be assessed as it reacts and changes in the field. The following field classification groups oils into categories having features common to both physical and chemical treatment. The four classes of oil are: • CLASS A: Low viscosity, high spreading rate oils • CLASS B: Moderate or high viscosity, waxy or paraffin-base oils • CLASS C: High viscosity, low spreading rate, asphaltic or mixed-base oils • CLASS D: Non-spreading oils. Table 301-1 summarizes representative oils, diagnostic properties, and physical/chemical characteristics for each class. Class A; Low Viscosity. High Spreading Rate Oils This class typically includes light fuel oils and many light crude oils. These materials are generally flammable when fresh. Class A oils can be identified by high fluidity, clarity, rapid spreading rate, strong odor, and high evaporation rate. They do not tend to adhere to surfaces and can usu- ally be removed by flushing. Their tendency to penetrate porous surfaces is high, and when incorporated in reducing substrates, Class A oils may be per- sistent. When fresh, oils of this class can be considered highly toxic. Class A oils tend to form unstable emulsions. Heavier Class A oils may partially evaporate, leaving a residue that may fall into one of the other response classes. Class B; Moderate or High Viscosity Waxy Oils This class includes medium to heavy paraffin-base oils distinguished by a waxy or non-sticky feel. The oils of this class adhere to rock, plant and other surfaces, but tend to be moderately removable by flushing. Their 300-1 ------- TABLE 301-1. SPILL RESPONSE OIL CLASSIFICATION Field-Determined Oil Type Designation Representative Oils Diagnostic Properties Physical/Chemical Properties 00 o o I Low viscosity, high spreading rate oils Moderate or higher viscos- ity paraffin base oils High viscosity low spreading rate oils Nonfluid oils (at ambient temperature) Distillate fuel and light crude oils (all types) Medium to heavy paraffin base refined and crude oils; water-in- oil emulsions Residual fuel oils; medium to heavy asphaltic and mixed-base crudes; weath- ered oil Residual and heavy crude oils (all types); weathered oil, water-in-oil emulsions Highly fluid, usually transparent but can be opaque, strong odor, rapid spreading, can be rinsed from surfaces by simple agitation. Moderate to high vis- cosity, waxy feel, can be rinsed from surfaces by low pressure water flushing. Typically opaque brown or black, sticky or tarry, viscous, cannot be rinsed from surfaces by agitation. Tarry or waxy lumps. May be flammable, high rate of evaporative loss of vola- tile components, assumed to be highly toxic when fresh, tend to form unstable emul- sions, may penetrate sub- strates, respond well to most control techniques. Generally removable from surfaces, soil penetration variable, toxicity variable. Includes water-in-oil emul- High viscosity, hard to remove from surfaces, tend to form stable emulsions, high specific gravity and potential for sinking after weathering, low substrate penetration low toxicity (biological effects due primarily to smothering). Will interfere with many types of recovery equipment. Nonspreading, cannot be re- covered from water surfaces using most conventional cleanup equipment, cannot be pumped without preheat- ing or slurrying, initially relatively nontoxic, may melt and flow when stranded in sun. ------- tendency to penetrate permeable substrates is variable, and increases as temperatures rise. Toxicity is variable depending on the percentage of volatile components. When weathered or subjected to low temperatures, they commonly become solid and fall into the Class D category. Water-in-oil emul- sions (Mousse) which still flow, generally fit into this class. Class C: High Viscosity. Low Spreading Rate Asphaltic Oils This class normally includes residual fuel oils and heavier asphaltic and mixed-base crude oils which are in the fluid state at ambient tempera- tures. Characteristically viscous, sticky or tarry, and brown or black in color, they generally adhere to substrates and resist removal by flushing. After natural light ends and cutter stock evaporate, their toxicity tends to be low. Biological effects are generally the result of smothering. The ability to penetrate substrates is typically low. Many Class C oils have a specific gravity near or exceeding that of water and may sink. Class C oils will weather to a tar- or asphalt-like consistency and then may be considered as Class D oils. The emulsions formed tend to be stable. Class D; Nonfluid Oils This class includes residual oils, heavy crude oils, some high paraffin crude oils, and weathered oils that are solid or nonfluid at spill tempera- tures. In solid form, they are essentially nontoxic. Class D oils may react as Class A, B, or C at temperatures above their pour point. Oil Identification The criteria for field categorization of oil type are shown graphically in Figure 301-1. The key diagnostic factors are described on the lower left portion of the figure. 300-3 ------- Is the source of the oil known? No Yes Gather information on quantity and type of oil. Is the oil opaque? Yes Does the oil feel waxy? Yes ,, No Is the oil in solid chunks? No Yes DEFINITION OF TERMS OPAQUE: Cannot see through coating of oil. WAXY: Feels slick but is not sticky, can be easily wiped off fingers or hand with a cloth, can be viscous. SOLID OR Does not flow, can have solid CHUNKY: consistency or be soft like putty. STICKY Oil is very sticky and has a thick consistency, OR it not easily removed from hands or fingers VISCOUS: without using detergents or solvent. Type 'C' oil Figure 301-1. Field identification of oil types. 300-4 ------- 302 SLICK MOVEMENT General Slick movement prediction is necessary to determine the location of potential shoreline and/or sensitive area contamination, and for direction of response actions. Helpful data to predict oil spill movement are (listed in order of importance): 1) surface current speed and direction, 2) wind speed and direction, and 3) oil spreading characteristics. An accurate assessment of spill volume is needed to determine cleanup equipment and chemical treat- ing agent requirements. In addition, an understanding of the slick surface behavior is important in the selection of control techniques and treatment dosages. Estimation of Spill Volume Spill volume determines, in part, the amount of equipment, manpower and other resources needed to execute the response. Because early estimates of spill size are often unavailable or of questionable accuracy, first-hand en- sile estimations are generally necessary. The following methods can provide rapid working approximations: • When tankers or oil barge casualties are involved, volumes can be estimated if the cargo capacity and extent of hull damage are known. Although the extent of hull damage and oil loss cannot often be reliably estimated, total cargo capacity (by tank or ship) can be useful in setting maximum spill size. • If a spill occurs during oil transfer, the total spill volume can be estimated if the pumping rate and the elapsed time between leak occurrence and pumping shutdown are known. The maximum pumping rate from the offloading source may be assumed to be the spill rate for a complete transfer, hose rupture, pipeline or manifold fail- ure. Spills resulting from improper flange makeup or from hose leaks would be likely to occur at significantly lower rates. • A rough estimate of spill volume can be calculated by considering slick area and average thickness. Figure 302-1 relates the appear- ance of oil on water to its thickness. These observations hold true for spills less than about 0.25 mm thick. Because large spills require significant time to spread to these thicknesses, a direct measurement of slick thickness would be preferable early in the spill. Prediction of Spill Movement The National Oceanographic and Atmospheric Administration (NOAA), under the NCP, has the responsibility of providing marine environmental data to the OSC. This data includes present and predicted meteorological, hydrological, and oceanographic conditions for the area in question. NOAA has developed computerized oil spill movement prediction models that can be used at the request of the OSC to predict which shoreline areas or offshore amenities are threatened by an oil spill. 300-5 ------- 10 cm 1 cm 0.1 cm 0.01 cm 1,000,000 o o 0.001 cm 0.0001 cm 0.00001 cm AREA COVERED AFTER 24 HR (m2) Shaded area indicates the range of oil slick observations for which thickness and area covered can be determined by appearance Any value below the shaded area would not be visible, and any value above would be a dark brown or black Figure 302-1. Volume, film thickness, appearance, and area covered by oil spills. ------- In the absence of sophisticated predictive modeling, on-scene personnel can predict initial oil slick movements by vector addition of the two main motive forces that apply: surface currents and winds. Observations from actual spill situations have shown that wind will cause an oil slick to move at between 0 and 4 percent of the wind speed, and in the same general direc- tion. The exact percentage appears related to oil viscosity. For estimation purposes, a factor of three percent is generally acceptable. Figure 302-2 gives an example of the vector addition method of oil slick movement predic- tion. The general methodology for use of this technique is as follows: 1. Draw ocean current and wind component vectors in their relative directions and lengths as shown in Diagram 1 (length of vector represents velocity: 10 mm = 0.1 km/hr). 2. Draw a line parallel to the wind vector starting from the tip of the current vector and measuring the exact length of the wind vector, as shown in Diagram 2. 3. Draw a line from the point of origin (present oil slick position) to the tip of the parallel wind vector line in Diagram 3. This final line is the resultant vector which gives the direction and speed of the oil slick movement. The direction can be measured by using the cardinal points of a compass. The speed is determined by the length of the resultant vector. The resultant vector can also be used to estimate slick arrival time at points of interest along the path of movement. In cases where winds and currents are unknown or variable, aerial reconnais- sance is a useful tool for supplying input to predictive estimates, and tracking actual movements. Oil spills eventually cease to increase in size if the spill source is stopped. In such situations, and when conditions are calm, Figure 302-3 can be used to approximate probable spill radius. Calcu- lations are based on a typical light crude oil (CLASS A) and may differ for other oils. Slick Characteristics The preceding discussion assumes the surface distribution of oil within a slick to be more or less uniform. While this assumption is adequate for gross movement and volume estimation, actual slicks are rarely uniform. Since the surface distribution of oil within a slick is important to treat- ment selection, it is useful to understand some basic characteristics of floating oil. Figure 302-4 depicts the typical evolution of a larger slick. The initial slick spread in Zone A is governed by gravity and inertial forces. During this period the slick is relatively thick and its surface distribution tends to remain continuous. As the initial spreading forces decrease and such environmental factors as wind become important, windrow development is common. Zone B indicates the zone of windrow development. In Zone C, addi- tional exposure results in windrow breakup and formulation of "minislicks." Typically the areas around and between minislicks and windrows are covered by 300-7 ------- 1. W-* Current component - 0.3 km/hr towards the north 10 mm = 0.1 km/hr Present oil slick position Wind component 3% of 10 km/hr from the northwest 2. 3. Figure 302-2. Vector addition for 10 km/hr NW wind and 0.3 km/hr north current. 300-8 ------- 16000 14000 - Figure 302-3. Maximum oil spill radius versus time (Fay-Hoult model). 300-9 ------- oi-ooe ------- thin sheens. These sheens reflect differential spreading rates encountered with some oils and the release of volatile fractions of more viscous oils. If sufficient time and distance are available, a slick will ultimately disappear in Zone C. If the slick movement is impeded, however, remaining floating material may concentrate. This occurs commonly in response to the presence of shorelines and coastal currents, and is shown on Figure 302-4 as Zone D. 300-11 ------- 303 FIRE/EXPLOSION HAZARD The threat of fire and explosion is associated with marine oil spills. The following rules should always be considered in the initial evaluation of an oil spill: • Until otherwise established, all oil spills - particularly those involving gasolines or continuous spillage (pipeline breaks, well blow outs, etc.) should be considered as fire hazards. • Any spills (light refined products and light crude oil in partic- ular) involving confined airspace in which vapors may concentrate (shipboard tankage and machine spaces, under docks, etc.) should be considered potentially explosive. Chemical dispersants may be particularly useful in fire control and reduction of fire and explosion hazard. In situations where such hazards threaten human life and property, federal regulations allow the On-Scene Coordinator to wave normal use restrictions and take immediate action. Figure 303-1 is a decision guide to assist in the determination of hazards and appropriate actions. As with any general guide, exceptions can exist. Each case should be evaluated with utmost caution. Fire hazard will normally diminish rapidly with time and distance from the source. When in doubt, the potential fire hazard an oil spill presents can be established by: (1) determining flash point of the oil, or (2) determining hydrocarbon vapor content of the air near the surface of the slick by using an explosive gas detector The flash point is the temperature at which the vapors rising from the surface of the oil will ignite with a flash of very short duration when a flame is passed over the surface. If the flash point of the spilled oil is close to or below the ambient air temperature, the oil poses a fire hazard. The minimum flash point and flammability limits for common refined petroleum products are given in Table 303-1. Prevailing weather conditions can affect the hazard potential of the spilled oil. A calm, hot day could accentuate vapor buildup. Strong winds (greater than 15-20 knots), on the other hand, will tend to disperse the vapors below the flammability limit, considerably reducing the fire hazard. In addition to the oil, flammability of the dispersant should be consid- ered in the control of fire and explosion hazard. Hydrocarbon base disper- sants should not be applied for control of fire hazard if nonflammable (water solvent) types are available, nor should they be used in the vicinity of open flame. Flash point data for EPA approved dispersants is given in the Annex X data submissions. 300-12 ------- O O Is material burning' Refined Products \ Crudes Low Flash Point High Flash Point \ 2 JJnconfmed Confined Confined Continuous Discharge Unconfmed Yes Is there a hazard to life or is property endangered? (Consider areas of potential spread) No -\ V Evacuate area Control spark sources Ventilate Allow to dissipate naturally Proceed with conventional actions (consider burning) Evacuate area Control spark sources Ventilate Allow to dissipate naturally Consider dispersion to reduce hazard if life/property theatened Check vapor levels Proceed with conventional actions Consider burning Consider chemical dispersion Allow to burn Figure 303-1. Decision guide - fire hazard and response. ------- Table 303-1. FLASH POINTS AND FLAMNABILITY LIMITS OF REFINED PETROLEUM PRODUCTS Aviation Gasoline Automobile Gasoline Naptha Kerosene Flash Point (°C) -59.8 -57.0 + 52.0 -20.9 23.6 + 29.1 Flammable Limits in Air 1. 27-7.17, 1.42-7.4% 0,.9%-6.0% 0.7%-5% Jet Fuels: JP-1 JP-3 JP-4 JP-5 23.6 29.1 + 51.3 -37.6 - -15.3 45.8 0.7-5% Not Known 1.3%-8.0% 0.6%-4.6% Diesel Fuels ID 2D Residual Fuel Oils 23.6 37.4 I ,,3-6.0% 1.3-6.0% No. 4 No. 5 No. 6 >40.2 >40.2 >51.3 1-5% 1-5% 1-5% Source: CHRIS, Hazardous Chemical Data, U.S. Coast Guard CG-446, 1974. 300-14 ------- SECTION 400 CRITERIA FOR DISPERSION OF OIL AT SEA 401 GENERAL This section provides a rationale for determining, case-by-case, the acceptability of chemical dispersion of oil at sea. This rationale, pre- sented graphically in Figure 401-1, consists of a series of basic questions. Does the spill present a threat to shorelines or sensitive areas or ameni- ties? If a threat is identified, is it probable that conventional control and recovery actions will be adequate? Is the oil type dispersible, and can an effective dispersion operation be implemented? Are the probable impacts associated with dispersed oil less than those expected without such action? The following subsections provide criteria for evaluating these basic ques- tions . 400-1 ------- Are shorelines or sensitive areas threatened ? (302, 402) NO o o N3 YES Allow to disperse naturally Are conventional control and recovery techniques adequate? (403) Are impacts associated with dispersion less than with other options ? (406, 407) YES Dispersion acceptable Treat onshore Implement Figure 401-1. Decision guide - dispersion of floating oil. ------- 402 IDENTIFICATION OF THREATENED AREAS In Section 302 general slick movement is projected. Amenities in the general path of movement including special features, resources, and uses that are of particular biological, physical, or cultural importance can be iden- tified and plotted. The relative importance of amenities in an area can vary with the season, severity, and duration of the expected impact and potential for recovery. Because of the high visibility of special features, resources, and uses in an area, and of the limitations of time, manpower, and equipment in responding to a spill, rapid identification of the amenities becomes a critical part of the dispersant question. Local and regional experts can provide necessary information on the nature and location of relevant environ- mental concerns. In general, the probable effects of oil and oil dispersions should be considered for the general amenities listed in Table 402-1. This table also provides brief evaluation criteria. 400-3 ------- TABLE 402-1. SPECIAL FEATURES, RESOURCES, AND USES 1. Rare, Threatened, Endangered, or Protected Species • Any species on federal or state special status lists. • Relatively few expected in marine areas, some in estuaries, most infresh water. • Sensitivity will depend on the reason the species uses the aquatic habitat, duration of use, importance of the habitat to successful completion of the species life cycle, and public and political- concern for the species. • In general, sensitivities in decreasing order are: 1) resides in aquatic habitat and completes whole life cycle in one place, 2) habitat essential for breeding purposes, 3) habitat essential for feeding purposes, and 4) habitat essential for resting and other intermittant uses. 2. Reserves, Preserves, and Other Legally Protected Areas • Areas protected by some legal mandate or areas locally recognized as important for scientific or ecological reasons. • Areas of special biological significance. • Ecological preserves. • Wildlife'and/or waterfowl sanctuaries and refuges. • Scientific research areas. 3. Waterfowl Rookery or Concentration Areas • Shoreline areas (rookeries) used for breeding, nesting, and fledging activities. • Open-water areas (concentration) used for resting, feeding, and breeding • Sensitivity will depend on which species are present; number, extent, reason for use of the habitat; and susceptibility to oil impacts. • In general, sensitivities in decreasing order are: 1) diving ducks, 2) swimming and surface-feeding waterfowl, 3) gulls, terns, etc., 4) shorebirds and 5) water-associated birds. 400-4 ------- TABLE 402-1 (Continued). SPECIAL FEATURES, RESOURCES, AND USES 4. Mammal Rookeries, Calving Grounds, and Concentration Areas • Sensitivity will depend on which species are present; number, extent, reason for use of the habitat; and susceptibility to oil and dispersion impacts. • In the marine environment, rookeries, and calving grounds are generally more sensitive to oil impacts than are concentration (haul-out) areas. 5. Species of Commercial Importance • Clams and oysters. • Crabs, shrimp, lobsters. • Finfish (including spawning areas offshore, intertidal, and in shallow streams). • Algae. • Aquaculture sites (shellfish, algae, finfish, lugworms etc.). • Fish bait (lugworms, clams, ghost shrimp etc.). • Sensitivity will depend on season, economic value of the local harvest to the area, and susceptibility to oil and dispersion impacts. 6. Species of Recreational Importance • Clams, oysters, mussels. • Crabs, shrimp, lobsters, ghost shrimp, lugworms, etc. • Finfish (shoreline fishing areas, spawning areas for grunnion, salmon, bass, and other fish). • Abalone. • Sensitivity will depend on season, use, and susceptibility to oil and dispersion impacts. 7. Ecologically Productive Areas • Eelgrass beds. • Marshes and other wetlands. 400-5 ------- TABLE 402-1 (Continued). SPECIAL FEATURES, RESOURCES, AND USES • Estuaries. • Coral Reefs. • Mangroves. • Some kelp beds. • Areas critical to survival of local population of species known to be of major ecological significance in structure, function, stability, and survival of the aquatic community. 8. Areas of Beach Stabilizing Vegetation • Vegetation stabilizing sand dunes important to protecting backshore areas. • Vegetation preventing shoreline banks from erosion. 9. Areas of Geological Significance • High erosion potential areas. • Specially designated geological study areas. • Fossiliferous formations. • Mineral-bearing sediment deposits. 10. Areas of Recreational Significance • Marinas and boat harbors. • State parks and beaches. • Sunbathing, surfing, and swimming beaches. • Beaches with shore-front homes. • Beaches with shore-front hotels and restaurants. • Beaches adjacent to roads and highways. 11. Areas of Commercial or Industrial Significance • Cooling water intakes. • Process water intakes. 400-6 ------- 403 ASSESSMENT OF CONVENTIONAL CONTROL AND RECOVERY Federal policy advocates physical control and recovery of spilled oil using conventional techniques (i.e., booms, skimmers, etc). The adequacy of physical control and recovery of an oil spill at sea is dependent on a vari- ety of factors including: • prevailing meteorological and oceanographic conditions • physical properties of the spilled oil • availability of suitable oil spill control and recovery equipment The decision guide (Figure 403-1) illustrates how these factors can be evaluated to determine the feasibility of containing and cleaning up an oil spill at sea. Sea State Conditions The first factor to consider is the prevailing and predicted meteorolo- gical and oceanographic conditions, which can be expressed as sea state. Figure 403-2 illustrates how sea state can be estimated from wind speed and wave heights. It also indicates the limitations of containment booms and oil skimmers for various sea states. Generally, even containment booms and skim- ming equipment rated for open sea conditions quickly lose effectiveness once sea state 3 is surpassed. Therefore, if a sea state of 4 (i.e., breaking waves over 5 feet) or greater is present and predicted for several days, mechanical containment and cleanup techniques would be of limited effective- ness or ineffective in controlling the spill. Oil Properties Skimmer recovery is affected by the physical state of the oil. High viscosity and nonflowing oils are more difficult to recover and can consider- ably reduce a skimmer's effectiveness. Logistics The availability of sufficient equipment and response time for implemen- tation comprises the final assessment factor. A checklist for determining the feasibility of containment and skimming operations is given in Table 403-1. If the answer to all questions is affirmative, then booming and skim- ming operations should be feasible. If one or more answers are negative, the physical control of the spilled oil might not be totally effective, and con- sideration is given to other alternate or supplemental techniques (i.e., chemical treatment). The length of boom needed to contain a fresh oil slick at sea is depen- dent on the time required for its deployment and the volume of oil spilled. As a slick spreads and thins out on the water surface it tends to break into long narrow windrows in response to wind and wave conditions. This action greatly increases the slick perimeter and consequently the amount of boom needed for containment. 400-7 ------- Are present and/or predicted sea state conditions greater than sea state 3 ? Determine Type of Oil 1. Light Distillate Fuels 2. Low-Medium Viscosity Distillates and Crudes Skimming operations normally effective Evaluate adequacy of containment and skimming operations 1. High Viscosity Distillates and Weathered Crudes 2. Nonspreading Oils Skimming operations only partially effective Mechanical cleanup and control equipment will not be effective. Examine dispersant applications ./ \ if not 100% adequate Figure 403-1. Assessment guide for mechanical control and recovery. 400-8 ------- o 1 VO * 1. WIND VELOCITY (knots) 4 2. BEAUFORT WIND AND DESCRIPTION 1 Air I I 5 6 I I 2 as. I I 7891 I I 3 0 4 Moderate Breeze I 5 I 20 | Fresh Breeze 3. REQUIRED FETCH (miles) Fetch is the number of miles a given wind has been blowing over open water. 4. REQUIRED WIND DURATION (hours) Duration is the time a given wind has , been blowing over open water. I I 5 20 I | 200 I I i 30 6 Strong Breeze | 7 Mod- erate Gale 300 4 8 Fresh Gate I I 0 50 60 I 9 Strong Gale 10 ,.. W,hole Storm Gale I 400 500 600 700 25 I If the fetch and duration are as great as indicated above, the following wave will exist. Wave heights may be up to 10% greater if fetch and duration are 5. WAVE HEIGHT - CREST TO TROUGH (feet) 6. SEA STATE AND DESCRIPTION 1 1 Smooth 4 WhitP 2 Caps Form 2 3 Slight Moderate I 6 8 I 4 Rough I 10 I 5 Very Rough I I 30 I I I 35 I conditions greater. I 15 I 20 6 High I ! 25 30 | | I I 40 50 60 7 Very High | | 8 Precipitous •« — Small skimmers and booms with freeboard less than 16" — ^s. Large skimmers and booms ^^ Note' Corresponding values lie on a vertical line. This table applies only to waves generated by the local wind and does not apply to swell originating elsewhere. WARNING: Presence of swell makes accurate wave observation exceedingly difficult. NOTE: a. The height of waves is arbitrarily chosen as the height of the highest 1/3 of the waves. Occasional waves caused by interference between waves or between waves and swell may be considerably larger. b. The above values are only approximate due both to lack of precise data and to the difficulty in expressing it in a single easy way. Figure 403-2. Wind waves at sea. ------- TABLE 403-1. CHECKLIST FOR LOGISTICS OF CONTAINMENT AND RECOVERY OPERATIONS Containment or Protection Yes No 1. Is there sufficient length of boom(s) available for use (Length needed - approximately 60% of the perimeter of the oil slick or slicks or 125% of perimeter of area to be protected) 2. Are vessels and crews available to transport and deploy boom 3. Can the boom(s) be deployed before the slick con- tacts shoreline (Compare ETA of oil on shore with estimated deployment time of booms) Recovery 1. Are skimmers available which can operate under open sea conditions 2. If so, is the combined pickup rate of the skimmers sufficient to pick up most of the oil in a reasonable time* 3. Is there sufficient storage available for the skimmers to offload recovered oil without dis- rupting or delaying the skimming operations *If the discharge is continuous, can the skimmers pick up the oil volume discharged daily, or if the discharge is of short duration, can the skimmers pick up the spilled oil in 10 to 15 days. 400-10 ------- The areal extent and thickness of an oil slick is important in deter- mining the number of skimmers needed for recovery operations. The amount of oil a skimmer encounters during a skimming operation is the primary factor in determining recovery rate. Many large ocean skimmers are capable of pumping 6,000 to 10,000 gallons of oil per hour; however, that large a volume of oil would rarely be encountered. Figure 403-3 can be used to estimate the encounter rate of a skimmer with a known sweep width and skimming speed for various surface concentra- tions of oil. The encounter rate multiplied by the skimmer efficiency gives an estimate of oil recovery. For instance, if a skimmer with a sweep width of 20 feet was operating in a 0.1 mm oil slick at a skimming speed of 2 knots, it would encounter approximately 600 gallons of oil in one hour. If the skimmer has a recovery efficiency of 90 percent (i.e., it recovers 90 percent of the oil it encounters) it would pick up approximately 540 gallons of oil per hour. The encounter rates do not reflect any time lost for manu- vering, offloading of recovered oil or transit time to an offloading site. Therefore, when estimating skimmer recovery rates only the actual time spent in skimming should be used to determine an expected daily recovery rate. Partial Effectiveness In many cases conventional control and recovery techniques may be lim- ited to certain parts of the spill due to adverse conditions or the sheer magnitude of the spill. In this event, both chemical treatment and conven- tional techniques should be considered to provide maximum overall effective- ness and minimum damage. 400-11 ------- 10.0 5|S Ikt 2kt 3kt 4kt 5kt 11,000 20 SO 100 200300 500 1.000 40 100 200 4006001,000 2.000 6O 150 300 6009001,500 3,000 80 400 800 1,200 2,000 4,000 -U 100 250 500 1,0001.5002,5005.000 GALLONS PER HOUR 10,000 20,0190 30.000 40,000 50,000 1,100 5 IE LU O u. O O -110 11 Figure 403-3. Encounter rates of skimmers for different sweep widths and vessel speeds versus slick thickness. 400-12 ------- 404 OIL DISPERSABILITY Dispersant Selection The effectiveness of any particular dispersant application is dependent on a combination of factors including oil type and condition, dispersant type and dosage, mixing energy, and temperature. Typically, dispersants are most effective on the least persistent (more volatile) oils and less effective on the more persistent oils. In some cases (i.e., nonspreading oil) chemical treatment may have little or no effect. Dispersants contain surface active agents which reduce the oil-to-water interfacial tension. In the presence of energy supplied by natural or mechanical mixing - or in some cases by molecular diffusion, formation of oil droplets is enhanced. Coatings on each oil droplet prevent their reforming. Dispersant formulations may be divided into three basic types: those which contain surface active agents carried in a hydrocarbon (hydrocarbon base) solvent; those which contain surface active agents carried in an aqueous solvent (commonly water or alcohol-water base); and those which contain high concentrations of active ingredients in relation to the carrier (concen- trate). Table 404-1 lists the compatibility of major oil categories with dis- persant types. From this table, a few general rules can be developed. • Oils having a pour point less than the ambient water tem- perature cannot be successfully chemically dispersed. • High viscosity (low spreading rate oils) may be difficult to disperse effectively. 400-13 ------- TABLE 404-1. OIL TYPE: DISPERSANT COMPATABILITY Oil Category Water Base Dispersant Type Hydrocarbon Base Concentrate A Low viscosity, high spreading rate oils and products B Moderate or high vis- cosity waxy oils C High viscosity low spreading rate oils D Non-spreading oils X X Chemical dispersion not effective ^Dispersion of highly volatile products not recommended except to control extreme fire/explosion hazard ^Effectiveness may be limited 400-14 ------- 405 DETERMINATION OF APPLICATION TECHNIQUE, PRODUCT, AND DOSAGE Application Technique Application techniques compatible with each generic type of dispersant are listed in Table 405-1. A number of techniques may be applicable to each type, however, there is no established formula for selecting among the pos- sibilities. Selection may be dictated by dispersant and equipment availabil- ity, any limiting operating conditions, and spill magnitude. In the event of a large spill, all available systems may be required. Factors to consider in selecting the optimum technique should include sea state, spill characteristics, logistics, desired treatment rate, need for supplementary mixing energy, and cost. Table 405-2 can assist the user in the selection process by comparing advantages and disadvantages of respective application techniques. Product Selection A dispersant product must comply with federal requirements concerning the submission of technical data to be considered for use. Figure 405-1 pre- sents a product selection approach which uses a screening and ranking pro- cess. Generally, products are generically identified by their manufacturer. In cases where they are not, they may be categorized using data required by Annex X. Candidate products can be listed in the dispersant selection work- sheet provided in Figure 405-2. By recording appropriate data, products having undesirable properties can be preliminarily screened. Undesirable properties, criteria for their evaluation, and data references required by Annex 10 are listed in Table 405-3. The acceptability of each criteria will probably involve subjective user evaluation. Products remaining after this screening are then ranked for relative effectiveness and toxicity using the test data required by the worksheet. These data are based on laboratory tests and are therefore only suggestive of what may be encountered in the field. Dosage Most products are supplied with dosage recommendations, normally in terms of dosage per acre or as a dispersant-to-oil ratio. These recommenda- tions are based on manufacturers' experimentation'and experience and are suitable starting dosages. Dosages beyond that required to achieve a satis- factory dispersion should not be used. Manufacturers' representatives may be consulted for unusual oils or conditions. Typically, experimentation with initial applications will be required. In field situations oil distribution is commonly irregular and quanti- ties difficult to estimate. Under such circumstances an average or optimum dosage must be used. Accordingly, some manufacturers supply a recommended dosage per acre for general use. Such dosages are acceptable for initial application, with adjustments made as appropriate after test applications. For products where dosage is given in terms of a dispersant-to-oil ratio, calculation of a usable application rate is necessary. Figure 405-3 400-15 ------- TABLE 405-1. APPLICATION SYSTEM: DISPERSANT TYPE COMPATIBILITY o o i Application System Hand Spray Neat Vessel Spray Systems < 20 GPM Neat Injection into seawater stream > 20 GPM Injection into seawater stream Eduction into seawater stream Fire Systems (portable and fixed) Eduction into seawater stream Aerial Systems Neat Dispersant Type Water. Base X X X X X X X Hydrocarbon Base X X X Concentrate X X X X X X ------- TABLE 405-2. ADVANTAGES AND DISADVANTAGES OF MAJOR DISPERSANT APPLICATION SYSTEMS SYSTEM ADVANTAGES DISADVANTAGES Hand Spray Vessel Systems (General) Vessel Systems (<20 GPM) Vessel Systems (>20 GPM) Vessel Systems (Fixed fire moni- tor or pump/hose systems) Vessel Systems (Trained fire monitor or pump/ hose systems) Aerial Systems (General) Aerial Systems (Helicopter) Aerial Systems (Light agricul- tural aircraft) Aerial Systems (Heavy aircraft) Equipment readily available, spray may be accurately directed May be used on vessels of oppor- tunity, larger vessels provide high dispersant capacity and duration on station, effective in treating windrows Packaged systems available (WSL- type), can be used in conjunction with breaker boards to supply ad- ditional mixing energy, good con- trol of dosage Packaged systems available, can be used with breaker boards to sup- ply additional mixing energy, with dilutable dispersants effective operating characteristics extended Pumps, monitors, eductors commonly built into vessels, minimal oper- ator requirements, spray imparts some mixing energy, can operate in slightly higher sea states than outrigger systems Dispersant may be directed to oil concentrations, may use existing fire systems, spray may be used for mixing High application rates and low response times, can operate in higher sea states than most ves- sels, better visual monitoring of slick than vessels Highly manueverable, rapid re- sponse, many systems adapt to most aircraft, operating base requirements minimal Fair availability in most areas, adaptation of agricultural sys- tems rapid and simple (nozzle modification), good maneuver- ability, minimal airfield require- ments (dirt air strip) High capacity and extended oper- ating range Limited coverage rate, dosage difficult to control, no provision for external mixing Slow operational and transit speeds limit total coverage per day, operation in high seas may be hazardous, spotter aircraft may be required Flow rate too low for eduction of con- centrate dispersants, outriggers and breaker boards limit maximum opera- tional sea state Output is generally too high for heat applications, outriggers and breaker boards limit maximum operational sea state Spray distribution may be irregular No control of dosage, operator(s) required Operation precluded in low visibility, no provision for adding external energy, high or cross winds tend to interfere with application Limited dispersant capacity, cargo must be traded for fuel for long-range appli- cations Limited dispersant capacity, typically must operate in sight of land, may be difficult to achieve desired single- pass dosage Systems not common, maneuverability limited during application, spotter planes required, full-size airfield required, may be difficult to achieve desired single-pass dosage 400-17 ------- o o I I—' 00 Generic Dispersant Cf Product A Product B 1 1 Product C 1 Product D 1 ) y K \ / y K V K ) V Undesirable Property Screening K Acceptable j V k k Relative Effectiveness Highest , V k Lowest j Relative Toxicity Lowest , k Highest ) y y K Unacceptable . Relative Ranking 1 2 3 4 Do not use Figure 405-1. Product selection procedure. ------- 1. OPERATIONAL PARAMETERS Product A B C D Special Handling Flash Point Pour Point Acceptable? 2. CHEMICAL CONSTITUENTS Product A B C D 3. EFFECTIVENESS - Product A B C D Solvents Additives NO. 2 NO. 6 (chose elos* M<*»* SSSSn, Acceptable? sst type) Initial Relative Rank Final Relative Rank 4. TOXICITY Product A B C D P. Promelas Dispersant Disp.+Oil Rel. Rank F. Heteroclitus Ditpersant Disp.+Oil Rel. Rank A. Sal ma Oispersant Disp.+Oil Rel. Rank Figure 405-2. Product selection worksheet (using data required by Annex X). 400-19 ------- TABLE 405-3. PRODUCT SCREENING CRITERIA PROPERTY EVALUATION CRITERIA ANNEX X REF. Special Handling or Worker Safety Re- quirements Shelf Life Flash Point Excessive special handling or worker safety precautions are undesirable Age of product stock should be less than stated shelf-life (check for component fractionation, etc.) Flash point should not be low enough to create fire hazard or ignite if used near fire 2003.3 - 4.4 2003.3 - 4.5 2003.3 - 4.9 Pour Point Heavy Metals or Chlorinated Hydrocarbons Pour point of product should be below ambient water temp. Formulations should not contain appreciable quantities of heavy metals and/or chlorinated hydro- carbons 2003.3 - 4.10 2003.3 - 4.17 Availability Short-term product availability should be sufficient for initiation of use None 400-20 ------- 10.0 - 5.0 - 1.0 - UJ 0.5 - O I I- O 0.1 _l V) 0.05 - 0.01 - 11,000 1.0 (Source: SC-PCO, f978) 10 100 1,000 1,100 O O cc. o < 110 O Q. 11 10,000 Figure 405-3. Dispersant requirements at manufacturer's recommended application ratios (gallons per acre). 400-21 ------- has been prepared to speed this calculation. To use this graph, it is neces- sary to estimate the approximate volume of oil per area. Using the recom- mended application ratio, the dispersant requirements in U.S. gallons per acre can be determined. Example: Thickness of the slick is estimated at 0.1 mm. The manufac- turer recommends his product be used at one part dispersant to 20 parts oil. Using the graph, a dosage requirement of 5 gal- lons per acre can be determined. Dosage adjustment may be necessary and will require trial applications and visual assessment. In some cases multiple applications may be required to achieve the desired dosage. The lowest dosage which results in effective dispersion represents the most cost-effective and environmentally acceptable application rate. To visually assess the effectiveness of an application, dispersion can be thought of as a two-phase process. Initially, oil and dispersant are mixed and individual droplets formed. Although technically dispersed, drop- let density may be sufficient to give the appearance of an intact slick, especially if mixing energy is low. Distinguishing dispersed oil at this stage can be extremely difficult. The time required for the initial phase of dispersion may vary from instantaneous to several minutes,, depending on the product and mixing energy. Nature conducts the second phase of dispersion by physically separating the treated droplets both vertically and horizontally. Oil is being rapidly dispersed when a coffee-colored cloud forms in the water column after treatment. In an effective final dispersion,, little or no floating or reforming oil should be detected. 400-22 ------- 406 DISPERSED OIL MOVEMENT AND CHARACTERISTICS Dispersed oil forms a plume in the upper water column which may or may not travel in the same direction and speed as would untreated floating oil. Since ecologic effects associated with dispersed oil and dispersant are directly related to their nature and concentration, prediction of plume move- ment, composition, and concentration at any point of interest is desirable. This section provides guidelines for field estimation of mixing depths in the water column, initial concentration of oil and dispersants, direction of plume movement, concentration of oil and dispersants at various points of interest, and general types of degradation which can be expected. Evaluation of dispersed oil movement and characteristics includes: • estimation of initial mixing depth • estimation of initial concentrations of oil and dispersant over a specified mixing depth • prediction of movement of the dispersed material • estimation of maximum plume center line concentrations at any point of interest • evaluation of probable changes in composition with time Figure 406-1 is a worksheet for the computation of dispersed oil move- ments and dilution. Estimation of Initial Mixing Depth Dispersants and dispersed oil will mix relatively rapidly with near sur- face waters by turbulent diffusion and other processes. Mixing depth is con- trolled largely by the amount of available energy supplied by wind waves, swells, tidal currents, wind-induced currents, density currents, and artifi- cially supplied energy (breaker boards, fire streams, propellers, etc.). Determination of "initial" mixing depth is necessary for predictive modeling of the dispersion plume and may be conducted by several methods. Direct Observation. Mixing depths may be monitored visually in the field using divers (visibility permitting) or more precisely with field chemical measurements. Calculation. If direct observations are not possible, initial mixing depths may be approximated from observable features such as wave height. Although no simple formulas exist for vertical diffusion and mixing processes in the ocean, the guidelines presented in Table 406-1 may be used. When using these guidelines, the greatest applicable mixing depth should be selec- ted. Field observations suggest oil dispersed in the open ocean will remain near its initial mixing depth unless the mixing phenomenon changes. 400-23 ------- INITIAL MIXING DEPTH Wind Waves Swell Artificial Max INITIAL CONCENTRATION (Co) Oil Dispersant SURFACE WATER MASS MOVEMENT Direction Speed THREATENED AREAS 1 (Specify) Dist ETA Cmax. 2 * 3 Figure 406-1. Dispersed oil movement worksheet. 400-24 ------- TABLE 406-1. ESTIMATED INITIAL MIXING DEPTHS Situation Mixing Mechanism Depth Guideline Open Ocean Windwaves Swell Near Shore Mixing depth highly vari- able, may mix to bottom Artificial Breaker Boards* Mixing Modified Breaker Boards* Vessel Wake and Propeller* Fire Stream* 50% of observed wave height 10% to 25% of observed swell height 1/2 meter 2-3 meters Propeller Depth 1/2 Meter *Smith, G.F. and McCracken, W.E., 1977, "Techniques for Mixing Disper- sant-Treated Oil Slicks into the Water," Proceedings, 1977 Oil Spill Conference. 400-25 ------- Estimation of Initial Concentrations of Oil and Dispersants The initial concentration of oil and dispersant introduced into the water column can be calculated on the basis of oil thickness and dispersant applied, effectiveness of the dispersion (percent oil remaining dispersed), and the initial mixing depth. Figures 406-2, 406-3, 406-4, and 406-5 may be used to calculate concentration of dispersed oil (in parts per million) for various depths and degrees of dispersion effectiveness. To use these figures, the volume of oil present must be estimated. It may be entered in the figures as average slick thickness or as estimated oil per unit area. To reach an acceptable representation of total oil entering the water column under such circumstances, oil volume estimates should be based on averages over large areas (acres). Dispersion effectiveness testing is among the data required by Annex X. Test data is given in terms of percent initial dispersion (after 10 minutes) and percent final dispersion (after 120 minutes) for no. 2 and no. 6 fuel oils. If used carefully, this data may be used to estimate effectiveness sufficiently to permit planning-type calculations. Effectiveness should be approximated from Annex X data (rounded to the nearest 25 percentile) for the most similar oil type. Final effectiveness values given in Annex X data are probably most representative. For any particular dispersant, final effec- tiveness values that are greater than the initial values suggest the contin- uing effect of the dispersant. Final values that are less than initial values can be associated with the resurfacing of larger oil droplets with time. Based on the mixing depth previously determined, the calculated dispersion concentration may be read directly off the figures. (Values pro- vided by the figures do not reflect overall or component losses resulting from dissolution or other processes during weathering). Example: Estimate the concentration of No. 6 fuel oil dispersed by pro- duct A in seas with 2 meter wave height. No supplementary mixing is used. From Table 406-1 the estimated initial mixing depth is half the wave height, or 1 meter. Test data required by Annex X for product A suggests a final effectiveness with No. 6 fuel oil of 40 percent for a dispersant/oil ratio of 1:10. Average thickness of the slick is estimated at 0.1 mm. Using Figure 406-3 (50 percent effectiveness) concentration of dispersed oil in the upper meter of water can be estimated at 50 ppm. Estimation of dispersant concentration in near surface waters is less complicated than for oil, as dispersant application is more or less uniform. Based on an application in gallons per acre, Figure 406-6 can be used to estimate dispersant concentration at depth. For example, the dispersant con- centration in the upper meter of water at an application rate of 10 gallons per acre is approximately 10 ppm. Figures 406-7, 406-8, 406-9, and 406-10 can be used to estimate water column concentrations when dosage is given as a dispersant-to-oil ratio. For example, it is desired to estimate the dispersant concentration in the upper 3 meters for a slick averaging 0.1 mm at an application ratio of 1:20. Using Figure 406-8 the concentration can be read as approximately 1.2 ppm. 400-26 ------- o o I 0.01 1.0 10.0 100.0 1,000.0 10,000.0 Figure 406-2. Concentration of dispersed oil at various depths at 25 percent dispersion effectiveness (ppm). ------- a i CD 0.01 10.0 1000 1,000.0 0 10,000.0 Figure 406-3. Concentration of dispersed oil at various depths at 50 percent dispersion effectiveness (ppm). ------- .p- O O I 0.01 0.1 1.0 10.0 1000 1.000.0 Figure 406-4. Concentration of dispersed oil at various depths at 75 percent dispersion effectiveness (ppm). ------- o o I y o o _l in 0.01 10.0 100.0 1,000.0 10.000.0 Figure 406-5. Concentration of dispersed oil at various depths at 100 percent dispersion effectiveness (ppm). ------- o o I 0.01 0.1 1.0 10.0 100.0 1,000.0 Figure 406-6. Dispersant concentration (ppm) homogeneous mixing at indicated depth. ------- o o I LU Lt O < IT ill Q. o CO z o _l < 0 1 1 0 10.0 100.0 Figure 406-7. Concentrations of dispersants in upper meter for various D/O application ratios (ppm). ------- O O I LU z * O X O _l c/I LU oc CJ cc LU a. _l 5 u_ o z o _1 < 0.001 0.01 1000 1 1,000.0 Figure 406-8. Concentrations of dispersants in upper 3 meters for various D/0 application ratios (ppm). ------- .p- o o I E £ v: o i cc o < QC LU Q. o LL O 2 O _J _l < 0.1 i.o 10.0 100.0 1 1,000.0 Figure 406-9. Concentrations of dispersants in upper 10 meters for various D/0 application ratios {ppm). ------- -e- o o I U) HI DC O < DC LU CL O CO z o o 0.001 0.01 1.0 10.0 100.0 1 1,000.0 Figure 406-10. Concentrations of dispersants in upper 30 meters for various D/O application ratios (ppm). ------- Prediction of Movement of the Dispersed Oil and Dispersant In most cases the movements of floating oil are dominated or strongly influenced by wind. Once dispersed into the water column, however, the effect of wind diminishes and other processes including oceanic and nearshore circulation may be more important. The direction and rate of the near sur- face water movement must be estimated for each situation. Sufficient hydro- graphic information may be available to permit estimation of movement and direction by graphic methods. If sufficient information is not available, direct field measurements of water movement such as with dye-drops and sub- sequent tracking or by tracking of subsurface drogues may be required. Estimation of Plume Centerline Concentrations Based on diffusion theory (Fickian) for surface plumes in oceanic envi- ronments, it is possible to estimate the theoretical maximum concentration of unaltered oil and dispersant at any desired downcurrent distance. Resulting concentrations will be extremely conservative in that evaporation, dissolu- tion, and other subtractive processes cannot be directly considered due to lack of representative decay or rate constants. The basic formula* for cal- culation of maximum plume centerline concentration is: 3/2 (1+2/3 C = C erf max o x where: 0 - = with C = maximum concentration in plume at distance (x) max ^ downcurrent C = initial concentration at initial mixing depth x = distance downcurrent (cm) b = initial plume width (width of treatment zone perpendicular to direction of movement) (cm) U = average current velocity (cm/sec) a = 0.01 cgs units (factor relating horizontal eddy diffusivity to lateral plume spread) erf = standard error function which is defined as *Note: The model presented is based on standard ocean outfall design prac- tice. The objectives of the original model and properties of the materials it deals with are felt to be reasonably similar to the oil dispersion issue. 400-36 ------- -t2dt erf x The equation may be solved in terms of the ratio C : C by calcula- /, t max ° ting p x/b where: x 0.12 x Ub 2/3 The equation may be solved in terms of the ratio C : C by calcula- ting the factor x/b and using the graph provided in Figure 40o-ll. Para- meters used in the calculation of x/b can all be readily estimated in the field. It is important to note that concentrations projected using this formula can be taken as maximum values. Not included in the calculation are decay factors such as evaporation, photo oxidation, biodegradation, and so on. Changes in composition due to these factors are discussed in the following section. Additionally, when applying the formula it should be kept in mind that the resulting dispersion may not be uniform. In cases where dispersion is not totally effective, the amount of oil actually dispersed in the water column can be reestimated and concentrations recalculated. In such instances, consideration must be given to assessment of the fate of the resurfaced oil. Incomplete oil dispersion should not seriously affect the calculation of dispersant concentrations in the water column. Example: Estimate the water column concentrations of oil and disper- sants where the dispersion plume is expected to encounter a shellfish bed. At the time dispersion can be implemented, the floating slick has spread to a width of approximately 1000 feet (b = 3.05 x 10 cm). Water velocity (^) has been measured at 0.3 knot (15 cm/sec). The shellfish bed is 20,000 ft (6.1 x 10 cm) from the dispersion line. Using data from a previous example, initial concentrations (C ) in the surface meter were estimated at 50 ppm dispersed oil and 10 ppm dispersant. Therefore: x & - b 0.12 x 0.12 (6.1 x 10 ) 15(3xl04) 2/3 - 5.04 Using Figure 406-11 the max ratio can be determined as 400-37 ------- 8C-001? MAXIMUM CONCENTRATION, to 8 8 S o, §| fi Q 3 o CD II 3 3 131 o cr|x o 11 8 DO ;o w TO o-ix o ca O o> X DILUTION FACTOR, C0 ------- 0.15. Applying this ratio, maximum concentrations at the shellfish bed can be calculated as 7.5 ppm oil and 1.5 ppm dispersant. Travel time for the plume can be calculated at about 11 hours. During this time a substantial loss of light molecular weight hydrocarbons can be expected, decreasing both the total con- centration, and reducing toxic properties. Evaluation of Changes in Composition with Time Toxic effects are generally associated with lower weight carbon mole- cules (C..-C.., and lower), most of which will dissolve or evaporate in the early hours or the spill. Evaporation will usually account for the greatest percentage of loss. Table 406-2 presents typical evaporative/dissolution losses with time and wind exposure. The data indicates most of the lighter, more toxic fractions of oil are lost within 24 hours. Field evidence sug- gests that dispersion can increase the naturally occurring loss rate due to evaporation and dissolution. 400-39 ------- TABLE 406-2. TYPICAL EVAPORATION-DISSOLUTION LOSS o o i Fraction Paraffin (C&-CU) Paraffin (ci5~C22^ Cyclo-Paraf f in (c5-cn) Aromatic (Mono-cyclic) (c6-c10) Aromatic (Poly-cyclic) Residual PERCENT OF FRACTION REMAINING2 Wind 5 kt 10 kt 20 kt Evap:Dissol. ' Exposure 12 24 48 hrs 12 24 48 hrs 12 24 48 hrs 60:1 30 10 1 511 111 97 95 89 97 95 89 97 95 89 12:1 25 7 1 511 111 6:1 20 4 1 511 111 20:1 99 98 96 99 98 96 99 98 96 100 100 100 100 100 100 100 100 100 Calculated for 10 kt wind These values are approximate and dependent on factors including temperature, oil film thickness, emulsification, etc. Estimated time for 10 percent remaining is 40 days Estimated time for 10 percent remaining is 110 days orM rn/"t? . T „ v ~i <• I O"7 1 \ ------- 407 IMPACT COMPARISON General Procedure Oil spill response decisions should aim for the minimum probable envi- ronmental damage whether chemical dispersion is used or not. This section provides a means for identifying amenities threatened by various actions and assessing their probable impacts. It also provides onscene criteria for weighting resulting impacts. Evaluations may be conducted for the entire spill or for specific geographic areas of a large incident. Impacts can be evaluated and compared using the following steps: A. Using information provided in Sections 302, 402, and 406, list the amenities threatened by both conventionally or nontreated oil, and by chemically treated oil. B. Assess the probable severity of each type of impact for both conventionally or non-treated and chemically treated cases for each amenity as appropriate. C. Weigh the impacts and identify the case resulting in the least probable impact for the situation. Note: When conducting the assessment and comparison, it is important to remember that chemical treatment will likely not be 100 percent effective. Oil not dispersed in the upper water column at the point of contact with the threatened amenity may react as untreated oil and require assessment in both categories. Impact Comparison Matrix Figure 407-1 provides a matrix to be used in organizing the impact assessment and comparison. Before using the matrix, predicted movement and extent of untreated and dispersed oil (as determined in Section 302 and 406) should be plotted an appropriate charts. In consultation with local repre- sentatives, amenities of concern within both zones of exposure should be identified (Section 402) and listed in the threatened amenity column of the matrix. The general types of impacts can then be assessed. Three levels of impact should be considered: probable severe impact; unknown impact; and probable low impact. More specific guidelines for defining a "probably severe" impact to an amenity are given in Table 407-1. Where the extent of possible contamination is uncertain, evaluations should assume a worst-case situation. Subjective judgements about non-biolo- gical impacts are relatively straightforward and self-explanatory. Biologi- cal questions are more complex. The following discussion will help the user assess "biological" questions related to treated and untreated cases. The Chemically Treated Case Extensive information exists regarding the toxic effects of oil and dis- persants but this information must be used with caution in regard to direct field application. Laboratory tests and field observations regarding the effects and performance of the high toxicity Torrey-Canyon era dispersants 400-41 ------- CONVENTIONALLY OR NOT TREATED CHEMICALLY TREATED THREATENED AMENITY + = Probable severe impact 0= Unknown impact -= No or probable low impact Figure 407-1. Impact comparison matrix. 400-42 ------- TABLE 407-1. CRITERIA FOR "SEVERE" IMPACT RATING IMPACT CATEGORY SEVERE RATING CRITERIA ECONOMIC If the temporary or long-term loss of an amenity will affect the local or regional economy directly (e.g., clos- ing of commercial fishing grounds) or indirectly (e.g., decreased tourism because of contaminated recreational beaches), then the the particular action is considered to have a "prob- able severe Impact" on the amenity. AESTHETIC TOXICITY SMOTHERING SUBLETHAL PERSISTENCE RECOVERY If the temporary or sence of oil will ch value of an amenity. If the amenity is va because of its appea on sailboat hulls, o tlonal beach), then action is considered able severe impact longer-term pre- ange the esthetic and especially lued in part ranee (e.g. , oil 11 on a recrea- the particular to have a "prob- on that amenity. If the presence of oil, dlspersant, or dispersion, through the action of its chemical properties, will adversely affect a major portion of a biological amenity (e.g., a commercial shellfish bed) then the particular action is considered to have a "probable severe impact" on that amenity. If the oil will adversely affect a major portion of a biological ameni- ty through the action of physical contact (I.e., smootherlng, covering, clogging, suffocating) then the parti- cular action is considered to have a "probable severe Impact" on that amenity. Oil, dlspersant, or components there- of will interfere with a significant portion of a population or community at a sublethal level. Interferences can include disruption of reproduc- tive or other functions, carcinogen effects, and so on. If contamination by oil, dlsper- sant, or dispersion will result in the incorporation of oil and/ or toxic substances in the envi- ronment (e.g., burial on a beach) such that they become a long-term fixture of that environment, then the particular action is considered to have a "probable severe Impact" on that amenity. If the temporary or longer-term pre- sence of oil, dlspersants, or disper- sions will physically or chemically delay or prevent the recovery of the amenity to pre-splll conditions, then the particular action is considered to have a "probable severe impact" on that amenity. 400-43 ------- are not germane to, nor should be used in the assessment of modern, low toxi- city products. Data on modern dispersants are difficult to compare due to the considerable variability in test oils, procedures, test organisms, and duration of exposure, and can seldom be compared or applied directly to the field. Test data required by Annex X does provide a measure of uniformity and, while not directly applicable to field use, may be used to rank pro- ducts. Toxicity rankings should be used in terms of order(s) of magnitude differences and not absolute values. In the broadest sense, the joint IMCO/ FAO/UNESCO/WMO Committee (1969) proposed grades of toxicity for pollutants in the aquatic environment can be used to indicate how order of magnitude differences relate in scale (Table 407-2). Grades proposed by other experts are also shown in this table. After identifying lower toxicity dispersants using the EPA toxicity data, estimates of dispersant and oil concentrations in the water column, as described in Section 406, can be used for predicting potential ecological effects. Although no field-worthy models exist for predicting the ecological effects associated with a given concentration of oil or dispersant, approx- imate toxic concentration limits for each dispersant product and each generic oil type can be delineated by relating estimated dispersant concentrations with EPA LC data for approved dispersants (an LC-- is the concentration at which 50 percent of the test organisms do not survive over a given time period). Figure 407-2 (impact severity chart) can then be used to estimate the impact severity a particular dispersant could have on a particular biolo- gical amenity. The figure should be used in the following manner: 1) Obtain the most sensitive LC,._ from the EPA data for the proposed dispersant(s) (i.e., use the lowest ppm LC of the three bioassays). 2) Find the LC value on the vertical axis of the figure and draw a horizontal line from that point. 3) Obtain the estimated concentration of the dispersant or oil/dispersant at the desired location from Section 406. 4) Find the dispersant concentration on the horizontal axis (for the appropriate safety factor) and draw a vertical line from that point. 5) If the two lines intersect above the diagonal line, the dispersant can be expected to have "probable low impact" on the biological amenity. If the two lines intersect below the diagonal line, the dispersant can be expected to have a "probable severe impact" on that amenity. Three safety factors are incorporated in the horizontal axis of the chart. In 1972, the NAS-NAE Committee on Water Quality proposed that "the prediction of safe levels be made by carrying out bioassays for acute lethal toxicity and multiplying the lethal concentration by a, suitable application factor." The committee recommended that the maximum concentration not exceed 400-44 ------- TABLE 407-2. GRADES OF TOXICITY Practically non-toxic Slightly toxic Moderately toxic Toxic Very Toxic TLmdng/l)1 MO.OOO 1,000-10,000 100-1,000 1-100 1 2 LC50(ppm) 10,000-1,000,000 1,000-10,000 100-1,000 10-100 10 LC50(ppm) >10,000 1000-10,000 100-1000 100 1 IMCO/FAO/UNESCO/WMO Group of Experts (1970). -Jeffery, P.G., and J.A. Nichols (1974). Beynon and Cowell (1974) 400-45 ------- NO OR PROBABLE LOW IMPACT PROBABLE SEVERE IMPACT (0.10 safety factor) (0.01 safety factor) (0.001 safety factor) CONCENTRATION IN WATER COLUMN (ppm) Figure 407-2. Impact severity chart. 400-46 ------- one one-hundredth (0.01) of the LC values. This 0.01 factor is intended for application to single species, and is subject to some question when applied to ecosystems whose component members may exhibit varying levels of toxic response. The accuracy of the resulting impact prediction improves if the procedure is used on a number of local species. When only EPA test data are available the resulting predictions should provide a general indication of overall impact. For highly sensitive situations demanding additional pre- caution, a 0.001 safety factor (one one-thousandth of the LC,-_) can be applied; for less sensitive situations, concentrations using a 0.1 safety factor (one tenth of the LC_Q) can be used. Selection of the appropriate factor is at the discretion of the OSC in consultation with his support staff and local scientists. Exposure time is another important consideration. Typically, the longer an organism or aquatic community is exposed to a given concentration, the higher the potential for adverse impacts. In using Figure 407-2, it is assumed that organisms will be exposed indefinitely. In reality, concentra- tions actually encountered likely to be short-term phenomena owing to natural mixing and rapid dilution phenomena. EPA LC bioassays are run for 48 or 96 hours, depending upon the test organisms and concentration is not diluted over time. The use of the most sensitive (lowest ppm) of the three bioassay tests for the dispersant's base LCc0 skews the outcome toward the "probably severe impact" designation. Example: A valuable shellfish bed lies 3 m deep and 2 km from the pro- posed dispersion point. The estimated concentration of dis- persant at the bed is calculated at 2 ppm, and EPA toxicity data shows the lowest LC__ concentration for this dispersant to be 2500 ppm. Using Figure 407-2 the point where 2500 ppm and 2 ppm intersect (using the 0.01 safety factor) is clearly in the "probable low impact" area. Thus, the specified dose of this dispersant should not acutely affect the shellfish bed. If the most sensitive LC_0 for the dispersant had been 100 ppm instead of 2500 ppm, tne conservative prediction would have been different (i.e., the dispersant should have a prob- able severe impact). Multiple Dispersant Applications and Maximum Permissible Dosage. Figure 407-2, can also be used to estimate safe maximum concentrations for multiple dispersant applications or the permissible maximum concentration for a given LC_0 toxicity. The maximum allowable (sublethal) concentration of dispersant in the water column is divided by the anticipated concentration from each application to determine the number of applications that can be safely under- taken. This number will be quite conservative in areas with high circulation rates as continual dilution will preclude the buildup of high dispersant con- centrations. Under no circumstances should the indicated maximum acceptable concentration be exceeded. Dispersed Oil Effects After determining the potential effects of the dispersant, the potential effects of the dispersed oil must be evaluated. Unlike dispersants, no stan- dardized toxicity test for oil exists, as the composition of oils and refined 400-47 ------- products vary widely. Should the user have access to toxicity data for an oil similar to the one spilled, Figure 407-2 can be used to predict the severity of the potential impact in a fashion similar to one for dispersants. Again, use of the 0.01 safety factor and the assumption that all the toxic components of the oil are transferred into the water column (when, in fact, the more volatile fractions are usually quickly lost through evaporation) should ensure an adequately conservative outcome. If no oil toxicity data are available, background information on the effects associated with generic oil types and past spill events (as discussed for the untreated case) will have to be used in making assessments. Some laboratory and field evidence suggests that chemically produced oil dispersions may be more toxic than naturally produced dispersions. It has been hypothesized that this phenomena is a synergism between oil and disper- sant which produces more toxic end products. The "increased toxicity" of a dispersion is probably more related to the increased availability of the oil to marine organisms. By breaking the oil up into minute droplets, the dis- persant enhances the uptake and incorporation of certain oil components by many marine organisms through their breathing and feeding mechanisms. For this reason, dispersed oil may have a more adverse impact on a biological amenity than untreated oil at the same concentration. This differential could be extremely important in relation to the incor- poration of certain polycyclic aromatic hydrocarbons and complex hydrocarbons and tars into edible fish and shellfish as they may result in tainting. In addition, these substances have been implicated as possible carcinogens though the dose/response relationships for both large, single-dose exposures and low-level, chronic exposures to such carcinogens are far from resolved. The breakdown of oil into fine droplets has some environmental advan- tages which may outweigh its possible drawbacks. By increasing the surface area exposed per unit volume of oil, biodegradation is accelerated thus decreasing persistence in the marine environment. Similarly, the dispersant, by coating the oil droplets may prevent the oil from sticking to plant, rock, and sediment substrates. Little information is available regarding sublethal long-term effects of dispersed oil. Chronic low-level exposure could occur if oil or disper- sant is incorporated into sediments and gradually released with time. This is most likely to occur in estuaries and near-shore environments. Sublethal concentrations and effects are difficult to detect and measure in the envi- ronment. Such sublethal effects include possible change in fecundity, fer- tilization, larval development, respiratory rate, and escape and feeding responses. Recognizing the possible consequences in a population or marine community, some researchers have proposed that standard toxicity tests should measure the lowest median concentrations that affect biological functions important for survival of individuals in an ecosystem. Many modern disper- sants are, however, biodegradable and should not create chronic toxicity problems. Until better information is available prediction of biological effects expected with dispersants, dispersions, and untreated oil must be dictated by lethal concentration considerations and prudent use of safety factors. 400-48 ------- The Untreated Case The deleterious effects of untreated oil on marine life are largely due to physical rather than chemical action [i.e., interference of respiration through clogging (smothering) of gill filaments versus physiological effects of uptake of toxic components]. Although certain components of oil are extremely toxic, the smothering and mechanical interference of biological activity often cause greater damage. Low-boiling aromatics and saturated hydrocarbons (e.g., in light fuel oils) appear to be more directly toxic than the higher-boiling saturated hydrocarbons (e.g., in heavy crudes). Typically, those fractions with low boiling points are lost first. Table 407-3 gives the estimated concentra- tions (ppm) of the soluble aromatics required to cause toxicity in various classes of organisms and the amount of No. 2 fuel oil and a representative crude oil needed to produce an equivalent dose of aromatics. It is apparent from the table that No. 2 fuel oil owes its high toxicity to its high aro- matic content. Larval forms are more susceptible to impact than are the adults of the same species. In the case of an offshore spill moving onshore, chemically toxic, unweathered oil may never come into contact with marine organisms other than plankton populations in the immediate spill vicinity. Tainting and the accumulation of potentially carcinogenic agents in com- mercial fish and shellfish can and do occur with an untreated oil slick through natural dispersion, solubilization, and long-term persistence. The higher molecular weight polynuclear fractions in oil may be particularly sig- nificant in their persistence and subsequent accumulation in the food web, although many of the edible fish and shellfish species depurate (or elimina- te) the petroleum hydrocarbons that they accumulate when no longer exposed to contamination. When a weathered oil does reach the nearshore area, massive mortalities can result. The most visible class of organisms affected are usually birds, particularly those species that feed by diving. Oil penetrates and clings to the plumage, matting the feather structure and causing loss of insulative properties. The bird can then become chilled and susceptible to severe meta- bolic stress, exhaustion, and disease. In addition, an oiled bird can ingest quantities of oil during preening which can cause poisoning, inflammation of the digestive tract, or disturbance of other physiological processes. Oil can also have a profound direct effect on the viability of bird eggs and on the capability for incubation of fertile eggs if the breasts of nesting birds are contaminated. Invertebrate populations may suffer dramatically when in physical con- tact with the oil. Recruitment and recovery can be rapid if the affected organisms represent only a portion of a larger, regional population and the oil does not persist. Successional recovery of an intertidal marine commu- nity ranges from weeks or months to a decade, depending on the structural complexity of the community, the amount and type of oil present, the persis- tence of the oil, and the degree of the initial damage. Persistent contamination by petroleum, or frequent chronic spills, may hinder natural succession and slow recovery. 400-49 ------- TABLE 407-3 SUMMARY OF TOXICITY DATA CLASS OF ORGANISMS FLORA FINFISH LARVAE (All species) PELAGIC CRUSTACEANS GASTROPODS (Snails, etc.) BIVALVES (Oysters, clams, etc. ) BENTHIC CRUSTACEANS (Lobsters, crabs, etc.) OTHER BENTHIC INVERTEBRATES (Worms, etc.) Es timated Concentration (ppm) of Soluble Aroma tics Causing Toxicity 10 - 100 5-50 0.1 - 1.0 1 - 10 10 - 100 5-50 1 - 10 1 - 10 Estimated Amount (ppm) of Petroleum Substances Containing Equivalent Amount of Aromatics #2 FUEL OIL FRESH CRUDE 50 - 500 104 - 105 25 - 250 104 - 105 0.5 - 5 102 - 103 5-50 103 - 104 50 - 500 104 - 105 25 - 250 104 - 105 5-50 103 - 104 5-50 103 - 104 Stephen Moore. 1973. Background Papers for a Workshop on Inputs, Fates, and Effects of Petroleum in the Marine Environment. National Academy of Sciences. 400-50 ------- Comparing Impacts The completed comparison matrix forms a basis for determining the most acceptable overall mode of treatment. The individual impact cells of the matrix are not additive and therefore the most appropriate action will not necessarily be the one with the least number of severe impacts. The matrix has been designed as a qualitative rather than a quantitative tool because different amenities can have dramatically different values at different times of the year and in different local and regional settings. For example, a waterfowl feeding area along a coast may be considered more valuable during a winter spill when large numbers of birds are present than would a recreation- al swimming area that is used almost exclusively in summer. Their relative standing might be reversed during a summer spill depending on the type and expected persistence of the oil, relative recovery times for both the water- fowl feeding and swimming areas, and the availability of similar areas out- side the zone of contamination. Conceivably a local or regional community that depends solely on tourism for its livelihood would consider a single severe impact to their recreational beaches more important than a combination of other types of impacts. The purpose of the matrix is to ensure that the major potential effects of each action are considered. In consultation with local and regional experts, the user must compare the different weightings of the amenities in determining the most acceptable alternative. Example: A crude oil spill occurs in coastal waters and threatens to move into an area characterized by the special features and amenities as identified by the OSC and listed in Figure 407-3. Environmental conditions preclude conventional control actions in all areas with the exception of the larger estuary. Even in this area the adequacy of any conventional effort is uncer- tain. Considering the sensitive nature of the shoreline, it is decided to evaluate the feasibility of chemical dispersion offshore to reduce the overall damage. Estimated zones of contamination are calculated using procedures presented earli- er in this manual. The results are shown in Figure 407-3. With the assistance of local and regional experts, evaluations of the impact severity on each amenity are conducted. The results are listed on the comparison matrix shown in Figure 407-4. As indicated, "probable severe impacts" can be expec- ted with oiling of all threatened shoreline amenities. Chem- ical dispersion is an attractive alternative because it may reduce or eliminate contamination of these areas. Plume dis- persion modeling suggests that an important commercial shell- fishing area lies in the path of the dispersed oil plume, and that the concentration of dispersant in the waters over the shellfish bed may reach 1.5 ppm. Toxicity data on the dis- persant used include a lowest LC of 1000 ppm. Using Figure 407-2 a "probable low impact rating" is determined using a 0.01 application factor. The concentration of dispersed oil at the shellfish area has been previously estimated at 100 ppm. Travel time has been previously estimated at 20 hours, 400-51 ------- ': "ipf • Waterfowl rookery • Industrial water intake .2ijS**&'~'} I . ,.J%®> Figure 407-3. Hypothetical spill event. 400-52 ------- CONVENTIONALLY OR NOT TREATED CHEMICALLY TREATED THREATENED AMENITY Waterfowl rookery Industrial water intake Endangered species Recreational beach Commercial shellfishing area - + - + + - - + 0 - + - + - 0 - 0 - 0 - - - 0 - 0 - + - 0 - - - - - - - - 0 - - - 0 + = Probable severe impact 0= Unknown impact - = No or probable low impact Figure 407-4. Hypothetical spill event impact comparison matrix. 400-53 ------- sufficient to allow significant reduction in this concentra- tion through loss of volatile fractions. In addition, the calculations consider only the upper several meters; the shellfish beds are at a depth of 60 meters. Thus, risks to the amenity appear far less than the probable effects of untreated oil impact on the amenity shoreline. Chemical treatment is recomended at the indicated site. 400-54 ------- SECTION 500 CRITERIA FOR USE OF DISPERSANTS ON SHORELINES 501 GENERAL PROCEDURE Dispersants can aid in the restoration of shorelines by loosening or dissolving oil coatings or preventing the adherence of physically loosened oil particles on other surfaces. Due to difficulties in controlling dosage and the potential for environmental side effects, dispersants should only be considered for cleaning contaminated shorelines when mechanical cleanup and natural recovery are judged very difficult, ineffective, or potentially more environmentally damaging. To consider products for shoreline use, they should be recommended for that purpose or designated as beach-cleaners by their manufacturers. Figure 501-1 gives a sequence of considerations required to evaluate the probable acceptability of dispersant use for shoreline cleaning. Supporting sections of the manual have been referenced when appropriate. 500-1 ------- O O I ro K Determine area of effect (402) Contamment imminent y K Oil onshore V •Manual of Practice for Protection Vnlnmec 1 anri 7 (EPA-600/7-79- V K Effective y adequacy ^f of surface ' collecting agents k Ineffective ^ V K Adequate y Evaluate conventional clean-up techniques (502) K Inadequate y V and Cleanup of Shorelines- 187aand 187b) V K Acceptable . V Evaluate natural k potential \ (503) Acceptable J \^elect ' "I/ (504) r "•••»-=K»U,O y Evaluate ^^_^_^ / Impacts k I/ (firm) JV Unacceptable y V Implement (Appendix D) Go to oil onshore Implement manual* Allow to clean naturally Consider use of dispersants (Appendix C! Consider extraordinary actions Figure 501-1. Sequence for consideration of dispersant use on shorelines. ------- 502 CONVENTIONAL PROTECTION AND CLEANUP POTENTIAL Mechanical Cleanup of Shorelines Physical removal is generally the preferred method for cleaning oil con- taminated shorelines. The EPA Manual of Practice for Protection and Cleanup of Shorelines (EPA-600/7-79-187a and 187b) describes cleanup techniques and sets guidelines for the selection of the proper technique for various spill and shoreline conditions. Dispersant use on shorelines may be acceptable if one or more of the following conditions exist: 1. Insufficient physical cleanup equipment and/or manpower to effec- tively clean the shoreline in a timely manner. 2. No land or water access for mechanical cleanup equipment. 3. Contaminated beach sediment cannot be removed and replaced without causing unacceptable environmental damage. Insufficient Resources. This condition may occur in the event of a large oil spill where many kilometers of shoreline are contaminated and there is insufficient cleanup equipment available locally or regionally. The same condition may also arise for a smaller spill in a remote area where required equipment is not available. Lack of Access. Certain shoreline areas may be inaccessable to cleanup equipment from land because there are no roads in the region, or there are marshlands or cliffs behind the beaches. Access from the water may not be possible because of heavy surf conditions or shoals. Sediment Removal. Removal of contaminated sediment from a shoreline may cause unacceptable environmental damage. This may occur if (1) sediment removal upsets a delicate habitat, (2) natural replacement of the removed sediment by littoral processes would not be sufficient, (3) sediment removal would cause excessive erosion of backshore areas, or (4) a local supply of similar sediment was not available to replace the sediment during the cleanup operation. 500-3 ------- 503 NATURAL CLEANING POTENTIAL The acceptability of allowing an oiled shoreline to clean naturally is based on the rate and degree of natural cleaning and their compatibility with desired recovery and resumption of use of the area. Several factors influence the natural cleaning potential of a shoreline area. These factors in the order of their importance are: 1. The energy level of the shoreline area. 2. The type and volume of the spilled oil and its depth of penetration. 3. The prevailing climate. Energy Levels The energy level of a shoreline can be defined as the mechanical energy imparted to the shoreline by waves and wind and is generally indicated by the size and frequency of waves which impact the shoreline. Shorelines which have predominately onshore winds will have higher energy levels than shore- lines where the wind blows predominately offshore. Fetch is an indication of the degree of exposure or shelter for a given shoreline and is defined as the length of water surface area over which winds can generate waves. Other indications of shoreline energy levels for sediment beaches are the height of a beach berm or ridge and sediment sorting on a given shoreline. The height of the berm (on sand beaches) or ridge (on pebble/cobble beaches) is a direct function of wave height; increases in wave height and wave energy create higher berms or ridges. The degree of sorting of beach sediments can be a useful indicator of shoreline energy levels. High wave-energy beaches are usually characterized by well-sorted sediments (i.e., only one size of sediments). In sheltered, low-energy locations the beach is usually composed of a mixture of sediment sizes. The higher the energy, the higher the probability of high natural cleaning rates. Figure 503-1 indicates the relationship between the factors discussed above. It can be used to approximate the energy level of various coastline areas. Oil The type and volume of oil and its depth of penetration will influence the natural cleaning potential of a shoreline. Viscous sticky oils (Class C) will tend to stick to impervious surfaces like rocks and sea walls, but will not penetrate sediment beaches in depth. Lighter, less viscous oils (Class A) will only thinly coat impervious surfaces but can deeply penetrate sedi- ment beaches. Penetration and burial insulate the oil from surface radiation and wave energy. Oil will generally penetrate larger grain sediments and will be buried most readily in areas characterized by high sedimentation rates (e.g., longshore sand transport, freshwater sediment loading). Thick viscous oil coatings on impervious surfaces resist wave scouring to a greater extent than thin, less viscous coatings. 500-4 ------- FETCH Lor (>20C i Sh «5C ^g Ikm) h art km) PREVAILING WINDS Ons / Offsl 'lore L lore COASTAL EXPOSURE Stra (Op t Inde (Shell ght en) i nted ered) BERM/RIDGE HEIGHT HI i Lc gn L w SEDIMENT SORTING Go A Pa od k or ENERGY LEVEL H i L igh k 3W Figure 503-1. Shoreline energy levels. 500-5 ------- Climate Prevailing air and water temperatures can effect the persistence of oil on a shoreline. The colder the air and water temperatures, the more likely the oil will persist. Rates of physical and biological (microbial) degrada- tion decrease as temperatures decrease. Conversely, as temperatures rise, oil becomes more mechanically and biologically susceptible to removal. Assessment Accurate estimates of the natural cleaning potential of a shoreline can be difficult without taking long term field measurements. However, Figures 503-2 (sediment beaches) and 503-3 (non-sediment beaches) can be used to indicate whether a specific shoreline has a high or low potential for natural cleaning. A high potential would mean that most of the oil should be removed naturally from a shoreline in several days to months. A low potential for natural cleaning means that a majority of the oil would remain on the shore- line for months to years and that some oil may remain for decades. 500-6 ------- Substrate Type O O I Mud Sand Gravel Cobble Energy Levels High (Exposed) Low (Sheltered) Degree of Penetration or Burial All or most of oil exposed Amount of Oil Contamination Extensive oil penetration or burial V All or most of oil exposed Extensive oil penetration or burial ^> Light Heavy Light Heavy Light Heavy Light Heavy Natural Cleaning Potential of Shoreline Hi 1 Lo gh w Figure 503-2. Natural cleaning potential for sediment shoreline. ------- Ol o o I oo Substrate Type Rock cliff Rock ledge Man-made structures Boulders Energy Levels High (Exposed) Low (Sheltered! Amount of Oil Contamination Low Light thin coating High Heavy viscous coating Low Light thin coating High Heavy viscous coating Prevailing Temperature Natural Cleaning Potential of Shoreline High Low Figure 503-3. Natural cleaning potential for non-sediment type shorelines. ------- 504 SELECTION OF APPLICATION TECHNIQUES, DISPERSANT, AND DOSAGE Once dispersant cleaning has been deemed acceptable, the proper dis- persant, application technique, and dosage must be selected for the specific area to be cleaned. Selection is based on the nature of the surface to be cleaned and the mode of cleaning, rather than the oil type, which will be weathered and viscous in most cases. In general, dispersants are best suited for use on impervious surfaces such as rock cliffs or platforms, seawalls, docks, etc., but can also be used on sand or cobble beaches. Manufacturers' recommendations for dispersants should be reviewed prior to application. Selection of Dispersant Type There are two types of dispersants which can be used to clean oil- contaminated shorelines. These are: • hydrocarbon base dispersants • water base dispersants Table 504-1 indicates the type of substrate on which the two types of dispersants can be used. Table 504-2 relates the dispersant type to appli- cation equipment and methods. Hydrocarbon Base Dispersants. The use of hydrocarbon base dispersants to clean shorelines is generally limited to impervious surfaces contaminated with highly viscous or weathered oil. Application to sand, gravel, or cobble beaches may result in deeper oil penetration of the sediments. Typically, these dispersants are applied neat and allowed to stand for a short period of time before agitation by water jets or wave action. Successful use depends on uniform application, adequate contact time, and agitation of the oil/dis- persant mixture. The contact time allows the agent to penetrate and loosen the oil, and the agitation by wave action or water jets ensures thorough removal and dilution. Highly viscous or weathered soils may require several applications for effective removal. Stiff brooms can be used on solid surfaces to work the dispersant into the oil, thereby increasing effectiveness. Steam may be beneficial in final removal. Water Base Dispersants. Water base dispersants are usually applied in diluted form (1-10 percent in water) through a high-pressure spray system or fire hose. Their primary objective is to prevent the oil reforming or adher- ing to other surfaces as the force of the water spray striking the contami- nated surface provides the mechanism for oil removal. If used undiluted on unconsolidated surfaces, they may drive the oil deeper into the substrate. Therefore, application to sand, gravel, or cobble beaches should be uniform and conducted just prior to the rising tide. Application to seawalls, rock cliffs, docks, and other impervious surfaces is generally more effective using very high pressure hydroblasting equipment but can also be accomplished at lower pressures using fire hoses. For highly viscous or weathered oils, 500-9 ------- TABLE 504-1. DISPERSANT TYPE VERSUS SUBSTRATE TYPE DISPERSANT TYPE SUBSTRATE TYPE Hydrocarbon Base Water Base Mudflats X Sand/Gravel X Cobble X Boulder X X Rock Platform X X Rock Cliffs X X Man-made Structures X X 500-10 ------- TABLE 504-2. EQUIPMENT AND APPLICATION METHODS FOR DIFFERENT DISPERSANT TYPES DISPERSANT APPLICATION EQUIPMENT DILUTION TYPE METHOD USED METHOD Hydrocarbon Applied neat at Hand-held or back- Not Applicable base low pressure and pack sprayers, low volume pressure/volume pumps, single or multi-nozzle spray lances, or agricul- tural spraying equip- ment (fire pumps, hoses, and nozzles for flushing) Water base Applied in solu- Hand-held or back- Premixed, or tion at concen- pack sprayers, high diluted through trations of 1-10%; pressure/volume eduction or usually at high pumps, injection injection. pressure and puiaps, fire nozzles volume. or spray lances, or agricultural spray- ing equipment. 500-11 ------- a presoak using hydrocarbon base or concentrate dispersant applied full strength may be necessary. The dispersant/water solution can be prepared by premixing, eduction, or injection into a high pressure water stream. The high pressure nature of the application system not only delivers the dispersant to the oil but also mixes it in and removes the dispersed oil from the substrate. Sand, gravel, or cobble beaches may require repeated applications after every few tidal cycles. This permits wave action to turn over cobbles or the top layers of sediment exposing previously untreated oil. Selection of Dispersant Cleanup Techniques Several different methods can be used to implement dispersant cleaning of a shoreline. Table 504-3 lists two techniques and several application methods for using dispersants on a shoreline. The following factors influ- ence the selection of a dispersant shoreline cleaning technique: type of substrate shoreline energy level sensitivity of the shoreline to oil and dispersant type and amount of oil contamination vehicle access and trafficability on a shoreline Two decision guides have been prepared to help the user evaluate these fac- tors for a given shoreline and select the preferred dispersant cleanup tech- nique. Figure 504-1 discusses sediment-type shorelines, and Figure 504-2 discusses non-sediment-type shorelines. Implementing Dispersant Shoreline Cleaning The intertidal zone should be treated just ahead of the rising tide so that wave action can agitate the dispersant/oil mixture and disperse it into the sea yet still allow adequate contact time for maximum effectiveness. Contaminated substrate lying above the high water line should be treated with dispersant and pushed into the surf zone or flushed thoroughly with seawater. Field experience involving the use of dispersants in conjunction with flushing equipment indicates that dispersants do not necessarily improve cleaning rates but do disperse the removed oil, preventing it from coagula- ting and penetrating sediments. Dispersant Dosage Specific dosage rates for dispersant cleaning of shorelines have not been developed. Manufacturers' recommendations should be followed initially and adjusted based on the effectiveness of the cleaning operation. 500-12 ------- TABLE 504-3. DISPERSANT BEACH CLEANING TECHNIQUES Dispersant applied directly to oil on beach; tidal and wave action remove dispersed oil. A. Vehicle. Application of water base dispersant by spray bar from tank truck or beach vehicle. B. Manual. Application of water base dispersant by fire hose or hydrocarbon base dispersant by spray system. Dispersant applied to oil on shoreline (beach, rocks, sea walls, etc.) and oily runoff collected. A. Application of water base dispersant by fire hose or hydrocarbon base dispersant by portable spray systems to oiled area, collect runoff. B. Push loose substrate into stock pile on back shore area, apply water base dispersant to stock pile and collect runoff. C. Injection of water base dispersant into high pressure washing system—collect runoff. 500-13 ------- Shoreline Energy Level sdium \ rV Medium to High o o I I LOW I Can dispersed oil remain YCS in environ- ment? w 2.B Stockpile substrate, apply dispersant, collect runoff Is there vehicle access to beach and is beach trafficable to tracked or wheeled vehicles' NO YES Degree of oil contamination Surface medium- heavily contaminated Surface lightly contaminated 1.A Vehicle application 1 B. Manual application 1.B. Manual application If oil contamination extends beyond high tide line, use bulldozer or front-end loader to push dispersant treated oily sediments into surf zone Figure 504-1. Decision guide- dispersant beach cleaning techniques for sediment beaches (1.A. etc., refers to techniques listed on Table 504-3). ------- Beach Type Boulder Rock Man-Made Structures Shoreline energy level Medium to high Low Can dispersed oil remain in environment ? Yes No O o I Is stranded oil highly weathered or tar-like? Yes No Amount of oil contamination Surface lightly contaminated Surface heavily contaminated 1.B. Manual application 1. B Dispersant manually applied, then flushed 2. A. Dispersant manually applied, then flushed and runoff collected. or 2 C. Inject dispersant into high-pressure washer. N, I/ Amount of oil contamination Surface lightly contaminated Surface heavily contaminated 2. A. Manual application of dispersant, then collect runoff 2. B. Dispersant applied or manually, then C. flushed and runoff collected Figure 504-2. Decision guide - dispersant beach cleaning techniques for non-sediment beaches (1.B. etc., refers to techniques listed on Table 504-3). ------- 505 ECOLOGIC CRITERIA The final consideration in determining acceptability of dispersant use on shorelines is the relative ecologic effect. Dispersant use is acceptable when it results in the least overall environmental damage and facilitates the speediest return to normal conditions. The following criteria can guide decisions which regard the environmental consequences of dispersant use: 1. Existing Damage. If most or all shoreline organisms are already coated with oil and the nearshore waters are carrying heavy oil concentrations, the bulk of damage has probably been done and the additive effects of dispersant and dispersed oil will probably be minimal. When evaluating existing damage, it is important to con- sider the three-dimensional nature of the beach. Often contamina- tion is restricted to surface coatings; sub-surface or under-rock habitats may be unaffected. While removing surface contamination, dispersant treatment may contaminate these lower areas which previ- ously escaped the incoming floating oil. Chemical dispersion in the vicinity of emergent or submergent vegetation is not recommended. 2. Contamination of Adjacent Areas. In addition to effects on-site, dispersant application should be considered in terms of effects on adjacent areas. The case for chemical treatment may be considered from two related points of view: a) In some situations oil leaching from a contaminated site may pose a threat to a nearby resource or amenity. Any uncontrolled expansion of the zone of contamination is ecologically undesir- able. b) Oil removed by natural processes and by chemical treatment will ultimately be distributed on adjacent beaches and near-shore waters. When left to natural processes, removal is usually com- paratively slow and the resulting concentrations in the surround- ing environment are low. In addition, the weathering processes tend to facilitate removal of the more toxic components. In chemical treatment the removal rate is rapid and local short-term concentrations of removed material can be expected to be higher. The toxicity of the dispersant itself should also be considered. The movement and fate of materials dispersed in the near-shore environment are not clearly understood. Until the controlling mechanisms can be evaluated more accurately, shoreline chemical dispersion should be considered only when rapid mixing and dilu- tion with receiving waters is assured or when oily runoff can be collected. Areas with high mixing and flushing rates are typi- fied by open configuration and/or high tidal variation. 3. Persistence. All forms of treatment are designed to reduce persistence, and none should be used in situations where they may result in an increase. Generally, if dispersion results in oil penetrating shoreline or nearshore sediments, its persistence will 500-16 ------- be increased. Persistence should be considered both in terms of the initial site of contamination and the ultimate fate of the removed oil. Oil has been observed to adhere to suspended sediments and sink. The effect of dispersant treatment on this phenomena is uncertain. In areas of high turbidity, sediment sinking of dispersed oil should be considered possible. Note: Actual persistence of buried oil should consider the role of littoral processes. If a shoreline is undergoing seasonal or storm-related offshore sediment movement, any buried oil may be quickly removed. Recovery. Recolonization of a shoreline largely depends on the suitability of that shoreline for settlement and survival of recruits. Oil left exposed on the shoreline surface or gradually released there will inhibit the recovery process. Spores and larvae that recolonize a polluted shoreline will largely originate from adjacent unpolluted shores and not from the survivors of that shore- line. The proximity of such "seed" areas improves the opportunities for accelerated recovery. In general, dispersant use should not expand environmental damage if extensive mortality has already occurred. However, dispersant use may be desirable if treatment will decrease the persistence of the oil on the shoreline and encourage the biological recovery process. 500-17 ------- SECTION 600 CRITERIA FOR USE OF SURFACE COLLECTING AGENTS 601 GENERAL Surface collecting agents (SCA) are defined by the EPA as surface film forming chemicals for controlling oil layer thickness. By regulating the thickness, the film formed by the agent temporarily keeps the oil from spreading excessively. The application of SCA is discussed in Appendix D. The primary use is to concentrate the oil, thus making physical recovery more effective. It may also be used to temporarily protect a shoreline by fending off the oil slick from a particular area. SCA use requires the verbal permission ot the Federal DCS which may be granted either in person or by telephone. The OSC may authorize use of an SCA if: (1) it will result in the least overall environmental damage or inter- ference with designated water use. (2) provide a key element in the most effective system for removing oil or hazardous substance discharge from the water environment. The OSC must also ascertain that the prevailing environmental, meteoro- logical, and oceanographic conditions at the spill site are compatible with the agent's use. 600-1 ------- 602 ENVIRONMENTAL CRITERIA CONTROLLING USE Limitations on SCA Use Collecting agent surface tension forces are comparatively weak and approximately equivalent to those generated by a 3 mph wind or a surface current of 0.1 knot. Therefore, an SCA cannot keep oil from moving against most winds and currents. The agent can, however, control oil slick spread in moderate currents and in winds up to 20-25 mph, thereby facilitating cleanup and reducing the area of contamination if a slick comes ashore. SCA effectiveness will lessen with time. A properly applied film can usually maintain its integrity for a period of several hours although this is highly dependent on meteorological activity and the surface conditions of the water. Choppy wave action and wind can break the continuous chemical film formed by the agent, allowing the oil to resume spreading through the breaks. Additional applications can prolong the effective containment period. The effectiveness of SCA is reduced in waters which are heavily con- taminated with soaps or detergents. In addition, they are ineffective on oils in a solidified or semisolidified state such as weathered viscous oils, oils with high paraffin content, or water-in-oil emulsions. Table 602-1 provides a summary of conditions under which the agents are effective and not effective. When To Use Surface Collecting Agents The decision to use a surface collecting agent to control an oil slick depends on several factors. Table 602-2 presents a series of questions which can guide determination of the feasibility of SCA use for a given spill situation. If the answers to the questions of the checklist are affirmative, then the spill is a good can- didate for the use of an SCA for oil containment or shoreline protection. Ecologic Considerations While SCA have a measurable level of toxicity, they are typically applied in very low dosages and over limited areas (i.e., along the perimeter or leading edge of a slick). They also operate at the surface and evaporate relatively rapidly. (SCA contain carrier solvents that may be partially sol- uble). Open water application in accordance with manufacturers' recommenda- tions should not res-ult in concentrations causing quantifiable effects. Greater ecologic concern should be given to shoreline application, where direct agent-amenity contact and higher concentrations are possible, espe- cially with continual or repeated applications. Surface collecting agents hold promise for the temporary protection of wetlands and mangroves if applied properly. Since their impacts on vegetation are not well-known, use should probably be limited to application where significant contamination is indicated. A final consideration should be directed to the possible misapplication of an SCA. If applied seaward of the oil and shoreline, the oil may be forced ashore greatly compounding cleanup and damage. Wind and tidal shifts 600-2 ------- TABLE 602-1. CONDITIONS UNDER WHICH SURFACE COLLECTING AGENTS ARE EFFECTIVE AND ARE NOT EFFECTIVE Condition Effective Not Effective In Waves Currents Wind Temperature Oil type Debris or vegetat.ion swells up to 4 to 6 ft in height currents up to 0.1 kt. May be useful in deflecting oil from shorelines at higher currents, or in controlling the growth of a slick moving in a higher current winds up to 20-25 mph air temperature above pour point of collecting agent fluid petroleum oils breaking waves, white caps, or surf against currents greater than 0.1 kt Time areas with little or no floating debris or oiled vegetation short periods of time (up to 6 hr) against winds of greater than 3 mph air temperatures below pour point collecting agent weathered viscous oils, high parafin oils and water-in-oil emulsions areas with floating debris or where oil has contaminated aquatic vegetation 600-3 ------- TABLE 602-2. CHECKLIST FOR DETERMINING FEASIBILITY OF USING SURFACE COLLECTING AGENTS FOR OIL CONTAINMENT AND SHORELINE PROTECTION DETERMINING FACTOR YES NO 1. Are waves nonbreaking and less than 4 to 6 feet in height? 2. Is surface current less than 0.1 knots? 3. Is wind less than 20-25 mph (containment) or less than 3 mph towards shoreline (protection)? 4. Is air temperature greater than pour point of agent? 5. Is spilled oil in a fluid state? 6. Is there an absence of floating debris or aquatic vegetation in spill area? 7. Are there areas of special biological significance (i.e., bird nesting areas, shellfish beds, marshlands, etc.) or commercial significance (high-amenity beaches, etc.)? 8. Is an oil skimmer available to collect contained oil? 9. Is there equipment available to supply the surface collecting agent? 600-4 ------- can result in the generation of similar problems. Inshore use requires a clear understanding of its performance and the nature of area to be treated. Application Rates Current maximum application rates have been set by EPA at 2 gallons per linear mile or 1 ounce per 20 feet with allowances for reapplication every six hours but not to exceed three times in any 24-hour period. An increase in these maximum rates is currently being reviewed by EPA. Current approved application rates can be obtained through the OSC. 600-5 ------- 603 APPLICATION SCA can be effective in controlling spilled oil when used in conjunction with booms and skimmers. If applied in a timely manner to the slick perime- ter the agent can reduce the amount of oil boom required for slick contain- ment and concentrate oil in a smaller area for more effective skimming. However, belt and disc skimmers may lose effectiveness when used in the pres- ence of SCA. If a disc or belt becomes wetted by a collecting agent, it may tend to repel oil instead of recovering it. Therefore, when these skimmers are used on an oil slick surrounded by a collecting agent, they should be deployed in the middle of the slick and not driven into the slick through the chemical barrier. Similar precautions should be taken when using sorbents with an SCA. The sorbents should be placed directly on the oil slick inside of the chemical barrier and not dragged through the barrier. In quiet harbor or marina areas SCA can be applied to the water between the oil and the shoreline, structures, boats, etc. to repel oil until recov- ery can be implemented. They can be used in inaccessible locations between ships and under docks by applying the chemical to the water behind the oil, causing it to move out to areas where recovery techniques can be applied. General Application Method Application of SCA should be conducted as follows: • Apply the agents as quickly as possible. Agents are most effective when applied during the early stages of a spill when the oil is in the initial phases of spreading. • Apply the agents full strength and not diluted. • Apply the agents as a stream or coarse spray in a narrow path close to the edge of the oil slick. • Do not apply the agent to the slick itself. Agents sprayed onto an oil slick will be ineffective. Figure 603-1 illustrates methods of applying a collecting agent under several different conditions. Selection of SCA Application Techniques There are several different agent application techniques for controlling an oil spill. The most common methods incorporate the use of spray units mounted on airplanes, helicopters, boats, or carried by hand. In the absence of spray equipment, the agents can be applied using drip pots or squirt bot- tles. For small spills occurring in semi-confined areas such as docks, har- bors, estuaries, etc., the collecting agents should be applied with backpack sprayers or hand-held spray lances. Moderate to large spills occurring in the nearshore area or out to sea are best treated with vessel or helicopter mounted spray equipment. Very large offshore spills may require application by light, fixed-wing aircraft. Table 603-1 summarizes application techniques in relation to different spill situations. 600-6 ------- Apply Agent Here Water Current ••.-•. • • *• -T^'^'* o»-...<. .•;..•.•; ;.-•..- ^ Do not Apply Agent Here Apply Agent Here Do not Apply Agent Here Shoreline Protection Shoreline Protection Apply Agent Here Do not Apply Agent Here Apply Agent Here Apply Agent Here Skimmer Slick Concentration Windrow Concentration Figure 603-1. Collecting agent application. 600-7 ------- TABLE 603-1. APPLICATION TECHNIQUES FOR SURFACE COLLECTING AGENTS o o i 00 Surface Collecting Agent Use Concentrate oil — agent is applied to edges of oil slick to concentrate oil for subsequent boom contain- ment or pickup by a skimmer Move oil from underneath structures — collecting agent is applied behind an oil slick underneath a dock or wharf to drive oil out from underneath structure to facilitate cleanup Shoreline protection — collecting agent is applied in water ahead of an oil slick Small Spill 1. Back pack or hand-held sprayer 1. Back pack or hand-held sprayer 1. Back pack or hand -held sprayer Application Technique Moderate Spill 1. Helicopter spray system 1. Hand-held lance with chemical pump 1. Boat spray system Large Spill 1. Fixed wing aircraft n/a 1. Fixed wing wing aircraft and on front of the shoreline area to be protected 2. Drip pots 2. Helicopter 2. Helicopter ------- APPENDIX A ANNEX X - SCHEDULE OF CHEMICAL AND OTHER ADDITIVES^ TO REMOVE OIL AND HAZARDOUS SUBSTANCES DISCHARGES 2001 General 2001.1 This Schedule has been prepared by the U.S. Environmental Protection Agency pursuant to section 1(2) of Executive Order 11735. This Schedule applies to the waters of the United States and adjoining shorelines, the waters of the Contiguous Zone, and the high seas beyond the Contiguous Zone in connection with activities under the Outer Continental Shelf Lands Act or the Deep Water Port Act of 1974, or which may affect natural resources belonging to, appertaining to, or under the exclusive management authority of the United States (including resources under the Fishery Conservation and Management Act of 1976). 2001,2 This Schedule applies to the use of any chemicals or other additives as hereinafter defined that may be used to remove oil and remove or neutralize hazardous substances discharges. Any chemical agent or other substance not specifically defined in this schedule will be considered by EPA on a case-by-case basis for use in the removal of oil and hazardous substances discharges. 2001.3 This Schedule favors development and utilization of sorbents, skimmers,, booms and other mechanical control methods to remote or mitigate oil and remove, mitigate, or neutralize hazardous substances discharges from the environment with subsequent proper disposal. 2001.4 It is the intent of this Schedule that the use of chemicals and additives to remove or mitigate the effects of oil or hazardous substances discharges shall cause the least overall environmental impact. 2001.5 In implementing this Schedule and in maintaining its relationship with other Federal and State agencies, EPA shall recognize that some States may have more stringent laws, regulations or written policies regulating the use of chemicals in the removal of oil and hazardous substance discharges, in which case such laws, regulations or policies shall govern. 2001.6 It has been determined that because of the overriding need for prompt initiation of discharge removal actions no formal permit, as provided for by Sec. 402 of the Act, shall be required before application of chemicals to mitigate the effects of a discharge. The provisions of Sec. 1510.21 (f) and 1510.36(a)(3) of this Plan shall apply. 2002 Definitions Materials applied to oil or floating hazardous substances discharges are defined as follows: 2002.1 Chemical agents are those elements, compounds, or mixtures that disperse, dissolve, emulsify, neutralize, precipitate, reduce, solubilize, oxidize, concentrate, congeal, entrap, fix, gell, make the pollutant mass more rigid or viscous, or otherwise facilitate the mitigation of deleterious effects or removal of the pollutant from the water. 2002.2 Dispersing Agents are those chemical agents which emulsify, disperse, or solubilize oil into the water column or act to further the surface spreading of oil slicks in order to facilitate dispersal of the oil into the water column. 2002.3 Surface Collecting Agents are those chemical agents which are a surface film forming chemical for controlling oil layer thickness. 2002.4 Biological Additives are microbiological cultures, enzymes, or nutrient additives that are deliberately introduced into an oil or hazardous substance spill for the specific purpose of encouraging bio- degradation to mitigate the effects of a spill. 2002.5 Burning Agents are those materials which, through physical or chemical means, improve .the combustibility of the materials to which they are applied. 2002.6 Sinking Agents are those materials which are applied to oil and hazardous substance spills to sink floating pollutants below the water surface. 2002.7 Mechanical removal methods include the use of pumps, skimmers, booms. *Council on Environmental Quality. National Oil and Hazardous Substances Pollution Contingency Plan: Final Revision. 40 CFR Part 1510 (Federal Register. Vol. 45, No. 55, March 19, 1980). A-l ------- earthmoving equipment, and other mechanical devices. 2002.8 Sorbents are essentially inert and insoluble materials which are used to remove oil and hazardous substances from water through a variety of sorption mechanisms. Examples include: straw, expanded perlite, polyurethane foams, reclaimed paper fibers, peat moss. 2000 Dispersing Agent Program for Spills of Oil and Applicable Hazardous Substances 2003.1 Authorization for Use of Dispersing Agents 2003.1-1 Major and medium discharges. Dispersing agents may be used in any place, at any time, and in quantities designated by the OSC when their use will: 2003.1-1.1 In the judgment of the OSC, prevent or substantially reduce hazard to human life. 2003.1-1.2 In the judgment of the EPA RRT member on a case-by-case basis, in consultation with appropriate State or Federal agencies, prevent or reduce substantial hazard to a major segment of the population(s) of vulnerable species of waterfowl; or, 2003.1-1.3 In the judgment of the EPA RRT member on a case-by-case basis, in consultation with appropriate State and Federal agencies, result in the least overall environmental damage, or interference with designated water uses. 2003.1-2 Minor discharge. The provisions of section 2003.1-1 shall apply. 2003.2 Special Restrictions on Dispersing Agent Use: 2003.3.2-1 Chemical agents shall not be considered for use as dispersing agents unless technical product data have been provided and accepted in accordance with 2003.3 except when the judgment of the OSC the hazards discussed in 2003.1-1.1 are so imminent that the time delay for obtaining a dispersant agent that is in compliance with 2003.3 would be excessive. 2003.2-2 Federal officials responsible for oil and hazardous substance spill response activities at all levels shall develop effective programs to insure that dispersants that are available for use in appropriate spill response actions are dispersants with adequate technical data on file with EPA. This effort will help preclude the avoidance of the EPA technical data program by manufacturers or suppliers who might wish to take advantage of the emergency conditions provision of 2003.2-1. 2003.2-3 For all situations where dispersants are used, accurate records shall be kept on dispersant types, brands, application rates and methods, effectiveness, environmental impacts, plus any other pertinent observations. 2003.3 Technical Product Data For Dispersing Agents 2003.3-1 Technical product data as outlined in 2003.3-4 on the physical, chemical and toxicity characteristics of a dispersing agent shall be submitted to the Oil and Special Materials Control Division [WH-548), Environmental Protection Agency, Washington. D.C. 20460, at least 60 days prior to the use of the agent. Within 60 days of receipt of the data, EPA will inform, in writing, the submitter on the adequacy of the data provided. If additional information is requested or EPA desires to perform tests, the dispersing agent may not be considered for use until the additional needs have been satisfied and the submitter so notified. 2003.3-2 Information furnished in accordance with 2003.3-4 shall be maintained on file by the Environmental Protection Agency, Oil and Special Materials Control Division, (WH-548) Washington, D.C. 20460, to provide technical guidance to OSCs on the acceptable circumstances of use and dosage rates for dispersing agents. Any changes in the composition or formulation of the dispersing agent that will affect any of the data being requested in 2003.3-4 shall be immediately brought to the attention of EPA and testing of the agent will be repeated prior to the use of the revised dispersing agent. 2003.3-3 The acceptance and maintenance of product data by EPA does not constitute approval of the dispersing agent nor does it imply compliance with any EPA criteria! or minimum standards for such agents. The OSC will determine which dispersing agent may be used for a spill event on a case-by-case basis using all available information hi making such a decision To avoid possible misinterpretation and misrepresentation of the EPA's role in this technical product data program, the manufacturer's representatives may use only the EPA letter advising compliance with 2003.3-4 in any advertisements or technical literature on the dispersing agent. The EPA letter must be used in its entirety. Failure to comply with these restrictions or any other improper reference to EPA in attempting to demonstrate EPA approval of the dispersing agent for use on spills of oil or hazardous substances shall constitute grounds for removing the technical product data from EPA files, which would preclude use of the dispersing agent except as noted in 2003.2-3 for imminent hazards. 2003.3-4 Required Technical Product Data 2003.3-4.1 Name, brand, or trademark, if any, under which the chemical agent is sold. 2003.3-4.2 Name, address and telephone number of the manufacturer, importer or vendor. 2003.3-4.3 Name, address and telephone number of primary distributers or sales outlets. 2003.3-4.4 Special handling and worker precautions for storage and field application. Maximum and minimum storage temperatures to include optimum ranges as well as temperatures that will cause phase separations, chemical changes or otherwise damage effectiveness of the chemical agent. 2003.3-4.5 Shelf Life. 2003.3-4.6 Recommended application procedure(s), concentration(s) and conditions for use depending upon water salinity, water temperature and types and ages of the pollutants. A-2 ------- 2003.3-4.7 Dispersant Toxicity—Use standard toxicity test methods described in EPA Report "Standard Dispersant Effectiveness and Toxicity Test" (EPA R2-73- 201, May 1973) pages 22-34. This report may be obtained from the Oil and Special Materials Control Division (WH-548), EPA, Washington, D.C. 20460. 2003.3-4.8 Dispersant Effectiveness—Use standard effectiveness test methods in EPA R2-73-201, May 1973, pages 11-21. 2003.3-4.9 Flash Point—Select appropriate method from the following: ASTM—D 56-70; ASTM—D 92-72; ASTM—D 93-72; ASTM—D 1310-67. 2003.3-4.10 Pour Point—Use ASTM D 97- 66 2003.3-4.11 Viscosity—Use ASTM D 445- 72 2003.3~4.12 Specific Gravity—Use ASTM 01298-67 2003.3-4.13 pH—Use ASTM D1293-65 2003.3-4.14 Ionic Activity—Use Weatherburn Test as described below: Ionic activity tests (Weatherburn Test) Reagents: 1. Dye solution: 0.03 grams methylene blue, 12 grams concentrated sulfuric acid, 50 grams anhydrous sodium sulfate dissolved in water to make a total of one liter solution. 2. Anionic surfactant solution—0.5% Aerosol OT (Sodium dioctyl sulfo succinate). 3. Chloroform. Procedure: 1. Into a 25 ml. test tube, place 8 ml. of dye solution and 5 ml. chloroform. Add anionic surfactants solution drop by drop, shaking vigorously between drops and allowing phases to separate. Continue adding dropwise until the two layers are equal in color and intensity viewed in reflected light. Usually 10 to 12 drops of anionic solution are required. 2. Now add 2 ml. of 0.1% solution of the unknown and shake vigorously. Results: 1. Chloroform phase (lower) is deeper in color and aqueous phase is mostly colorless—anionic-is positive. 2. Water phase (upper) is deeper in color than the chloroform phase—cationic is positive. 3. Both phases are more or less the same color—probably a nonionic. 4. If the aqueous phase has become milky and hence slightly lighter in color, it may still be nonionic. Soaps do not react in this procedure. If both anionics and nonionics are present, the reaction of this test will be anionic positive. 2003.3-4.15 Miscibility—Use the test described below which is a modification of military specification MIL-€-22230 (ships): One part of the dispersing agent is mixed with 100 parts of synthetic sea water. The solution is agitated for one hour and any visible separation of the dispersing agent should be noted after this period of agitation. The test is to be performed with water temperatures at both 20°C and 0°C. The synthetic sea water shall be formulated as follows: Sodium Chloride (grams) 150.0 Magnesium Chloride, hexahydrate (grams) 86.0 Calcium Chloride dihydrate (grams) _ 9.6 Sodium Sulfate anhydrous (grams) 24.0 Distilled water to make a total of (liters) 6.0 2003.3-4.16 Dispersing Agent Components Itemize by chemical name and percentage by weight of each component of the total formulation. The percentages will include maximum, minimum and average weights in order to reflect quality control variation in manufacture or formulations. At least the following major components shall be identified in complying with 2003.3-4.16. (a) Surface active agents. (b) Solvents. (c) Additives. If requested by the submitter, information from 2003.3-4.16 will be handled as trade secrets under provisions of P.L. 90-23, the Administrative Procedures Act. 2003.3-4.17 Heavy Metal and Chlorinated Hydrocarbons Using reliable analytical chemistry techniques, state the concentrations or upper limits of the following materials: Arsenic, cadmium, chromium, copper, lead, mercury, nickel, zinc, plus any other metals that may be reasonably expected to be in the sample. Atomic absorption methods should be used and the detailed analytical methods and sample preparation shall be fully described; Cyanide using standard colorimetric procedures; Chlorinated hydrocarbons. Gas chromatography should be used and the detailed analytical methods and sample preparation shall be fully described, 2003.3-5 Analytical Laboratory Requirements for Technical Product Data: 2003.3-5.1 The required tests shall be performed by a qualified laboratory. 2003.3-5.2 The technical product data submission shall include the identity of the laboratory, the qualifications of the laboratory staff including professional biographical information for individuals responsible for any tests, and laboratory experience with similar tests. Laboratories performing bioassay tests for dispersant or surface collecting agent toxicity must demonstrate previous bioassay experience in order for their results to be accepted. EPA will not approve the selection of laboratories by intended submitters of technical product data prior to submission of the data. It is the responsibility of the submitter to select competent analytical laboratories based on the guidelines contained herein. 2003.3-5.3 EPA reserves the right to refuse to accept a submission of technical product data because of lack of qualifications of analytical laboratory, significant variance between submitted data and any laboratory confirmation performed by EPA, or other circumstances that will result in inadequate or inaccurate environmental information on the dispersing agent A-3 ------- 2004 Surface Collecting Agent fTu^.i.;: •-. Spills of Oil and Applicable Hazardous Substances 2004.1 Authorization for Use of Surface Collecting Agents: Major, Medium and Minor Discharges. 2004.1-1 The OSC may authorize use of surface collecting agents on a case-by-case basis when their use will:. 2004.1-1.1 Result in the least overe.U environmental damage or interference with designated water uses, and 2004.1-1.2 Provide a key element in the most effective system for removing uii 01 hazardous substances discharge from the water environment. 2004.1-2 Mechanism for authorizing ut~, The OSC may authorize the use of a surfs-e collecting agent verbally when on scene or by telephone prior to arriving on scene. In all cases, the OSC is obligated to comply with the provisions of 2004.2 prior to making such authorization. A review of the capabilities and expertise of the owner or operator or cleanup contractor prior to the occurence of the spill incident would be most beneficial in situations where telephone authorization is desired or contemplated. 2004.2 Restrictions on Surface Collecting Agent Use. 2004.2-1 The OSC may authorize the use of surface collecting agents only after being informed of the environmental conditions at the point of intended use. These environmental conditions include air and water temperatures, wind conditions, wave and current conditions, presence and relative density of debris and other floating matter on the water, type and condition of the oil or hazardous substance spilled, special biological factors such as waterfowl sanctuaries, wildlife refuges, spawning or nursery grounds, shellfish beds, swamp areas, etc., and the availability of removal equipment that could be employed to remove the collected material from the water. Information on environmental conditions should be evaluated by the OSC from the standpoint that conditions such as strong winds, choppy waters, low temperatureg, debris, and aquatic vegetation can adversely affect the performance of collecting agents or complicate further removal operations. The performance can also vary with types of oils, or hazardous substances. The agents can be effective with thin films of light oils but have little value with thick layers of heavy, \ iscous oils. The agents should not be used unless adequate removal equipment is available to remove the collected oil. 2004.2-2 A chemical agent shall not be used as a surface collecting agent urle,.*. Ji= provisions of 2004.3 are complied with and EPA has informed the manufacturer';, representative that the product is acceptable for use as a surface collecting agent. 2004.3 Technical Product Data foi Su,face Collecting Agents. 2004.3-1 Technical product data as specified in 2004.3-4 shall be provided to the Oil and Special Materials Control Division (WH-548), EPA, Washington, D.C. 20460, at least 60 days prior to the use of the agent. The use of existing surface collecting agents may be authorized by the OSC without complying with 2004.3 for 120 days from the effective date of this Annex. Within 60 days of receipt of the data, EPA will inform, in writing, the submitter on the adequacy of the data submitted. If additional data are requested or EPA desires to perform additional tests, the surface collecting agent may not be used until these additional needs have been satisfied and the submitter so notified. 2004.3-2 Information furnished in accordance with 2004.3-4 shall be maintained on file by the EPA, Oil and Special Materials Control Division (WH-548), Washington, D.C. 20460, to provide technical guidance to OSCs on the acceptable circumstances of use, dosage rates and special problems in the use of surface collecting agent. Any changes in the composition or formula I ion of the surface collecting agent that will affect any of the data requested in 2004.3 shall be immediately brought to the attention of EPA and testing of the agent will be repeated prior to the use of the revised formulation of the surface collecting agent. 2004.3-3 EPA will review technical product data for surface collecting agents and will issue approvals for agents meeting certain criteria. At present, the only minimum criterion established is for solubility which is described in 2004.13. This criterion classifies the substance as a surface collecting agent but is not an indication of the effectiveness or toxicity of the material. Other product data such as toxicity, chemical components, and physical characteristics will be reviewed and, if the combined effects of these data end other factors will result in excessive hazard to the aquatic life, work safety, or other elements of the environment in the judgment of EPA, the Agency may refuse to approve the use of the agent. EPA may, from time to time, establish minimum criteria for the data being requested and may also require additional data to assist in arriving at a judgment on the environmental acceptability of collecting agent usage. To avoid possible misinterpretation and misrepresentation of the EPA's role in the surface collecting agent technical product data program, the manufacturer's representatives may use only the EPA letter advising compliance with 2004.3-4 in any advertisements or technical literature on the collecting agent. The EPA letter must be used in its entirety. Failure to comply with these restrictions or any other improper reference to EPA in attempting to demonstrate EPA approval of the surface collecting agent beyond that stated in the letter for use on spills of oil or hazardous substances shall constitute grounds for removing the technical product data from EPA files which would preclude use of the surface collecting agent. 2004.3-4 Required Technical Product Data 2004.3-4.1 Name, brand, or trademark, if any, under which the surface collecting agent A-4 ------- is sold. 2004.3-4.2 Name, address and telephone number of the manufacturer, importer or vendor. 2004.3-4.3 Name, address and telephone number of primary distributors or sales outlets. 2004.3-4.4 Special handling and worker precautions for storage and field application. Maximum and minimum storage temperature to include optimum ranges as well as temperatures that will cause phase separation, chemcial changes, or otherwise damage effectiveness of the surface collecting agent. 2004.3-4.5 Shelf Life. 2004.3-4.6 Recommended application procedure(s), concentration(s) and conditions for us depending upon water salinity, water temperature and types and ages of the pollutants. 2004.3-4.7 Surface Collecting Agent Toxicity—Use standard toxicity test methods described in EPA Report "Standard Dispersant Effectiveness and Toxicity Test" (EPA R2-73-201, May 1973) pages 22-34. This report may be obtained from the Oil and Special Materials Control Division (WH-548), EPA, Washington, D.C. 20460. 2004.3-4.8 Flash Point—Select appropriate method from the following: ASTM—D 56-70; ASTM—D 92-72; ASTM—D 93-72; ASTM—D 1310-67. 2004.3-4.9 Pour Point—Use ASTM D 97- 66 2004.3-4.10 Viscosity—Use ASTM D 445- 72 2004.3-4.11 Specific Gravity—Use ASTM D 1298—67 2004.3-4.12 pH—Use ASTM D 1293-65 2004.3-4.13 Interim Test to Distinguish Between Surface Collecting Agents and Other Spill Cleanup Chemicals. In order to distinguish between surface collecting agents and other chemical materials, this interim test procedure was developed. This test procedure is not an efficiency test. It is to be used only to distinguish between surface collecting agents and dispersants. Scope 1. Procedure to be used to determine the solubility in water under standard conditions of oil spill control chemicals. Method Summary 2. Five (5) milliliters of the chemical under test are intimately mixed with ninety-five (95) milliliters of distilled water, allowed to stand undisturbed for one hour, and then the volume of the upper phase is determined to the nearest 1 milliliter. Apparatus 3. (a) Mixing cylinder, 100 milliliter subdivisions and fitted with glass stoppers. (b) Pipettes: Volumetric pipette, 5.0 millileter. (c) Timers Procedure 4. Add 95 milliliters of distilled water 22° C + / - 3° C to a 100 milliliter mixing cylinder. To the surface of the water in the mixing cylinder, add 5.0 milliliters of the chemical under test. Insert the stopper and invert the cylinder 5 times in 10 seconds. Set upright for one (1) hour at 22°C+/ —3"C and then measure the chemical layer at the surface of the water. The major portions of the chemical added (75%) should be at the water surface as a separate and easily distinguished layer. 2004.3-4.14 Surface Collecting Agent Components Itemize by chemical name and percentage by weight each component of the total formulation. The percentages will include maximum, minimum and average weights in order to reflect quality control variations in manufacture or formulations. At least the following major components shall be identified. (a) Surface active agents (b) Solvents (c) Additives If requested by the submitter, information for 2004.3-4.14 will be handled as trade secrets under provisions of Pub. L 90-23, the Administrative Procedures Act. 2004.3-4.15 Heavy Metals and Chlorinated Hydrocarbons Using reliable analytical chemistry techniques, state the concentrations or upper limits of the following materials: Arsenic, cadmium, chromium, copper, lead, mercury, nickel, zinc, plus any other metals that may bs iis the sample. Atomic absorption methods should be used and the detailed analytical methods and sample preparation shall be fully described; C\ anide using standard colorimetric prcsed"rc8; Ch-'n-ip'-Ued hydrocarbons. Gas chrematography should be used and the detailed analytical methods and sample prepare lions shall be fully described. 2004.3-5 Analytical Laboratory Requirements for Technical Product Data: Follow stipulations in 2003.3-5 ZOOS Rio logical Additive Program for Spills of On' and Applicable Hazardous Substances 2005,1 Authorization for use of biological additives. 2005.1-1 All discharges, the OSC may authorize the use of biological additives on water or shorelines only after obtaining the approval of the EPA representative to RRT. The manufacturer or supplier of microbiological cultures or enzymes must obtain approval from State and local public health and pollution control officials and furnish evidence of such approval to the EPA RRT representative. 2005.2 Special Restrictions on Biological Additive Use 2005.2-1 Microbiological cultures and enzyme mixtures shall not be considered for use as biological additives unless technical product data have been provided and accepted in accordance with 2005.3. 2005.2-2 The OSC must be supplied with the chemical composition and ratios of A-5 ------- primary nutrients or nutrient additives prior to seeking approval for their use. 2005.3 Technical Product Data for Biological Additives 2005.5-1 Technical product data as outlined in 2005.3-4 on the constituents of a biological additive shall be submitted to the Oil and Special Materials Control Division (WH-548), Environmental Protection Agency, Washington, D.C. 20460, at least 60 days prior to the use of the additive. Within 60 days of receipt of the data, EPA will inform in writing the submitter on the adequacy of the data provided. If additional information is requested or EPA desires to perform tests, the biological additive may not be used until the additional needs have been satisfied and the submitter so notified. 2005.3-2 Information furnished in accordance with 2003.3-4 shall be maintained on file by EPA to provide technical guidance to OSCs on the acceptable circumstances of use and application rates for biological additives. Any changes in the composition of the biological additive that will affect any of the data being requested in 2005.3-4 shall be immediately brought to the attention of EPA, and testing of the additive will be repeated prior to the use of the revised biological additive. 2005.3-3 The acceptance and maintenance of product data by EPA does not constitute approval of the biological additive nor does it imply compliance with any EPA criteria or minimum standards for such additives. The OSC will determine which biological additive may be used for a spill event on a case-by-case basis using all available information in making such a decision. To avoid possible misinterpretation and misrepresentation of EPA's role in this technical product data program, the manufacturer's representatives may use only the EPA letter advising compliance with 2005.3-4 in any advertisements or technical literature on the biological additive. The EPA letter must be used in its entirety. Failure to comply with these restrictions or any other improper reference to EPA in attempting to demonstrate EPA approval of the biological additive for use on spills of oil or hazardous substances shall constitute grounds for removing the technical product data from EPA files which would preclude use of the biological additive. 2005.3-4 Required Technical Product Data 2005.3-4.1 Name, brand, or trademark, if any, under which the biological additive is sold. 2005.3-4.2 Name, address and telephone number of the manufacturer, importer or vendor. 2005.3-4.3 Name, address and telephone number of primary distributors or sales outlets. 2005.3-4.4 Special handling and worker precautions for storage and field application. Maximum and minimum storage temperatures. 2005.3-4.5 Shelf Life. 2005.3-4.0 Recommended application procedure(s), concentration(s) and conditions for use depending upon water salinity, water temperature and types and ages of the pollutants. 2005.3-4.7 Statements on the expected effectiveness of the additive including degradation rates and the test conditions and data on effectiveness. 2005.3-4.8 For microbiological cultures furnish the following information: Listing of all microorganisms to species,' Percentage of each species in the composition of the additive,l Optimum pH and temperature range for use of the additive, Special nutrient requirements, if any. Separate listing of the following a'nd test methods for such determinations: Salmonella, fecal coliform, Shigella, Staphylococcus Coagulase positive, and Eleta Hemolytic Streptococci. 2005.3-4.9 For enzyme additives furnish the following information: Enyzyme name(s), International Union of Biochemistry (I.U B.) iiumber(s), Source of the enzyme, Units, Specific Activity, Optimum pH and temperature range for the use of the additive. 2005.3-5 Laboratory Requirements for Technical Product Data: Follow stipulations in 2003.3-5. 2006 Burning Agent Program for Spills of Oil and Applicable Hazardous Substances 2006.1 Authorization for Use of Burning Agents 2006.1-1 All discharges. The OSC may authorize the use of burning agents only when they will: 2106 1-1.1 Prevent or substantially reduce imminent threats to human life, limb, or property; 2006.1-1.2 Result in the least environmental harm when compared to other removal or disposal methods. 2006.1-2 Prior to authorizing use under 2006.1-1.2, the OSC must obtain approval of the EPA RRT representative and all applicable State and local public health pollution control officials. 2006.2 Special Restrictions on Burning Agent Use 2006.2-1 The OSC will evaluate the suitability of burning agents on a case-by- case basis. Burning agents should be inert materials that will not, in themselves, be a water pollutant. The addition of oils (such as gasoline or solvents) as an igniter shall be avoided unless it is necessary under 2006.1-1. 2006.2-2 A technical data program for burning agents will not be established at this time. 'If requested by the submitter, these items will b« handled as trade secrets under the provisions of the Administrative Procedures Act (Pub. L. 90-23). A-6 ------- 2007 Sinking Agent Program for Spills of Oil and Applicable Hazardous Substances 2007.1 Authorization for Use of Sinking Agents 2007.1-1 All Discharges Sinking agents shall not be applied to discharges of oil or hazardous substances on the navigable water of the United States or the contiguous zone. 2008 Mechanical Methods and Sorben ts Program for Spills of Oil and Hazardous Substances 2008.1 Authorization for Use of Mechanical Methods and Sorbents 2008.1-1 All Discharges 2008.1-1.1 As stated in 2001.3, it is the policy of this Schedule to favor the use of mechanical methods and sorbents for removal of oil and hazardous substances spills. The OSC has the authority to use or prohibit specific mechanical methods and sorbents on a case-by-case basis. The OSC will select methods and materials that, in his judgment, will be most effective in expeditiously removing the spilled material and mitigating the related damages, and will minimize secondary pollution from the removal or mitigation operation. Prior to authorizing the use of sorbents, the OSC shall take into consideration hydrographic and meteorological conditions as well as the characteristics of the sorbent and the availability of adequate containment and removal equipment. 2008.1-1.2 A technical data program for mechanical methods and sorbents will not be established at this time. (FR Doc. 60-821) Filed 3-18-80: 8 45 am] A-7 ------- APPENDIX B TECHNIQUES FOR DISPERSION AT SEA GENERAL This appendix provides a general description of the major types of application systems suitable for oil spill treatment at sea. The informa- tion presented is not meant for use in equipment construction but rather to describe operation principles and methods for calibration and dosage control. Detailed information regarding design specifications can be found in the American Petroleum Institute's Dispersant Application Manual or directly from equipment manufacturers. Vessel and aircraft application systems are discussed in this section. Hand spray equipment has been used for some applications at sea, but is con- sidered limited in capacity and application rate. Hand spray systems are described in Appendix D. VESSEL APPLICATION SYSTEMS Vessel application systems may be divided into three general categories: low-pressure spray booms, high-pressure spray booms, and single-jet or fire systems. The basic types and specifications of vessel systems are listed in Table B-l. Vessels suitable for dispersant application must be seaworthy under the spill conditions, relatively fast, and capable of carrying a reasonable amount of chemical, either as deck cargo or integral tankage. Ocean-going tugs, work boats, and some larger fishing vessels generally meet these requirements. Smaller craft can be used for close-to-shore application and when surface conditions permit. Low Pressure Spray Boom-Systems Low pressure systems (such as the Warren Spring Laboratory [WSL]-type) are intended for installation on vessels of opportunity, and consist of pump- ing systems which deliver dispersant solutions through spray nozzles that are attached to outrigger booms. The nozzles produce flat sprays and are spaced to overlap slightly at the water surface. Designed to deliver undiluted dis- persant, these systems operate at low pressures and volumes (<20 psi and <20 gal/min respectively). Several variations of the WSL-type system have been developed, including one for offshore use and a light-duty unit for inshore use. Both are designed to apply hydrocarbon base dispersants (full-strength) or water base B-l ------- TABLE B-l. BASIC VESSEL APPLICATION SYSTEMS System Type Sprav Boom Low-Pressure Spray Boom High-Pressure Single Jet Spray Representative System WSL-offshore WSL-inshore Injection type (Halliburton) Eduction type (Exxon) Onboard fire systems Portable pump system Dispersant Type Application Hydrocarbon Full strength Base Concentrate, 10:1 Water-base Hydrocarbon- Full strength base Concentrate, Water-base Concentrate Variable and Water- dilution base Concentrates Variable and dilution Water-base Concentrates Variable and dilution Water-base Concentrates Variable and dilution Pump Parameters 91 1/mln (20 gpm) Seawater: 20 gpm Injector: 2 gpm 32 1/mln (7 gpm) Seawater: 90-100 psi; 300 gpo disper- sant injector: variable to 25 psi; 25 gpm 80-100 pel; 100-150 gpm Variable Variable Method of Dosage Control Vessel speed; dosage can be doubled by shutting off one boom Vessel speed; dosage can be doubled by shutting off one boom Vessel speed; dosage can be doubled by shutting off one boom Vessel speed; eductor setting Vessel speed; eductor setting Vessel speed; eductor rate; spray angle Vessel speed; eductor rate; rate angle External Mixing Yes Yes Yes May be required May be required May be required May be required B-2 ------- or concentrate dispersants using adaptor kits. The primary components of the offshore system for full strength application are shown in the schematic diagram in Figure B-l. The basic system uses a pump which draws undiluted dispersant directly from a tank or drums, and supplies it to the booms. To apply water-diluted dispersants, the main pump draws water from the sea while a second pump injects the dispersant into the seawater stream at a fixed rate as shown in Figure B-2. (Due to the low flow rate, eductors cannot be used on this sytem). The booms are mounted to each side of the vessel and sup- ported by two masts and a series of guy wires. To facilitate mixing, breaker boards can be towed behind the spray booms to provide mixing energy. The smaller WSL-type inshore system is essentially a scaled down version of the offshore system. It is designed for use on small boats having a fully loaded freeboard of 2 to 2-1/2 feet. The system consists of a single spray boom extending out both sides of the vessel, pump, breaker boards (optional), and rigging. The dispersants are applied through two nozzles at a total rate of 5 to 7 gal/min and pressure of 12 psi. As with the offshore system, water diluted dispersants can be applied by modification with an adapter kit. High Pressure Spray Boom Systems This system is similar in appearance to the low pressure offshore system; however, the dispersants are applied in an aqueous solution at pres- sures of 90 to 100 psi and volumes ranging from 80 to 300 gpm. The increase in application pressure permits use of eductors to introduce the dispersant and provides greater initial mixing energy. In addition, the spray booms are typically mounted forward, ahead of the bow wake to insure dispersant-oil contact without bow wave disturbance. This position also takes advantage of the mixing energy supplied by the bow wave. The primary components of these systems include spray booms, a seawater pump, an eductor or metering pump, a dispersant supply, a mast or other means of boom support, rigging, and hoses. If a metering pump is used, it must be coupled to the seawater pump motor or have its own power source. Eductors require no additional source of power. A schematic of a system using educ- tors is given in Figure B-3. Systems using metering pumps are similiar to that shown in Figure B-2. High Pressure Jet Spray Systems The single jet spray system is used only with water-base or concentrate dispersants. The system is similar to the spray boom system except that single nozzles are used instead of booms with multiple nozzles, and a slight- ly larger capacity pump may be required. A schematic of a typical single jet spray system is given in Figure B-4. Adjustable fire nozzles which can produce sprays from a course stream to a fine wide cone are generally used. They can be hand-held or attached to monitors which are operated manually or automatically. A nozzle can be located at either side of the vessel, preferably ahead of the bow wave, to increase coverage. Fire fighting systems are found on many vessels of opportunity and may be used in place of the portable components of the high pressure jet spray B-3 ------- Spray booms Spray pump Flow meter Dispersant tank Figure B-1. Schematic of low pressure vessel spraying system — full-strength application. B-4 ------- Injection or Metering pump INJECTION/METERING PUMP SYSTEM Spray booms Seawater Figure B-2. Schematic for vessel spraying system — diluted applications. B-5 ------- Spray booms Spray pump Alternate . connection EDUCTOR SYSTEM Seawater Figure B-3. Schematic for high pressure vessel spraying system using eductors to introduce dispersant. B-6 ------- Injection or Metering pump Sea Water Spray Nozzle Eductors Spray Nozzle Figure B-4. Schematic — high pressure jet spray system. B-7 ------- system. Simple installation of an eductor in the main line to the nozzle(s) usually provides all the necessary modification. Figure B-5 shows installa- tion as used on a small U.S. Coast Guard fire fighting system. Calibration To accurately regulate dosage rates, the system must first be calibrated so the actual output or application rate of dispersant is known. Once cali- brated, actual dosage can be regulated by controlling vessel speed. Spray Boom Systems. The first step is to determine the total output of the system. (Pump output ratings may not reflect actual system output.) The pump is started and all valves and equipment are set in normal operating position. The output volume is determined by holding a graduated container under one of the spray nozzles for one minute or another convenient period. The amount of liquid collected is multiplied by the number of nozzles to yield the system output gallons per minute (gpm). This procedure should be repeated for a few different nozzles and the results averaged. Pressure caa be checked by installing a pressure gauge on or between the discharge port of the pump and the spray boom. In some cases the discharge and/or pressure can be altered to fall within the desired output specifications. The pump speed may be increased or decreased until the desired performance is obtained. The speed should not be altered too much as this will decrease efficiency and may result in pump and motor damage. Other methods for adjusting output include: installing gate or pressure compensating flow control valves, enlarging or decreasing nozzle size, or a combination of both. It is generally very difficult to change volume without affecting pressure and vice versa. If pressure is altered significantly, the spray angle of the nozzles and droplet size should be checked. The spray angles can be checked by observing the spray overlap when operating the system at normal volume and pressure. A 10 to 20 percent spray overlap at the water surface is desired. If there is no overlap, or it is too great, nozzles may be replaced with ones which have the required spray angle. The .nozzles should produce coarse (raindrop) size droplets, and never a mist or fog. If metering or injection pumps are used to introduce the dispersant into solution, the pump setting determines the chemical output of the system. If a standard, low-volume pump is used, it can again be checked and calibrated by installing a flow meter in the line or by holding a graduated container under the discharge port of hose for a known period. Eductors have adjustments which control the approximate percentage of dispersant in solution. The amount of dispersant introduced into solution is directly related to the quantity of seawater flow. Figure B-6 allows compu- tation of the gallons per minute of dispersant in solution at various educ- tion rates and discharge volumes. Using this figure the eductor can be set at the percentage that produces the desired amount of dispersant in solution. B-i ------- Foam Eductor System Modified Eductor System Turrent Nozzje Metering Valve Check Valve Hand Nozzle Seachest Valve Turrent Nozzle Check Valve Metering Valve Hand Nozzle 114" Checkl Ball Valve \ Valve Tygon Tubing 1/2 In Pump Seachest Valve Dispersant Pump Figure B-5. U.S. Coast Guard - foam eductor system. B-9 ------- I i—> O 14- 12- g 3 ion 8- OC LU O. u. 6 O Q. 4- 2- T 25 4% Eduction Rate 3% Eduction Rate 2% Eduction Rate 1% Eduction Rate 50 75 100 125 150 175 TOTAL DISCHARGE VOLUME IN GPM 200 225 Figure B-6. GPM of dispersant in solution at various eduction rates and discharge volumes. ------- For absolute accuracy, a flow meter should be installed between the eductor and the dispersant supply. Single Jet Spray System. Typically, the output volume of this system can- not be calibrated directly by physical measurement. A flow meter inserted inline between the hose and nozzle can monitor total output; if placed between the eductor and the dispersant supply it will monitor dispersant flow. Pressure can be determined by installing a gauge inline between the pump and nozzle. If the volume is excessive, a bleed line may be installed between the discharge port of the main pump and the eductor or metering pump. A bleed line consists of a "T" fitting placed between two sections of hose with a gate valve coupled at the tail of the fitting. A discharge hose is fitted to the valve and dropped over the side of the vessel. With the pump operating, the gate valve is opened permitting water to flow through the hose and back into the sea. The valve is adjusted slowly until the desired volume and pressure is attained at the spray nozzle. Procedures for calibrating metering pumps and eductors are similar to those described for spray boom systems. The swath width for these systems can be visually estimated in the fol- lowing manner: when all system components operating normally and nozzles set at an arc or manipulated back and forth, the distance the spray reaches on either side of the vessel should be estimated. The sum of these distances and the beam of the vessel will give the approximate swath width. Dosage Control Dosage is a function of the output volume or application rate of dis- persant, the swath width, and vessel speed. The recommended dosage for a given situation can be determined from Section 405. Figure B-7 provides a means for determining the vessel speed required to produce a desired dosage. If the dispersant is applied undiluted the pro- cedure is as follows: 1) Plot the calibrated system output volume on the horizontal axis of the large graph. 2) Draw a vertical line to the point of intersection with the desired diagonal dosage line. 3) From that point draw a horizontal line extending through the vessel speed/swath width graph. 4) The intersection of this line with the vessel swath width indicates the relative speed necessary to achieve the desired dosage. For those systems applying diluting dispersants and using an injection or metering pump, the above procedure is followed with the metering pump output substituted for the total system output. B-ll ------- SWATH WIDTH (ft) 80 . 60 40 20 0 UJ 85 100 1000 E §> a. H O •f 0 20 40 eo 80 100 120 140 16° 180 200 220 240 260 280 300 -1%- •3% \ V1 Equivalent Dispersant Output or. Full Strength Application Output or, Dispersant Injection Rate (U.S. gpm) EDUCTION RATE (percent or eductor setting) Figure B-7. Vessel speed-dosage rate graph. ------- If an eductor is used to dilute the dispersant, the following procedure is used: 1) Plot the total system output on the vertical axis of the small, lower graph. 2) Draw a horizontal line to the point of intersection with the proper eduction rate curve. 3) From that point draw a vertical line to the point where it inter- sects the desired dosage line in the large graph. (The point where the line crosses the horizontal axis of the large graph gives the equivalent dispersant output of the system). 4) Follow steps 3 and 4 described above for undiluted dispersants. If suitable vessel speeds cannot be achieved, system output must be varied. Example: It is desired to know the vessel speed required for applica- tion of a dispersant at a dosage of five gallons per acre. The system uses an eductor set at two percent and has an output of 100 gpm and a swath width of 40 feet. Using Figure B-7 an approximate vessel speed of five mph is determined as required. AIRCRAFT APPLICATION SYSTEMS Aircraft application is normally discussed in terms of helicopter systems, light and medium agricultural systems, and large or heavy air- craft systems. Aircraft should be used only to apply undiluted dispersants. Table B-2 lists typical operating ranges of a few aircraft in each category. General descriptions of each basic application system, calibration proce- dures, and dosage control are discussed in this section. Helicopter Spray Systems Helicopters prefitted to use agricultural spraying equipment are gener- ally available in most parts of the country. However, agricultural spraying systems usually produce fine mists or fogs and as such are not directly suited to dispersant application. Tests have shown that most can be quickly modifed to produce coarse sprays sufficient for dispersant use by changing nozzles. Two basic types of helicopter systems exist, the on-board (or integral) system and the bucket-type system, which is slung below the air- craft. The systems differ mainly in the method of attachment to the aircraft and in the type of pump power supply. On-Board Spray Systems. An on-board system consists of a spray pump which supplies chemicals from storage tanks to spray booms fixed below the aircraft. Figure B-8 illustrates a typical system. Depending on the type of helicopter, the spray pump is powered in one of three ways: B-13 ------- TABLE B-2. REPRESENTATIVE AIRCRAFT SPECIFICATIONS (a) Cruise Cruise Cruise Useful Speed Range Endurance Pay load (knots) (naut. miles) (hours) (pounds) HELICOPTERS Light Hughes 300 C Continental MKV-A Medium Bell 206 B Hughes 500 D Heavy Bell 205 A-l Sikorsky S-GIN FIXED-WING Light Piper Pawnee D-235 Cessna AC wagon Medium Grumman G-164B Emair MA- IB Heavy DC-6B Sup. Constellation 65 65 122 130 106 120 75(0 105(c) 91 105 225 174 (c) 195 81 290 240 270 438 203(c) 256(c) N/A N/A 1,375 N/A 3 938 1.5(c) 991 2.3 1,560 2 1,582 2.4 4,387 3.4 6,464 2.l(cl 1389 2.6(c) 1772 3.5 2,980 2.3 3,648 5.5 30,000 5.5 N/A Liquid(b) Pay load Equivalent (gallons) 111 118 186 188 522 770 165 211 355 434 3,571 3,500 'a^Maximum sling load for helicopters ( 'Assuming specific gravity of 1.0 and does not include spray system weight 'c Figures are for working, not cruise B-14 ------- of i—• U1 LEGEND (T) Mam boom assemblies (?) Tank assemblies (3) Rear boom (4) Pump and spray valve (5) Clutch (6) Spray boom extensions Figure B-8. On-board helicopter spray system. ------- • directly by power takeoff from the helicopter engine • hydraulically by an engine-driven pump • electrically using the aircraft's electrical system. In some systems pump output and pressure can be regulated from the cockpit Helicopter spray systems are generally installed on light and medium air- craft. Chemical capacity of these systems usually ranges from 50 to 250 gallons. Agricultural spray booms are generally around 40 feet in length and equipped with downward misting or atomizing nozzles. These nozzles must be replaced with hollow-cone spray nozzles which produce rain-size drops. Bucket-Type Spray Systems. Bucket-type systems are modular and designed to be slung under the helicopter. They consist of a chemical holding tank, gasoline-powered spray pump, and spray booms which are sche- matically shown in Figure B-9. The pump is operated at a preset speed and constant pressure is maintained with a pressure regulator. On and off cock- pit controls are provided. The entire system is slung beneath the helicopter using a quick-release hook and an antiyaw device to maintain correct boom orientation. Chemical capacity of most bucket systems ranges up to 200 gallons, with systems of up to 600 gallons available for large helicopters. Similar to on-board systems, bucket-type spray systems are generally supplied with agricultural type nozzles which must be replaced as before. Fixed-Wing Spray Systems Fixed-wing aircraft are routinely used for agricultural spraying and can treat terrestrial areas ranging from a few acres to tens of thousands of acres in relatively short periods of time. As in helicopter systems, modi- fications are generally restricted to nozzle changes. The most common type of equipment are specially modified light agricultural spraying aircraft and converted multi-engine piston-powered military and commercial aircraft. Fixed-wing aircraft generally require the use of spotter aircraft to direct spraying. Light to Medium Agricultural Aircraft Spraying Systems. These air- craft have the following ranges of operational capabilities: working speed: less than 110 knots working range: less than 500 nautical miles working endurance: 2-4 hours useful payload: 1000-2000 pounds tank capacity: 100-500 gallons The dispersant solution is carried in an integral tank, usually forward of the cockpit or in external wing tanks. A pump located below the tank delivers solution to the distribution or boom system attached either below the fuselage or directly to the wings. Spray pumps are generally mechani- cally driven by an air-driven propellor (which provides a pump rate propor- tional to air speed) (Figure B-10) or by a hydraulic system operated off the aircraft engine (Figure B-ll). For dispersant modification, the aircraft B-16 ------- I I—1 -^1 To boom - Boom pressure adjustment Discharge pipe Control cable to cockpit Lifting yoke Bucket tank Gasoline engine Spray pump Electrically controlled spray valve - To boom Figure B-9. Bucket-type helicopter spray system. ------- w I—• 00 LEGEND (T) Chemical tank @ Spray pump (3) Spray control valve (J) Strainer (5) Discharge tube (f) Spray boom Figure B-10. Light agricultural spray system wind driven pump. ------- w I LEGEND (T) Hydraulic pump (5) Spray pump (D Oil filter (§) Heat exchanger ^5, Relief valve (6" Master valve 7 Reservoir Figure B-11. Light agricultural spray system: hydraulic pump. ------- must be equipped with spray booms which have replaceable nozzles, and pre- ferably a boom width approaching the aircraft's wingspan. Heavy Aircraft Spraying Systems. A variety of heavy commercial and military aircraft have been converted for large-scale aerial spraying appli- cations. These aircraft are typically multi-engine piston-powered machines. Aircraft characteristics include: • working speed: 100-250 miles per hour • working range: 500+ miles • useful payload: 18,000 - 30,000 pounds • equivalent dispersant capacity: 2,500 - 4,000 gallons High capacity pumps are necessary for the outputs required by these large, high-volume spray systems. These pumps are generally driven by one or more of the aircraft's engines. Dispersant solution is pumped from tanks within the craft to spray booms attached to the bottom or top of the wings. System components are interconnected by piping which is valved for turn- ing the system on and off and recirculating the solutions. The valves are usually operated from the cockpit and electrically activated. As with many types of aerial spraying systems, most existing equipment will require modi- fication. Calibration Calibration of aircraft application systems includes consideration of droplet size and the output volume or application rate. Droplet Size. Droplet size is critical in aerial application. Very small droplets may evaporate before reaching the sea surface. Small droplets are also highly subject to wind drift, complicating control of coverage and dosage. Excessively large droplets may result in inefficient surface distri- bution of the dispersant and may penetrate through the slick. Test programs suggest aerial application is effective when droplets are in the 250 to 1000 micron size range, with the larger end of the range probably being most effective. Manufacturers' recommendations should be followed when available. Droplet size can be estimated by performing a test run over land at the desired speed and altitude, and with the system at normal operation. Non- absorbent 4 to 5 inch square cards are randomly placed perpendicular to the flight path. The cards are collected after a single pass and the droplet splats measured. An average size or range of sizes can then be determined. It should be noted, however, that the diameter of the splat on the card will be larger than the diameter of the droplet itself due to the flattening effect of the droplet striking the card. The dosage can be field calibrated as mentioned above. The drops on the cards are not only measured but counted, and the results averaged. Dosage can be estimated using the formula, D = Nr (4.5 x 10 ), where D = gal- lons per acre, N = number of drops per square centimeter, and r = droplet radius in microns. B-20 ------- Nozzle Selection. Most agricultural spraying systems available for application of dispersants are supplied with atomizing or misting nozzles. These nozzles must be replaced with nozzles which produce a coarse spray and usually a larger output. Test experience indicates that hollow cone nozzles fitted with cores which impart rotation to the existing flow, produce accept- able sprays. If the pumping system is adjustable, the pump rate may be modified until acceptable drop sizes are obtained. To increase drop size, alternate nozzles may be blocked off, permitting use of fewer, larger bore nozzles. Tests also suggest that orienting nozzles directly aft increases both droplet size and swath width. At speeds above 120 mph, i.e., heavy aircraft, nozzles may not be required. Wind shear is sufficient to create uniform spray formation and satisfactory droplet size. Tests using pipe nipples (facing aft) instead of nozzles produced acceptable (although less regular) spray patterns of satis- factory drop diameter (toward the large end of the desired range). Output Volume. Ground calibration of the output volume is done the same way as for vessels. The pumping system is operated at working speed (with water) with a graduated container held under a nozzle for a given time to collect the discharge. The quantity collected is multiplied by the number of nozzles to give the output in gallons per minute (gpm). This procedure should be repeated at several nozzles along the boom and the results averaged. Systems using wind-driven pumps, however, cannot be physically cali- brated on the ground. These pumps must be calibrated by calculation at a given airspeed, using the pump performance curves supplied by the manufac- turer or by test application. A pump output at a midrange airspeed should be used for calculation. Figure B-12 can be used to estimate required pump capacities at various air speeds and swath widths. To estimate pump requirements compare the anticipated range of operating speeds and estimated effective swath widths (ground width) with the desired dosage. The right hand column can then be used to estimate pump requirements. To use this nomogram, draw a line from the calculated ground speed through the effective swath width to find a coverage rate. From that point draw a line through the desired dosage rate to the system output column. The point of intersection gives the required output. Dosage Dosage is a function of pump capacity and pressure, effective swath width, and ground speed. It is recommended that system output be held con- stant and calibrated as described above. Application should also be held constant (altitudes of 25 to 50 feet have been shown to be effective). Dosage can then be controlled by varying airspeed. In cases where it is not practical to design or modify a system to deliver a determined dosage, multiple applications may be necessary to achieve the desired effect. B-21 ------- Requ Pump ( (9P Coverage Rate — (ac/min) Ground Speed (mph) (air speed ± wind factors) - 300 - 260 - ** Effective Swath Width Itr l - 150 - 100 - 90 - 80 - 70 - 60 - 56 • 50 • 45 - 40 - 35 - 30 • 25 - 20 - 15 11 • 10 • lb - 20 - 30 - 40 • 50 - 60 - 100 - 150 - 200 • 250 - 300 - 400 B - 10 A ; Dosage (gal/ac) i- 3 _^ - 4 1- 5 - 6 - 8 - 10 • 12 - 16 - 20 - 30 - 40 - 50 - 60 - 80 - 20 - 15 >- 12.5 - 10 • 8 - 6 . 4 - J - 2.5 - 2 - 1 - .5 ired Output m) - 2000 - 1600 - 1200 - 10OO - 800 - 600 - 500 400 - 300 - 250 200 - 150 - 120 - 100 • 80 - 60 - 50 • 40 - 30 - 26 - 20 - 15 E - .25 Figure B-12. Pump output calculation nomogram. B-22 ------- The application or air speed required to give a specific dosage can be determined using Figure B-12 if system output and effective swath width are known. (The effective swath width is greater than the boom width, typically by 1.5 to 2 times. Determination of its actual width requires field measure- ment ) . Example: A spray system has been calibrated as delivering 40 gpm; the desired application rate is 10 gallons per acre. The effec- tive swath width has been determined to be 60 feet. A line is drawn connecting these points and intersecting column A, where a ground speed of 35 mph is obtained. Weather reports indi- cate a headwind of 5 mph in the desired direction. As such, the required application airspeed is 40 mph. Field calculation of dosage can be made using the procedure for calibra- tion of droplet size. B-23 ------- APPENDIX C SHORELINE APPLICATION DISPERSANT SYSTEMS DISPERSANT EQUIPMENT AND PROCEDURES The type of equipment used to apply dispersants to shorelines varies with the type of dispersant, the type and amount of oil contamination, and the application technique selected. The following discussion identifies equipment suitable for application of dispersant types specified in Section 504. Hydrocarbon Base Dispersants Areas with limited contamination can usually be treated with a backpack or hand-held garden sprayer. Hand-held sprayer lances are generally fitted with a single, wide-angle nozzle which produces a coarse spray. Larger areas require a stationary or mobile high-volume pump with dispersant tank and capable of serving one or more spray lances with long hoses. Hydrocarbon base dispersants are generally required to treat viscous or weathered oil. They dissolve or soften coatings which permits their removal by flushing, high-pressure blasting, or steaming. In some cases, natural wave action may be sufficient. Only light applications of dispersant should be made, together with a suitable reaction period before flushing or addi- tional dosage is attempted. The amount of time should be determined on a case-by-case experimentation. For thick or heavily weathered deposits, repeated application may be required. Water Base Dispersants Water base dispersants can be applied by several different methods. The extent of contamination, the type of substrate, the availability of equip- ment, and the desired effect determine the proper method. Water base disper- sants can be used to (1) directly assist in removal of oil, or (2) prevent the reformation of slicks from loosened material. Table C-l lists different application methods for three types of oil contamination. Generally, small contaminated areas can usually be treated with a back- pack or hand-held garden sprayer containing a premixed solution of dispersant and seawater. After a suitable reaction period, the treated area may require supplementary flushing. Larger areas are more efficiently treated with spray lances or fire hoses. If the oil coating is viscous, water base dispersant can be injected into a high pressure water washing stream (hydroblaster). Mobile agricultural spraying equipment can be used for extensively con- taminated flat-lying areas, if eductors or injection pumps are incorporated C-l ------- TABLE C-l. WATER BASE DISPERSANT APPLICATION METHODS Extent and Location of Oil Contamination Application Method Mixing Method small area (vertical or horizontal vertical area large horizontal area backpack sprayers premixed hand-held lances premixed and pumps injection into induction hydroblaster fire hose, fire eduction pump and eductor mobile agricultural premixed spraying system aerial undiluted fire hose, fire pump, educted eductor on vehicle with salt water tank C-2 ------- into the system and an adequate seawater storage tank is fitted on board or towed behind the spraying equipment. Fire pumps, fire hoses and eductors can also be placed on a vehicle with a salt water storage tank to apply disper- sants over a large area. Effectiveness may be increased by discing the con- taminated area prior to treatment or pushing treated material into the surf thereby facilitating natural cleaning. Shoreline trafficability or lack of access may preclude use of vehicles on a beach. DOSAGE CONTROL Control of the application rate on shorelines can be extremely difficult and is important when dispersant and removed oil cannot be recovered. Al- though most individual application systems can be calibrated and regulated, their operators cannot. The tendency to overtreat areas of higher contami- nation may be difficult to avoid. The potential for overdosage is greatest with hydrocarbon base disper- sants. With water base dispersants, dosage can be controlled to some degree by limiting the initial concentration. When very low concentrations are used to prevent removed oil droplets from reforming, overdosage should not be a major problem. Field instruction and supervision of application personnel will reduce the potential for overdosage. Unless oily runoff is collected, shoreline treatment should be limited to periods just prior to high tide, when rapid dilution of treating agent and removed material will be greatest. C-3 ------- APPENDIX D APPLICATION OF SURFACE COLLECTING AGENTS APPLICATION PROCEDURES Manual Application Manual application of surface collecting agents (SCA) can be done using commercial backpack sprayers or hand-held garden sprayers with hand operated pumps and the nozzle of the spraying wand set to deliver a stream or coarse spray. If spray equipment is unavailable, squirt bottles or other containers can be used, provided the application of excessive quantities of SCA is avoided. In any case, SCA should be applied as close to the water surface as possible to avoid wind losses. SCA should only be applied between the oil and the area to be protected, or around the perimeter of the oil. Vessel Application. For moderate to large spills occurring in open water, application of SCA from vessels of opportunity can be done by modifying low output vessel dispersant spray equipment. A single dispersant spray boom should be mounted in a position toward the rear of the vessel so that the SCA are sprayed on the area least affected by the bow wake and propeller wash. The inboard nozzles on the spray boom should be shut off or plugged, leaving only the outboard nozzle open for application. The outboard nozzle will probably have to be modified to make a stream or coarse narrow spray pattern. The pumping system may also require modification or a valve placed in the line to provide a lower flow rate. Vessel speed must be slow enough to pre- vent turbulent mixing of the SCA by the vessel wake. Aerial Application. Both helicopters and fixed wing aircraft can be used to apply SCA. Aerial agricultural spraying systems which are modified for dispersant spraying can also be adapted for collecting agent application. Modification of the spraying systems primarily involves changing or plugging the nozzles to make a single stream or coarse narrow spray. The outboard nozzles on the aerial spray booms should be shut off or plugged, leaving one or two inboard nozzles in operation. If a coarse spray is required, the noz- zles can simply be replaced with those producing the desired spray configura- tion. For applications requiring a fine stream, the nozzles again can be interchanged. If the proper nozzles are not available, several other modi- fications can be made. In some cases the disc or core of the nozzles can be removed, producing a single stream discharge. If not, a short length of rubber hose can be fitted around the nozzle, resulting in the spray hitting the inside of the hose and subsequently running out the end as either a single stream or a stream of large drops. As a last resort, the nozzles can be removed altogether, allowing the agent to be pumped directly out the re- sulting holes. D-l ------- For helicopters using the bucket-type application system, there is a bucket available that does not use spray booms, but rather a single discharge nozzle located directly under the storage container or bucket. The nozzle can be modified as described earlier to produce a coarse spray or fine stream. Bucket-type systems are usually best suited for applying SCA to moderate size spills as they can be fitted to most helicopters with a minimum (if any) number of modifications and do not require FAA approval. When SCA are applied from the air, the aircraft should be as low as pos- sible and move as slowly as is safe to avoid excessive wind shear and disper- sion of the agent over a large area. Helicopters are best suited for this method of application. Other Application. In cases of oil seepage, persistent leaks, or small continous spills in an area having unidirectional currents, a drip pot may be used to apply SCA to the water surface in metered amounts over a long period of time. A drip pot is a drum or container of the agent fitted with a drip- type metering device. It'is usually placed on the deck of a stationary ship, or structure downstream from the source of contamination. The flow should be adjusted to the stream or current velocity and in quantities that will con- form to approved application rates. DOSAGE CONTROL Dosage control of SCA is simple, provided the output of the system is known. Output can be determined by operating the equipment at the normal speed or setting, and holding a graduated container under the discharge outlet or nozzle for one minute. The amount collected is the system output given in volume per minute. If multiple outlets are used the amount is multiplied by the number of outlets. Once the outlet is known, the dosage can be accurately controlled by varying the speed at which it is applied. The graph in Figure D-l can be used to determine the required application speed given the system output and desired dosage. D-2 ------- DOSAGE RATES Q. .§ Q 111 UJ 8, < o Q. a. 0.5 1 5 10 SYSTEM OUTPUT (gal/min) 100 Figure D-1. Surface collecting agent application speed guide. ------- |