1、/PETRO PUBL 4691-ENGL L999 0732290 Ob27338 320 FATE OF SPILLED OIL IN MARINE WATERS: WHERE DOES IT Go? WHAT DOES IT Do? How Do DISPERSANTS AFFECT IT? AN INFORMATION BOOKLET FOR DECISION-MAKERS HEALTH AND ENVIRONMENTAL SCIENCES DEPARTMENT PUBLICATION NUMBER 4691 MARCH 1999 American Petroleum Institut
2、e -b- American Petroleum Institute American Petroleum Institute -Environmental, Health, and Safety Mission and Guiding Principles MISSION The members of the American Petroleum Institute are dedicated to continuous efforts to improve tAe compatibility of our operations with the environment while econ
3、omically developing energy resources and Jupplying high qdiy products and services to consumers. We recognize our responsibility to work with the public, the government, and others to develop and to ustl natural resources in an environmentally sound manner while protecting the health and Jiy of our
4、employees and the public. To meet these responsibilities, API members pledge to manage our businesses according to the folloMing prim iples using sound science to prioritize risks and to implement cost-effective management psactices: PRINCIPLES e e a To recognize and to respond to community concerns
5、 about our raw materials, products and operations. To operate our plants and facilities, and to handle our raw materials and products in a manner that protects the environment. and the safety and health of our employees and the public. To make safety, health and environmental considerations a priori
6、ty in our planning, and our development of new products and processes. To advise promptly, appropriate officials, einployees, customers and the public of information on significant industry-related safety, health and environmental hazards, and to recommend protective measures. To counsel customers,
7、transporters and others in the safe use. transportation and disposal of our raw materials, products and waste inatenals. To economically develop and produce natural resources and to conserve those resources by using energy efficiently. To extend knowledge by conducting or supporting research on the
8、safty, health and environmental effects of our raw materials, products, processes and waste materials. To commit to reduce overall emission and waste generation. To work with others to resolve problems created by handling and disposal of hazardous substances from our operations. To participate with
9、government and others in creating responsible laws, regulations and standards to safeguard the cornmunit), w.orkplace and environment. To promote these principles and practices by sharing experiences and offering assistance to others who produce, handle, use. transport or dispose of similar raw mate
10、rials, petroleum products and wastes. STD=API/PETRO PUBL LibSL-ENGL 1999 0732290 Ob27340 T89 Fate of Spilled Oil In Marine Waters: Where Does It Go? What Does It Do? How Do Dispersants Affect It? An Information Booklet for Decision-Makers Health and Environmental Sciences Department API PUBLICATION
11、NUMBER 4691 PREPARED UNDER CONTRACT BY D.K. SCHOLZ, J.H. KUCKLICK, R. POND, A.H. WALKER, A. BOSTROM, AND P. FISCHBECK SCIENTIFIC AND ENVIRONMENTAL ASSOCIATES, INC. CAPE CHARLES, VIRGINIA MARCH 1999 American Petroleum I Institute STD*API/PETRO PUBL 4bSL-ENGL 1999 W O732290 Ob27341 9L5 FOREWORD API PU
12、BLICATIONS NECESSARILY ADDRESS PROBLEMS OF A GENERAL NATURE. WITH RESPECT TO PARTICULAR CIRCUMSTANCES, LOCAL, STATE, AND FEDERAL LAWS AND REGULATIONS SHOULD BE REVIEWD. API IS NOT UNDERTAKING TO MEET THE DUTIES OF EMPLOYERS, MANUFAC- TURERS, OR SUPPLIERS TO WARN AND PROPERLY TRAIN AND EQUIP THEIR EM
13、PLOYEES, AND OTHERS EXPOSED, CONCERNING HEALTH AND SAFETY RISKS AND PRECAUTIONS, NOR UNDERTAKING THEIR OBLIGATIONS UNDER LOCAL, STATE, OR FEDERAL LAWS. NOTHING CONTAINED IN ANY API PUBLICATION IS TO BE CONSTRUED AS GRANTING ANY RIGHT, BY IMPLICATION OR OTHERWISE, FOR THE MANU- FACTURE, SALE, OR USE
14、OF ANY METHOD, APPARATUS, OR PRODUCT COV- ERED BY LETTERS PATENT. NEITHER SHOULD ANYTHING CONTAINED IN ITY FOR INFRINGEMENT OF LETTERS PATENT. THE PUBLICATION BE CONSTRUED AS INSURING ANYONE AGAINST LIABIL- All rights reserved. No part of this work may be reproduced, stored in a retrieval system., o
15、r transmitted by any means, electronic, mechanical, photocopying, recording, or otherwise, without prior written permission from the publisher Contact the publisher; API Publishing Services, 1220 L Street, N.N, Washington, D.C. 20W5. Copyright Q 1999 Amencan Petroleum Institute iii Previous page is
16、blank. - STD.API/PETRO PUBL 4b71-ENGL 1777 0732270 0627342 85L = ACKNOWLEDGMENTS THE FOLLOWING PEOPLE ARE RECOGNIZED FOR THEIR CONTRIBUTIONS OF TIME AND EXPERTISE DURING THIS STUDY AND IN THE PREPARATION OF THIS REPORT: API STAFF CONTACT Alexis Steen, Health and Environmentai Sciences Department MEM
17、BERS OF THE OIL SPILL SCIENCE AND TECHNOLOGY WORK GROUP David Fritz, Chairperson, Amoco Dan Allen, Chevron North America E this signifies that a more detailed explanation or definition is present in the right or left narrow margin at or near where the word(s) is first used within the main text. SECT
18、ION Il: OIL CHEMISTRY REVIEW lo review information on oil properties, composition and clasdfication systems. An oils physical properties and chemical composition are important fac- tors that influence fate processes. PHYSICAL PROPERTIES OF OIL Oils are typically described in terms of their physical
19、properties e.g., ITY, ASPHALTENE and WAX CONTENT, and the presence of TRACE CONSTITUENTS (Payne, 1994). These parameters (combined with various environmental information, e.g., wave height, wind speed, cur- rents, etc.) are used to determine how oil spilled on water will react under ambient conditio
20、ns. SPECIFIC GRAVITY and API GRAVITY, POUR POINT, VISCOS- DENSITY The density of oil relative to fresh water is typically expressed in terms of specific gravity or API gravity. Density can help the decision-maker determine if an oil is likely to sink or float in the water column follow- Specific gra
21、vity is defined as the ratio of the mass of a ing a discharge. given material (e.g., 01%) to the Specific Gravity mass of freshwater, for the same volume and at the same Most oils and refined products have a specific gravity of less than 1.0; temperature. ClarkandBrown oils with a specific gravity g
22、reater than 1.0 tend to sink or be neutrally (7979) determined that the majonfy of crude oils und re- fined RrOdUCtS have sDecific buoyant (neither sink nor float on top, but stay as a unit within the water column). When these products are released onto the water, they typi- gravity values (SGI betw
23、een cally float unless they gather sediment, undergo additional WEATHER- .- - and .Oo. As these values are less man the SG for fresh water (1.0 at 4OC1, thev will ING, or are consumed by various marine animals. The specific gravity of most crude oils and refined products lies between 0.78 and 1 .O0
24、(Table float on the water surface. Wedhering is the combina- tion of physical and chemical 1) (Overstreet and Galt, 1995). As an oil or refined product weathers (components are lost to the environment), the specific gravity of that oil will increase. With an oil that has a specific gravity near 1 .o
25、0 (in fresh- Changesin OilcOmPositiOn. It may result in the removal of oil from the waters surface to the water) or 1.03 (in saltwater), weathering may result in the oil having a specific gravity value greater than or equal to the surrounding water. atmosphere, water column, sediments, and shoreline
26、s. The weathered oil may sink or it may become neutrally buoyant (Scholz et al., 1994). 2 STD.API/PETRO PUBL 4bSL-ENGL 1999 0732290 Ob27354 573 c spedllc Rioduct Gravity Gciinhe Jet Fuel (JP-4) Kf3wEne Fuel Oil No. 2 (Diesei) ww-) Kuwait Light Crude Oil hei Oil No. 6 (Bunker) NOdhslopeCNdeol SanArdo
27、(CA)CnideG, - 0.74to0.73 0.75to0.80 0.8otoo.88 0.88 0.87 0.83 0.96to0.97 0.89 0.99 API Gravity Sto62 44.3t056.7 43to29 n 23 37.8 loto 17.5 17.5 to35 5t017.5 752 4.5 0.94 2.0 to 3.5 2.25 to 5.0 79to86 13.8 500 58.4 4754 1 -2 NA 8 56 -3p 400 -450 -590 1600 Table 1. A comparison of oil properties for a
28、 variety of crude oil and refined oil products. All numbered persistence data are based on the relative persistence of the product in the envi- ronment, divided by the least persistent oil product (gasoline). Adapted from Curl and ODonnel(1977). Gilfillan (1993).API (1990). and Markanan ef ui (1993)
29、. API Gravity This scale (ranging from essentially O to more than 60; Table 1) can provide insight as to the type of oil spilled and how it will generally react in the environment. In general, the larger the API gravity value, the greater amount of light-weight components an oil or refined product h
30、as (Figure 1). With decreasing API gravity values (less than 17.5), which means increasing the amount of medium and heavy-weight com- ponents, the oil or refined product is likely to remain in the system. As an oil or refined product weathers (components are lost to the environ- ment), the API gravi
31、ty of that oil will decrease. With an oil that has an API gravity at or near 10, additional weathering may result in the oil having an API gravity value less than or equal to the surrounding water. The weathered oil may sink, or it may become neutrally buoyant (nei- ther sink nor float on top, but s
32、tay as a unit within the water column) (Scholz et al., 1994). POUR POINT If the temperature of the water is as cold or colder than the oils pour point, the oil will stiffen up and no longer flow. In cold climates and cold waters, many of the heavy refined products which have high tem- perature pour
33、points must be heated during transport and pumping. When these types of oils are spilled into the water, they will not flow readily or API gravity is a scale for measuring ffuidspeciffc gravi- ties based on an inverse rela- tionship weih specific gravity. 7bk scale was primarily devel- oped to expan
34、d the scale for specific grawy so that larger values are used. An oil with a low specific gravity (e.g., gasoline; SG = O. 73) wl have a high API graviiy PAPI = 62); inversely, an oil with a high specific gravity (e.g., very heavy crudes; SG = 0.98) wili have a low AfI gravity value PAPI= 13). API g
35、ravity = (741.5 / SG *) - 131.5 *at60F Pour point is the tempera- ture below which oil will not flow. STD.API/PETRO PUBL 4b9L-ENGL 1999 I 0732270 Ob27355 4DT Viscosity is an oils internal resistance to flow. A highly vis- cous oil will not flow easily. This physical proper?/ of the oil or refined pr
36、oduct is important to understand as it helps de- termine the oils behaviordur- ing a spill. Centistoke (est) is a unit of measurement used in defining the KINEMATIC VISCOSIP/ of a fluid. CS = 7/700 St. Kinematic viscosify is a unit of measurement used to define an alternative viscosity measurement.
37、Thk alternative viscosity measurement is sim- ply the fluids dynamic viscos- iiy divided by its density. Mea- sured in St or stoke. Number of Carbon Atoms Cl cm c40 Go+ Gasoline Jet Fuel Fuel oil #2 Lube oils Bunker C Asphaltenes Residues I I I I I ti l .+ I I l I l I I I I I O 100 200 P v 300 i U E
38、 c t .- 400 a .- c - .- O m 500 600 700 Figure 1. Distribution of various refined petroleum products as developed from a “genetic” crude oil. No concentration data are provided because the exact composition of the oil product will vary due to the source and refinery. Adapted from Markarian er ai., (
39、1993). spread. In these instances, the oil can move “like semi-submerged strands of thick rope or icebergs; the majority of the bulk oil residing just below the water surface” (Lewis and Aurand, 1997). For refined oil products, pour point values can vary between -60 OC for jet fuels to 46C for waxy
40、No. 6 fuel oils (Overstreet and Galt, 1995). ViscosiTY Viscosity is measured in CENTISTOKES (cst). An oils viscosity influ- ences or controls the success of cleanup operations, since very viscous oils are difficult to recover with conventional technologies (e.g., disc skimmers) (Overstreet and Galt,
41、 1995). As oil spilled on the water un- 4 dergoes weathering processes, the natural viscosity of the oil increases with the loss of many of its components. ASPHALTENE AND WAX CONTENT Asphaltenes and waxes are non-hydrocarbon portions of the oil which are defined in terms of their solubilities, rathe
42、r than their compositions. Oils and refined products with high asphaltene content are typically heavier, more persistent oils. Waxes are also heavy-weight components of the oil that are in crystal form when the oil is below its pour point (Payne, 1994). These components in the oil do not undergo any
43、 signifi- cant weathering alterations (Lewis and Aurand, 1997; Payne, 1994) and are essentially considered inert RESIDUE. TRACE CONSTITUENT CONTENT Trace chemicals in an oils makeup, such as nickel, vanadium, iron, alu- minum, sodium, calcium, copper, and others can also be important in stabilizing
44、emulsions and affecting weathering (NRC, 1985; Payne, 1994). Oils with large concentrations of these trace constituents tend to emulsify readily. OIL COMPOSITION Oil is not one compound or chemical, rather it is a complex mixture of thousands of different compounds (Lewis and Aurand, 1997); there ar
45、e also many types of crude oils. Because each oil field was formed mil- lions of years ago from different components, crude oils can “vary in consistency from clear straw-colored liquids to viscous black semi-flu- ids with the consistency of ice cream“ (Gilfillan, 1993). In fact, Neff (1 990) report
46、s that crude oils drawn from different wells in the same region can have markedly different properites, and even the properties of oil taken from an individual well can vary with the depth of the well and year of production. Crude oils are composed primarily of five elements: carbon, hydrogen, sulfu
47、r, nitrogen, and oxyen. These five elements are present in various combinations within the oil. Hydrocarbons (composed solely from car- bon and hydrogen atoms) are the most abundant compounds found in crude oils, up to 85 percent of the overall mixture (Gilfillan, 1993) (Table 2). Refined products s
48、uch as gasoline and fuel oil No. 6 (bunker fuels) are produced by separating (through a distillation process) the crude oil into a number of “CUTS“ with specific BOILING POINT RANGES. The three most valuable refinery products are typically gasoline, jet fu- els, and fuel oil No. 2 (home heating oil
49、and diesel fuels) (Gilfillan, 1993). Whats the Difference Between Asphalt and Asphaltene? Asphalt is a product that con- tains oil that rapidly cools to form a solid mass (e. g., asphalt pavements); usphaltenes are Components in the oil that are considered relatively inert and resistent to most weathering Residue is the waste com- pounds remaining when crude oils are processed at refineries for the extraction of gasoline, diesel fuel, and other oil prod- ucts. Residue is offen blended with lighter-weight refined products for the development of residual fue
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