DETERMINATION OF PERSISTENCE IN PETROLEUM-BASED OILS Prepared for US Environmental Protection Agency Oil Program Prepared by Dagmar Schmidt Etkin, Ph.D. Environmental Research Consulting 750 Main Street, Winchester, MA 01890 Tel: 781-721-6705/Fax: 781721-6934 [email protected] www.environmental-research.com Under Contract with: Abt Associates Inc. 4800 Montgomery Lane, Suite 600 Bethesda, MD 20814-5341 EPA Contract No. 68-W-03-020 Work Assignment B-02, Work Order B-02

1 September 2003

TABLE OF CONTENTS Executive Summary …………………………………………………………………………… US Coast Guard Definition of Persistence in Petroleum-Based Oils ………………………. Oil Pollution Act of 1990 Definitions ……………………………………………………… USCG Hazardous Materials Standards Definitions ……………………………………... Oil Persistence in USCG Oil Spill Databases …………………………………………….. Official USCG Position on Persistent/Nonpersistent Oil Lists ………………………….. Application of Definition of Oil Persistence in by USCG Programs ……………………. National Oceanic And Atmospheric Administration Guidance On Oil Behavior ………… Continuum Approach To Oil Persistence in the Environment ……………………………. National Academy of Science Oil in the Sea III Study …………………………………… Washington State Department of Ecology Application of Oil Persistence Measures …. Other Continuum of Persistence Approaches ……………………………………………. Studies on the Variability of Oil Persistence in Technical Literature ………………….. International Maritime Organization Definition of Persistent Oils ………………………... MARPOL 73/78 …………………………………………………………………………….. Civil Liability and IOPC Fund Conventions ……………………………………………... National Definitions of Persistent and Nonpersistent Oil ……………………………….. Persistent and Nonpersistent Oil in Industry ………………………………………………... Insurance Perspective on Oil Persistence …………………………………………………. International Tanker Owners Pollution Federation Perspective on Persistent Oils …... Industry Definitions of Persistent- and Nonpersistent Oil ………………………………. American Petroleum Institute View on Oil Persistence …………………………………. Chemical Analysis of Persistence Properties in Petroleum-Based Oils ……………………. References ……………………………………………………………………………………… Appendix A: US Coast Guard Hazardous Materials Standards Division Oil Types ……… Table 1: Crude Oil and Refined Petroleum Products ……………………………………. Table 2: Edible Animal and Vegetable Oils ………………………………………………. Table 3: Other Oils of Animal or Vegetable Origin ……………………………………… Table 4: Other Non-Petroleum Oils ………………………………………………………. Table 5: Lube-Oil Additives ………………………………………………………………. Appendix B: Relevant ASTM Standards ……………………………………………………. D86-02 Standard Test Method for Distillation of Petroleum Products at Atmospheric Pressure ………………………………………………………………………………… D1298-99e1 Standard Test Method for Density, Relative Density (Specific Gravity), or API Gravity of Crude Petroleum and Liquid Petroleum Products by Hydrometer Method …………………………………………………………………………………. Appendix C: USCG Marine Information for Safety and Law Enforcement (MISLE) Marine Casualty and Pollution Database Data Fields (2001 – present) …………… Appendix D: USCG Chemical Hazards Response Information System (CHRIS) Manual Data Sheets for Petroleum-Based Oils ………………………………………………..

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1 2 3 3 4 5 6 8 9 9 9 10 13 14 14 15 17 17 17 17 18 18 20 22 25 25 26 26 26 27 28 28 28 28 35

TABLE OF CONTENTS (continued) Appendix E: Correspondence with USCG Officials Regarding Persistent/Nonpersistent Oil List ………………………………………………………………………………………….. Appendix F: Annex I of MARPOL 73/78: List of OILS Covered By MARPOL 73/78 ………. Appendix G: Nations Party To International Oil Pollution Conventions With Definitions Of “Persistent Oils” (as of August 2003) …………………………………………………….. Appendix H: International Oil Pollution Compensation Fund Definitions ……………………. Table 1: IOPC Fund List of Nonpersistent Oils ……………………………………………… Table 2: IOPC Fund List of Persistent Oils …………………………………………………... Appendix I: Environment Canada Environmental Technology Centre Oil Properties Database ……………………………………………………………………………………………. Appendix J: Oil Groupings Based on Published Values in Chemical Analyses ………………. Table 1: Petroleum-Based Nonpersistent Oils (Group I) ……………………………………. Table 2: Petroleum-Based Persistent Oils: Group II (Specific Gravity 17.5] Group IV - Specific gravity between .95 to and including 1.0 [API° ≤17.5 and >10.0] Group V - Specific gravity greater than 1.0 [API° ≤10.0]

The USCG stipulates that ASTM Standard D 1298, entitled “Standard Practice for Density, Relative Density (Specific Gravity), or API Gravity of Crude Petroleum and Liquid Petroleum Projects by Hydrometer Method” be used to determine specific gravity for the purposes of all USCG rules that refer to this classification of oil types. [A further description of this standard is provided in B and in the accompanying CD-ROM that contains the standard in its entirety.] Non-Petroleum Oil is defined as “any kind that is not petroleum based. It includes, but is not limited to, animal and vegetable oils.” These definitions are consistent with Appendix E of the EPA’s Facility Response Plan (FRP) rule (40 CFR 112) and other applications by the US Coast Guard. Oil Persistence in USCG Oil Spill Databases The USCG in various versions of its Marine Casualty and Pollution Database in use since 1973 through to its most recent database, Marine Information for Safety and Law Enforcement (MISLE), do not have any data field related to “persistence” in oil. (A delineation of all the data fields in the USCG MISLE and the previous versions of the Marine Casualty and Pollution Database are shown in Appendix C). In MISLE, there are six data fields related to the description of the material spilled. The first field contains the Chemical Hazards Response Information System (CHRIS) code, which is a three-letter code for oil or chemical spilled (e.g., OSX is No. 6 fuel oil). The three-letter code refers to the CHRIS Manual, which contain detailed information about each material. (See Appendix D). The CHRIS Manual provides information on boiling points and other physical and chemical properties of each substance, in addition to human health hazards and toxicity information, as available. In no part of the CHRIS Manual is there any mention of “persistence” as it applies to oil or any other chemical. MISLE also contains a data field for the substance name spelled out, e.g., “Oil, fuel: No. 6” or “Oil: diesel.” A field for substance class defines the material as “OIL” or “CHEMICAL” or “UNSPECIFIED.” The substance subclass is similar but it divides oil

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into “Petroleum” and “Other Oil”. There are two additional fields that further define the spilled material by substance subclass and substance type. This is applied as, for example, as “Oil, misc/lubricating” or “Gasoline/automotive.” There are no data fields for oil persistence in MISLE. The USCG Marine Safety Information System (MSIS), in use from 1992 through 2001, contained a data field that denoted “P” for petroleum, to distinguish these spills from vegetable oil spills (“O” for other oils), garbage spills (“G” for garbage), chemical spills (“C” for chemicals), and natural substances, such as pollen and algae (“N” for natural). There was also a code “U” for “unknown substance.” There was no distinction between “persistent” and “nonpersistent” oil. The data fields also included the CHRIS code and substance name spelled out. Similarly, in the Pollution Incident Reporting System (PIRS), in use from 1973 through 1991, the data fields included the CHRIS code and the substance group, “P” for “petroleum”, “C” for “chemical,” “O” for “other oil,” and “U” for “unknown substance.” There was no designation of “persistent” or “nonpersistent” oil. In practical application of data entry, the CHRIS codes was often used incorrectly and substance names were frequently misspelled. There was also inconsistent usage of CHRIS codes. There were also codes “invented” and applied inconsistently when there was no existing CHRIS code to use when entering data. These errors occurred throughout all versions of the USCG Marine Casualty and Pollution Database. These errors were corrected in the data extracted from these databases for inclusion in the EPA oil spill databases prepared by ERC in April 2003. Official US Coast Guard Position on Persistent and Nonpersistent Oil Lists Despite the existence of a definition of “persistent oils” and “nonpersistent oils” with respect to USCG regulations, as described above, there is not, and has never been, an official list of “persistent oils” or “nonpersistent oils.” ERC contacted by formal letter (see Appendix E) and email, and met personally with officials at USCG Headquarters concerning their "list" of persistent/nonpersistent oils and any data they may have on persistent/nonpersistent oils from Vessel Response Plan Hotline records or for any other purpose. Each official confirmed that there is not, and has never been, an official list of persistent and nonpersistent oils, and that any list that may allegedly have existed at one point was never used in any official capacity. As explained to ERC in a personal meeting with Robert Pond of the USCG Office of Response, the major reasons for the lack of a list of persistent and nonpersistent oils are two-fold:

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•

Different batches of a particular oil type can have different characteristics, including those related to persistence in the environment;

•

Any particular oil type can have different characteristics of persistence at different times in a spill (due to changes related to weathering) and in different

environmental conditions (e.g., differences in water salinity, air and water temperature). The USCG’s official position was confirmed by the official response received from Captain Joseph J. Saboe, USCG Chief of Response, on August 26, 2003, (see Appendix E), in which Captain Saboe states: Within the US Coast Guard there is no official list of oils by persistence or any other physical characteristics because batches of the same general type of oil can have different characteristics and the persistence of a particular oil can change with weathering and under different environmental conditions. Members of EPA’s Oil Program and the US Coast Guard’s Office of Response and Office of Hazardous Standards Division have attempted to establish an official list of oils that both the US Coast Guard and EPA’s Oil Program could agree upon. To date, no consensus has been reached as how to best classify scientifically what characteristics are inherently oil-like. In addition, Captain Saboe noted that US Coast Guard is not the agency responsible for defining oil and its properties. In his August 26, 2003, letter, he states: It is the understanding of the US Coast Guard that EPA is the agency responsible for defining oil and its characteristics. Therefore, when our office receives letters like this requesting an official lists of oils, or asking for clarification on what is or is not oil, we direct them to EPA’s Oil Program Office. Captain Saboe then suggested that for further questions on oil characterization ERC contact Ensign Jereme M. Altendorf at US Coast Guard or the EPA Oil Program Center. Telephone and email contact information was provided. Application of Definition of Oil Persistence in by USCG Programs and Rules From USCG’s response perspective, it is important not to confine parameters of oil persistence to specific lists of oils because there can be very different behavior of the oils in actual spill situations and the labeling of oils by “types” with related characteristics of persistence in the environment is often too general to apply to all batches of oils. The USCG emphasizes gauging response strategies in each spill situation based on the actual behavior of the oil in the environment and through time. At the same time, however, in its February 1996 Final Rule Response Plans for Marine Transportation-Related Facilities (CFR Parts 150 and 154. Federal Register. Volume 61(4): pp. 7,921 – 7,939. February 29, 1996), USCG specifies that marine transportationrelated facility owners must develop response plans that have different criteria for nonpersistent oils and persistent oils, as defined in the rule. The definition of persistentand nonpersistent oils is consistent with that that presented above. For example, there in the “Response Capacity Planning Table” (Table 2 of rule) on page 7,937, there are different criteria for “nonpersistent oils”, light crudes, medium crudes and fuels, and heavy crudes and fuels, as shown here in Table 1.

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Spill Location Sustainability of On-Water Oil Recovery Oil Group

TABLE 1: REMOVAL CAPACITY PLANNING TABLE Rivers and Canals Nearshore/Inland/Great Lakes 3 Days

Offshore

4 Days

6 Days

% % % Oil % Oil % % Oil % Natural Recovered % Natural Recovered % Natural on on Recovered on Dissipation Floating Dissipation Floating Dissipation Shore Shore Floating Oil Shore Oil Oil

Nonpersistent 80 10 10 oils Group I Light 40 15 45 crudes Group II Medium 20 15 65 crudes/fuels Group III Heavy 5 20 75 crudes/fuels Group IV Source: Federal Register Vol. 61(4): p. 7,937, Table 2.

80

20

10

95

5

–

50

50

30

75

25

5

30

50

50

60

40

20

10

50

70

50

40

30

The different oil groups are also treated differently in terms of the assumed distance that the oil might travel or spread in water based on maximum currents. Since there is no “list” of oils, but only a definition of the different oil groups, it is up to the facility owner to determine what type of oils the facility is handling based on the criteria of distillation fractions and specific gravity, at the time of shipment. On page 7,935 of the rule, sections 7.2 and 7.3, it states that in order to calculate the effective daily recovery capacity and the planning volume for identifying shoreline cleanup capacity, “the following must be determined: The worst case discharge volume of oil in the facility; the appropriate group(s) for the type of oil handled, stored, or transported at the facility (nonpersistent (Group I) or persistent (Groups II, III, or IV)) [emphasis added]; and the facility’s specific operating area.” Similarly, in its January 1996 Final Rule on Vessel Response Plans (33 CFR Part 155. Federal Register. Volume 61(2): pp. 1,081 – 1,108. January 12, 1996), USCG makes several references to nonpersistent- and persistent oils, as well as references to the specific gravity-related groups within the persistent oil category. For example, on page 1,093, the rule states: The response plan for a vessel carrying group II or III persistent petroleum oils as a primary cargo that operates in areas with year-round pre-approval for dispersant use may request a credit against up to 25% of the on-water oil recovery capability worst case discharge tier necessary to meet the requirements of this subpart.

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And on page 1,102, the rule states: 7.2 The following procedures must be used to calculate the planning volume used by a vessel owner or operator for determining required on-water recovery capacity: 7.2.1 The following must be determined: the total volume of oil cargo carried; the appropriate cargo group for the type of petroleum oil carried [persistent (groups II, III, and IV) or nonpersistent (group I)]; and the geographic area(s) in which the vessel operates. For vessels carrying mixed cargoes For a vessel that carries multiple groups of oil, the required effective daily recovery capacity for each group is calculated and summed before applying the cap. Presumably, if facility owners or vessel owners were having difficulty classifying different oil types that they handle or ship, the official USCG position would then be to refer them to the EPA Oil Program Center. NATIONAL OCEANIC AND ATMOSPHERIC ADMINISTRATION GUIDANCE ON OIL BEHAVIOR The National Oceanic and Atmospheric Administration (NOAA) Office of Restoration, which provides the USCG and the Regional Response Teams with scientific information related to oil behavior, including oil persistence, as it relates to oil spill response and restoration of the environment, does not maintain a specific list of persistent and nonpersistent oils. However, in its 1992 training manual, Introduction to Coastal Habitats and Biological Resources for Spill Response, and in other NOAA publications, NOAA Office of Restoration defines four types of oil for which a general assessment of the behavior and fate of the oil can be made: Type 1: Very Light Oils (Jet Fuels, Gasoline) • • • •

Highly volatile (should evaporate within 1-2 days). High concentrations of toxic (soluble) compounds. Localized, severe impacts to water column and intertidal resources. No cleanup possible. Type 2: Light Oils (Diesel, No. 2 Fuel Oil, Light Crudes)

• • • •

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Moderately volatile; will leave residue (up to one-third of spill amount) after a few days. Moderate concentrations of toxic (soluble) compounds. Will "oil" intertidal resources with long-term contamination potential. Cleanup can be very effective.

Type 3: Medium Oils (Most Crude Oils) • • • •

About one-third will evaporate within 24 hours. Oil contamination of intertidal areas can be severe and long-term. Oil impacts to waterfowl and fur-bearing mammals can be severe. Cleanup most effective if conducted quickly. Type 4: Heavy Oils (Heavy Crude Oils, No. 6 Fuel Oil, Bunker C)

• • • • • •

Heavy oils with little or no evaporation or dissolution. Heavy contamination of intertidal areas likely. Severe impacts to waterfowl and fur-bearing mammals (coating and ingestion). Long-term contamination of sediments possible. Weathers very slowly. Shoreline cleanup difficult under all conditions.

While there is no mention of “persistence” per se, NOAA’s oil-type groupings indicate that oil will remain in the environment, i.e., “persist” to varying degrees in oil types 2, 3, and 4. Oil type 1 is said to evaporate within one to two days, i.e., not persist in the environment. “CONTINUUM” APPROACH TO OIL PERSISTENCE IN THE ENVIRONMENT National Academy of Sciences Oil in the Sea II Study An approach consistent with NOAA’s oil types and their assumed persistence, was applied in the National Academy of Sciences 2003 study Oil in Sea III: Inputs, Fates, and Effects (National Academy of Sciences, 2003). In this study, oils were not defined as “persistent” or “nonpersistent,” but rather as to how long they generally persist in the environment. Gasoline and light distillates, including diesel, persist for “days.” Crude oils persistent for “months.” Heavy distillates, including heavy fuel oil persist for “years.” Washington State Department of Ecology Application of Oil Persistence Measures The state of Washington applies a compensation schedule that is based on characteristics of oil types – acute toxicity, mechanical injury and persistence – to determine natural resource damage compensations for oil spills (Washington Department of Ecology 2003). The compensation schedule, administered by the Washington Department of Ecology, contains a table with relative ranking scored for several oil types, as shown in Table 2. The rankings are entered into a formula with which state officials determine the natural resource damages for a particular spill in order to impose fines and penalties on the responsible party. An example of the application of this compensation schedule in an actual spill case is described in Heimowitz (1995).

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Table 2: Washington Department of Ecology Oil Spill Damage Compensation Schedule Relative Ranking Scores for Classified Oils1,2 Mechanical Oil Class Acute Toxicity Persistence Injury 0.9 3.6 5 Prudhoe Bay Crude Oil 2.3 5 5 Bunker C 2.3 3.2 2 No. 2 Fuel Oil 5 1 1 Gasoline 1.4 2.4 1 Kerosene 1.4 2.4 1 Kerosene-type Jet Fuel 1 2 Ranks are based on scale of 0 to 5 for least to most. Source: Washington Department of Ecology (2003).

Beyond the oils listed in Table 2, there are no other oils listed as “persistent” or “nonpersistent.” When the oil is not listed in this table, the rule provides formulae for determination of acute toxicity and mechanical injury. To determine persistence, the rule states, “A persistence relative ranking score is determined from empirical data describing the length of time the spilled oil is known to, or is likely to, persist in a variety of habitat types. Scoring is assigned on a 1 to 5 scale as follows: Score Anticipated Persistence Rank 5 = 5 – 10 years or more Rank 4 = 2 – 5 years Rank 3 = 1 – 2 years Rank 2 = 1 month – 1 year Rank 1 = 1 day – weeks. Other Continuum of Persistence Approaches ERC contacted Dr. Merv Fingas, Chief of the Emergencies Science Division of Environment Canada, Ottawa, Ontario, a group that conducts much of the oil testing that is applied by NOAA in its ADIOS 2 program, Minerals Management Services, and other agencies in the US and elsewhere. Environment Canada has published two lengthy volumes of Properties of Crude Oil and Oil Products (Jokuty, et al. 1999a, b). Dr. Fingas said that “oil is almost never classified as persistent and nonpersistent” with regard to oil properties. He also confirmed that there was no list that gives this classification currently in use in Canada. In his book, The Basics of Oil Spill Cleanup (Fingas 2001), Dr. Fingas avoids classifying specific oils by “persistence,” but presents oil properties of typical oils as shown in Table 3.

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Property

Units

Viscosity

mPas at 15ºC

Density

g/mL at 15ºC

Flash Point Solubility in Water Pour Point API Gravity Interfacial Tension

Distillation Fractions

ºC ppm ºC

mN/m at 15ºC % distilled at

Table 3: Typical Oil Properties Oil Types Light Heavy Intermediate Gasoline Diesel Bunker C Crude Crude Fuel Oil 5 to 50 to 1,000 to 10,000 to 0.5 2 50 50,000 15,000 50,000 0.78 0.88 0.96 to 0.72 0.84 to to 0.94 to 0.99 1.04 0.88 1.00 -30 to -30 to -35 45 80 to 100 >100 30 60 10 to 5 to 200 40 10 to 30 1 to 5 50 30 -35 to -40 to -40 to NR -10 to 10 5 to 20 -1 30 30 30 to 10 to 65 35 10 to 20 5 to 15 50 30 10 to 15 to 27 27 25 to 30 25 to 35 30 30

100ºC

70%

1%

200ºC

100%

30%

300ºC

85%

400ºC

100%

residual

2 to 15% 15 to 40% 30 to 60% 45 to 85% 15 to 55%

1 to 10% 2 to 25% 15 to 45% 25 to 75% 25 to 75%

Crude Oil Emulsion 20,000 to 100,000 0.95 to 1.0 >80

– >50 10 to 15

–

–

NR

2 to 5%

2 to 5%

NR

15 to 25%

5 to 15%

NR

30 to 40%

15 to 25%

NR

60 to 70%

75 to 85%

NR

Source: Fingas (2001) NR = not relevant.

Note that API gravity (APIº) can be converted to specific gravity using the following formula: specific gravity (at 15.5ºC) = 141.5/(APIº+131.5) Fingas (2001) also presents a table on properties of some basic oil types and their effect on the environment, as shown in Table 4. The four properties of viscosity, adhesion, penetration, and degradation are all related to persistence and the speed of “recovery” of the environment after a spill. A product like gasoline, considered a “nonpersistent oil” by the IMO/IOPC and USCG definitions, has the capacity to penetrate substrates deeply and takes nearly as long to actually degrade or break down as bunker fuel, generally considered a “persistent oil.” Degree of penetration is into the substrate is dependent on substrate permeability or porosity. Penetration can be affected by adhesive properties and

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NR

viscosity, which varies with ambient temperature. For crude oils, the presence of water in depressions and pores of a substrate can prevent penetration. Table 4: Properties of Different Oils and Their Effect on the Environment Petroleum Plant Toxicity Water Threat Viscosity Adhesion Penetration Degradation 5 5 1 1 5 4 Gasoline 2 3 2 2 4 1 Diesel fuel 4 4 3 3 3 2 Light crude 3 2 4 4 2 3 Heavy crude 1 1 5 5 1 5 Bunker fuel Source: Fingas 2001. Lower numbers indicate more favorable conditions for the environment and faster recovery after a spill.

Fingas (2001) points out that the recovery of the environment is dependent both on the properties of the oil type, as above, and the nature of the substrate or habitat into which the oil is spilled, as well as the degree of cleanup (Table 5). The recovery time, or, in essence, persistence, is presented in terms of ranges of time, similar to that given by the National Academy of Sciences (2003) study for persistence of different oil types. Table 5: Estimated Recovery Times in Various Habitats Recovery Time (years) Habitat Without Cleanup With Minimal Cleanup With Optimal Cleanup 1 to 5 1