A review of oil cleanup technologies: Booms and skimmers, in

situ burning, chemical dispersants and biological mechanisms

Zonglin Jiang

Shanghai, People’s Republic of China

Bachelor of Science, Rensselaer Polytechnic Institute, 2020

A thesis presented to the Graduate Faculty of the University of

Virginia in Candidacy for the Degree of Master of Arts in

Environmental Sciences

Department of Graduate School of Arts and Sciences

University of Virginia

May 2023

1
Contents
List of Figures ............................................................................................................ 3
List of Tables.............................................................................................................. 5
Definitions .................................................................................................................. 5
Acknowledgement ...................................................................................................... 7
Abstract ...................................................................................................................... 8
Introduction ................................................................................................................ 9
Booms and skimmers ............................................................................................... 17
Fence booms ............................................................................................................. 18
Curtain booms .......................................................................................................... 18
Skimmers.................................................................................................................. 19
Weir skimmers ......................................................................................................... 19
Oleophilic skimmers ................................................................................................ 20
Suction skimmers ..................................................................................................... 21
Factors governing booms and skimmers .................................................................. 22
Environmental impacts of booms and skimmers ..................................................... 26
Recovery efficiency of booms and skimmers .......................................................... 26
Cost of booms and skimmers ................................................................................... 27
In Situ Burning ......................................................................................................... 27
Fire-resistant booms ................................................................................................. 28
Igniters...................................................................................................................... 29
Surface-deployed igniters ......................................................................................... 29
Aerially deployed igniters ........................................................................................ 30
Dome igniter............................................................................................................. 30
Heli-torch ................................................................................................................. 31
Factors governing in situ burning............................................................................. 33
Burning efficiency and combustion efficiency ........................................................ 34
Cost of in situ burning .............................................................................................. 35
Health of cleaning workers and Air Quality of in situ burning................................ 35

2
 Chemical dispersants ................................................................................................ 36
From ships and boats ................................................................................................ 38
From fixed-wing aircrafts......................................................................................... 38
From helicopters....................................................................................................... 39
Factors governing chemical dispersants ................................................................... 40
Effectiveness of chemical dispersants ...................................................................... 48
Cost of chemical dispersants .................................................................................... 49
Environmental impacts of chemical dispersants ...................................................... 49
Health Concern of chemical dispersants .................................................................. 51
Biological mechanisms ............................................................................................ 52
Factors affecting microorganisms’ degradation ....................................................... 56
Case Study ................................................................................................................ 57
Results ...................................................................................................................... 59
Cost of biological mechanisms ................................................................................ 60
Environmental impacts of biological mechanisms................................................... 60
Removal efficiency of biological mechanisms ........................................................ 61
Discussion ................................................................................................................ 61
Conclusion................................................................................................................ 71
References ................................................................................................................ 72

List of Figures

Figure 1 Oil spills from 1985/3/5 to 2023/1/5 in United States Mainland (data from
NOAA, results produced by ArcGIS Pro 3.0.2, all units in US gallons) ...... 11
Figure 2A: Pattern of oil spill amount B:pattern of mortality rate of birds C: pattern
of mortality rates of sea turtles D: pattern of mortality rate of
mammals(Antonio et al.2011) ....................................................................... 13
Figure 3 Probability of shoreline threat (Ritchie et al.2013) ................................ 14
Figure 4 Media report after oil spill (Ritchie et al.2013)...................................... 15
Figure 5 Percentage of technologies used in Deepwater Horizon Oil Spill Response
(Chen et al.2011)............................................................................................ 17
Figure 6 Schematic of fence boom （Hoang et al.2018） .................................. 18

Figure 7 Schematic of curtain boom (Hoang et al.2018)...................................... 19

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 Figure 8 Schematic view of weir skimmer（Fingas,2011） ................................ 20

Figure 9 Different kinds of oleophilic skimmers (Hoang et al. 2018).................. 21

Figure 10 Side view and top view of suction skimmer (Fingas,2011) ................. 21
Figure 11 Demonstration of entrainment failure (Fingas,2011) ........................... 23
Figure 12 Demonstration of submergence failure (Fingas,2011) ......................... 23
Figure 13 Relationship between efficiency and current speed (Fingas,2004) ...... 24
Figure 14 Relationship between efficiency and wind speed (Fingas,2004) ......... 25
Figure 15 Demonstration of splashover failure (Fingas, 2011) ............................ 25
Figure 16 Relationship between efficiency and wave height (Fingas,2004) ........ 26
Figure 17 Burning residues by percentage (Stone et al.2020) .............................. 28
Figure 18 Schematic of pyro booms (Buist et al.1999) ........................................ 29
Figure 19 Demonstration of surface-deployed igniters (Goodman et al.2014) .... 30
Figure 20 Structure of dome igniter (Buist et al.1999)......................................... 31
Figure 21 Heli-torch structure (Buist et al.1999).................................................. 32
Figure 22 Mechanism of oil dispersants （Dave et al. 2011） ........................... 37

Figure 23 Chemical dispersants spraying in the Deepwater Horizon response

(NOAA,2015) ................................................................................................ 39
Figure 24 Relationship between effectiveness and ratio of dispersant to oil (Fingas
et al.1991) ...................................................................................................... 41
Figure 25 Relationship between effectiveness and temperature (Fingas et al. 1991)
........................................................................................................................ 43
Figure 26 Relationship between effectiveness and salinity in first experiment
(Fingas et al. 1991) ........................................................................................ 44
Figure 27 Relationship between effectiveness and salinity in verification run
(Fingas et al. 1991) ........................................................................................ 45
Figure 28 Relationship between effectiveness and saturate content (Fingas et al.
1991) .............................................................................................................. 46
Figure 29 Relationship between effectiveness and aromatics (Fingas et al. 1991)
........................................................................................................................ 47
Figure 30 Relationship between effectiveness and asphaltene content (Fingas et al.
1991) .............................................................................................................. 47
Figure 31 Relationship between effectiveness and polar compound content (Fingas
et al. 1991) ..................................................................................................... 48
Figure 32 Relationship between mortality and growth rates of microzooplankton
under different scenarios ................................................................................ 51
Figure 33 Percentages of patients with different symptoms (Andrea et al.2013). 52
Figure 34 General mechanisms of oil degradation by enzymes （Das et al.2011）

........................................................................................................................ 55
Figure 35 Mechanisms of alkane degradation (Hassanshahian et al. 2012) ......... 56
Figure 36 Time series of different components in studied areas (a: Total PAHs;
b:Total alkanes) (Mahmoudi et al. 2013) .................................................... 58
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 Figure 37 A guide to use the oil cleanup technologies （Fingas et al.2014） .... 62

Figure 38 BOP structure demonstration (Affleck et al.2021) ............................... 65

Figure 39 Number of oil spills >7 tons from 1970 to 2019 (Ejeromedoghene et
al.2020) .......................................................................................................... 67
Figure 40 Difference between single-hulled and double-hulled tanker (Decola,2009)
........................................................................................................................ 67

List of Tables

Table 1 Some examples of cause and sources of oil spills （from various resources）

....................................................................................................................... 10
Table 2 Distributions of money on different states and projects (Floroida
Department of Environmental Protection, 2015) ........................................... 14
Table 3 Types of different oil and corresponding residue thickness (Allen et al.1993)
........................................................................................................................ 35
Table 4 The requirements for fixed wings aircrafts (Fiocco et al.1999)............... 39
Table 5 Requirements for helicopters (Fiocco et al.1999) .................................... 40
Table 6 Relationship between survivorship of S.pistillata and concentration of
dispersants (Sharfir et al.2007) ...................................................................... 50
Table 7 Results of Deepwater Horizon Oil Spill Study (Mahmoudi et al. 2013) . 59
Table 8 Technologies and corresponding phase changes ...................................... 62
Table 9 Ranking of criteria of technologies from highest to lowest ..................... 63

Definitions

Aromatics: Aromatics are hydrocarbons, organic compounds that consist only the

elements carbon and hydrogen. For example, benzene, toluene and xylenes are typical

aromatics.

Asphaltenes: Asphaltenes are chemical compounds found in crude oil. Asphaltenes

consist carbon (C4-), hydrogen(H+), nitrogen(N), oxygen(O2-) and sulfur(S2-) primarily.

Cosubstrate: cosubstrates are coenzymes that bind tightly to a protein.

Deepwater Horizon incident: On 20 April 2010, Deepwater Horizon oil rig in Gulf of

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Mexico exploded and killed 11 crewmen. Deepwater Horizon

oil rig spilled approximately 205 million US gallons (4,880,952 oil barrels) of oil

which is the largest oil spills in U.S. waters.

Exxon Valdez incident: The incident occurred in the Prince William Sound, Alaska on

March 24, 1989. The supertanker Exxon Valdez struck the reef and spilled 10.8 million

US gallons (257,142 oil barrels) of crude oil and is the second largest oil spill in U.S.

waters.

Ixtoc I incident: It was one of the most disastrous oil spills in Gulf of Mexico caused

by the blowout of an experimental well Ixtoc I during the 10 months between June 1979

and March 1980.

Oleophilic: It describes the materials that have an affinity for oils and not for water.

One barrel of oil: 42 US gallon, 0.134 tonne

PM2.5: particulate matters with aerodynamic diameter less than or equal to 2.5 micron.

Polar compounds: Polar compounds are chemical compounds held together by polar

covalent bond. In other words, polar compounds are chemical species which consists

of two or more atoms that are held together by covalent bonds and not sharing the

electrons equally.

PU: PU is also known as polyurethane. It refers to a class of polymers composed of

organic units joined by carbamate links. It is typically produced by reacting isocyanate

with polyol. It is also one of the most commonly used chemical compounds to produce

plastics.

PVC: PVC is also known as polyvinyl chloride; the chemical formula is (C2H3Cl) n. It

6
is a chemical compound widely used to produce synthetic polymer of plastic.

Salinity: The concentrations of salts in water or soils.

Torrey Canyon incident: The incident was one of the world’s most serious oil spills.

The supertanker ran aground on rocks off the south-west coast of the UK in 1967 and

spilled 25-36 million US gallons (595,238 oil barrels-857,142 oil barrels) of crude oil.

Acknowledgement

I would like to express my special thanks to my committee members (Stephen A.

Macko, Lawrence Band and Yuankun Zhao) who supported and gave me valuable
advice and comments through the thesis. Secondly, I would also like to thank my
parents and friends who were willing to give me support and encouragement during the
master’s degree.

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Abstract

The goal of this research is to do a comparative analysis on oil cleanup

technologies which include booms and skimmers, in situ burning, chemical dispersants

and biological mechanisms. In this research, the relationship between the performance

of each technology and the weather factors will be analyzed. In addition, the research

will compare the efficiency, cost, environmental and health concern of these

technologies. Finally, the research also presents the lessons learned from large scaled

oil spills.

Literature reviews were done in this research. ArcGIS Pro 3.0.2 was also used to

produce a map layout of the pattern of oil spills from 1985/3/5 to 2023/1/5 in U.S.

waters. The data were from the National Oceanic and Atmospheric Administration.

There are several major findings of this research. Biological mechanisms have the

highest efficiency, booms and skimmers have the highest cost and in situ burning has

the highest level of environmental impact.

Moreover, laws and regulations helped reduce the risks of oil spills. A lot of laws

were updated and modified after the Deepwater Horizon oil spill. For example, in 2012,

the Bureau of Safety and Environmental Enforcement updated the laws on Drilling

Safety Rule and Production Safety Regulations were also updated by 2016 which stated

the new requirements on operations and safety. Oil Pollution Act of 1990 and National

Oil and Hazardous Substances Pollution Contingency Plan also played important roles

in reducing the risks of future oil spills.

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Introduction

Oil spill is one of the major environmental concerns. Oil can cause a lot of

environmental related issues. For example, it can damage the ecosystem including

marine lives, make negative impacts on local tourism and cause health concern of

residents especially in coastal area and cleanup workers. Oil spills can involve tankers,

barges, pipelines, refineries, drilling rigs and storage facilities (Setiajid,2016). There

were several major oil spills in the history of the United States. For example, Exxon

Valdez supertanker struck the reef in Alaska and spilled over 10.8 million gallons

(257,142 oil barrels) oil in the next few days (Wolfe et al.1994). Figure 1 shows the

major oil spills along the coasts of the United States mainland. With a kernel density

analysis in ArcGIS Pro, the density of oil spills was high in the northeast of the United

States and it’s also very high along the Gulf of Mexico. The data were retrieved from

the National Ocean and Atmospheric Administration (NOAA). The data were from

1985/3/5 to 2023/1/5 and 219,000 US gallons (5214 oil barrels) was used as filters

because oil spills greater than 219,000 US gallons (5214 oil barrels) were considered

as large oil spills (ITOPF,n.d.).

Table 1 showed the causes and some typical examples of oil spills in the history

of the United States. Some causes of oil spill may include people making mistakes or

being careless, equipment breaking down, natural disasters such as hurricanes, storm

surge or high winds and deliberate acts by terrorists, act of war, vandals, or illegal

dumping (Setiajid,2019).

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 Date Cause Source Amount of Amount of spills (in

spills (in US oil barrels)

gallons)

April 20,2010 Explosion Drilling rig 205 million 4,880,952

Deepwater

Horizon

March 24, 1989 Reef Collision Tanker Exxon 11 million 257,142

Valdez

Aug.-Sept. 2005 Hurricane Various sources 8.02 million 190,952

Katrina

Nov.28,2000 Ran aground Tanker 554,400 13,200

Westchester

June 9,1990 Explosion Tanker Mega 3 million 71,428

Borg
Table 1 Some examples of cause and sources of oil spills （from various resources）
Among all these oil spills, the largest one was the Deepwater Horizon Oil Spill.

The disaster began on 20 April 2010 not far away from the coast of Gulf of Mexico.

The federal government of the United States estimated that the total amount of the oil

spill was approximate 205 million US gallons (4,880,952 oil barrels) (Blum et al.2014).

The spill was caused by the explosion and inadequate cement outside the production

casing and at the bottom of the well while drilling an exploratory well about 41 miles

off the coast of Louisiana, and the oil rig sank after the explosion and caused the largest

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oil spills in history (Smith et al.2010; Hauge et al.2012). The process was known as the

“kicks” where the surrounding rocks have higher pressure than the wellbore itself and

led to the flow of hydrocarbon into the wellbore (National Research Council, 2012).

Figure 1 Oil spills from 1985/3/5 to 2023/1/5 in United States Mainland (data from
NOAA, results produced by ArcGIS Pro 3.0.2, all units in US gallons)
Research was done in Gulf of Mexico area after Deepwater Horizon incident. It

was shown that the incident has affected a lot on the mortality of long-lived marine

tetrapod vertebrates including birds, turtles, and other marine mammals at different

levels. Approximately 8.6% of shorebirds were trapped and showed visible signs of

oiling (Beyer et al.2016). In addition, it was possible that more than one million

migratory shorebirds including 28 species were exposed to crude oil after Deepwater

Horizon incident (Beyer et al.2016). Birds’ feathers are a very sophisticated structure.

Feathers are naturally waterproof because they are aligned in a specific structure so that

11
microscopic barbs and barbules will block water (Frith, 2019). The structure of the

feathers will keep birds buoyant which creates air pockets (Frith, 2019). When oil

intrudes into these structures, it would destroy the waterproofing and buoyancy of the

bird and cause drowning and deaths of the birds.

Carcasses were collected along the US coast. The Deepwater Horizon oil spill

lasted from 22 April to 16 July 2010. The data were recorded after 38 days of the spill

which is May 28, and the reporting window was 140 days. Figures 2 show the

observation results of these species (Antonio et al.2011). Figure A showed the volume

of oil leaks over time (Antonio et al.2011). Figure B showed the pattern of mortality

rates for birds (Antonio et al.2011). It had the largest mortality among all species. The

largest recorded number was nearly 10000. Figure C showed the morality for sea turtles.

The count increased from 225 to 600 during the experiment. In addition, there was a

significant increase in the stranding rate of sea turtles, possibly 5 times than before the

incident (Beyer et al.2016). Figure D showed the pattern of mortality for mammals.

The count increased from 30 to 100.

Marine mammals were also affected by oil spills. Increased mortality of sea

mammals was observed after the spill (Antonio et al.2011). The recovery was also very

low. For cetaceans, it was estimated that the recovery rate was as low as 2% of the

actual cetacean deaths (Williams et al.2011). The observation suggested that the death

rate may been severely underestimated for cetaceans (Williams et al.2011).

12
 Figure 2A: Pattern of oil spill amount B: pattern of mortality rate of birds C: pattern
of mortality rates of sea turtles D: pattern of mortality rate of mammals (Antonio et
al.2011)
In addition, there was a large impact on tourism due to oil spills. Figure 3 showed

a map describing the probability of shoreline threat of Deepwater Horizon incident

(Ritchie et al.2013). From the map, coastal lines from Texas to Florida were all affected

by the spill at different levels. Louisiana, Mississippi, and Alabama had the highest

probability of shoreline threat which were in 81-100% range. In this situation, media

also “helped” spread the information that coastal areas were polluted and thus declining

tourism. Figure 4 was one of the examples of media news. It says, “The BP oil leak is

ruining summer vacation plans for may Tri-State families.” (Ritchie et al.2013)

Statistical analyses were done on leisure visitor spending in Louisiana. The results

showed the spending in Louisiana alone dropped by $247 million in 2010 (Richardson

et al.2018). In addition, there is a total of 790 miles of coastline in Florida and 177

miles were polluted (Florida Department of Environmental Protection, 2015). $8.1

billion would be distributed to different states and projects to restore natural resource
13
damage. The following table showed the distribution of $8.1 billion (Florida

Department of Environmental Protection, 2015).

States Amount

Louisiana $5 billion

Florida $680 million

Mississippi $296 million

Alabama $296 million

Texas $238 million

Regionwide Projects $350 million

Open Ocean Projects $1.24 billion

Table 2 Distributions of money on different states and projects (Florida Department of
Environmental Protection, 2015)

Figure 3 Probability of shoreline threat (Ritchie et al.2013)

14
 Figure 4 Media report after oil spill (Ritchie et al.2013)
Oil spills also caused serious health effects to workers and non-workers. It was

reported that assorted respiratory issues, irritation of skin, eyes, nose, throat, chest pain,

gastrointestinal complaints, headaches, dizziness, fatigue, and blood issues will happen

when coastal residents exposed, had contact with spilling oil or consume food polluted

by oil (Nance et al. 2016). Moreover, during the process of oil cleanup, workers would

also have health issues when involving chemicals such as dispersants and residues after

in situ burning. It was reported that there would be acute respiratory symptoms during

oil cleanup (Alexander et al. 2018). Other health issues could involve headache,

difficulty concentrating, numbness/tingling sensation, blurred vision, memory loss,

skin issues for cleanup workers (Krishnamurthy et al.2019; Rusiecki et al.2018). In

addition, exposure to oil will increase the risk of cancer due to hydrocarbon such as

benzene and heavy metal presented in oil.

A lot of methods and mechanisms were applied to remove oil. Booms and
15
skimmers system, in situ burning, chemical dispersants and biodegradation will be

compared and analyzed based on their efficiencies, costs and side effects on

environment.

Booms were the first response technologies deployed during surface oil spills. As

oil was moving along the surface of the ocean by current and wind forces, booms can

hold the moving oil in a steady position to do the further responses include skimming

or burning. In the Deepwater Horizon Oil Spill response, a total of 13.3 million feet of

booms were deployed during the first stage of response; In situ burning and skimmers

were used after the use of booms; 411 burns were used in the Deepwater Horizon Oil

Spill response; a total of 1.8 million gallons chemical dispersants were used in the

response with 44 percent of the chemical dispersants, approximately 800,000 gallons,

directly injected into oil flowing from the wellhead in order to prevent oil from reaching

the surface of the ocean (Blum et al. 2014). Figure 5 showed the percentage of different

technologies applied in the Deepwater Horizon Oil Spill response (Chen et al.2011).

As the statistics showed, nearly half of the spilled oil was removed by natural dispersion

or evaporation, and the remaining 26% were untreated. Only 16% of the oil was burned,

skimmed, and chemically dispersed and 17% of the oil was directly recovered from the

well head.

16
 Figure 5 Percentage of technologies used in Deepwater Horizon Oil Spill Response
(Chen et al.2011)

Booms and skimmers

Booms are floating equipment that prevent the further spreading of spilling oil.

Booms could confine the oil and maintain an adequate thickness of oil which is

necessary to carry out further remediation operations (Dhaka et al.2021). Typical

booms are made of flotation devices, free-boards, skirts, ballast, and cables. The

flotation devices keep the booms at the surface level and traps spilling oil on the

surface; free-boards float on the top of the water surface in order to ensure no oil will

overflows the top of the boom; Skirt lie below the water surface in order to reduce the

amount of oil which lost under the boom; Ballasts are at the bottom of the boom

which keep booms hanging vertically which will prevent escaping of oil slick from

under the boom; Cables are used to hold the sections of boom together (Dhaka et

al.2021).

Booms could be classified into 2 categories. They are fence booms and curtain

booms. Fence booms and curtain booms are two major types of booms used in oil

17
treatment. The classification of these 2 types of booms is based on different types of 5

main components of the booms. Different types of booms could also be applied to

different environments.

Fence booms

Fence booms have high free-boards and flat flotations (EPA,2016). Fence booms

are made of rigid or semi-rigid materials such as PVC/PU fabric. For fence booms,

these materials provide a vertical screen against the spilling oil on ocean surface.

60 % of the boom remains under the water and 40 % remain above the surface of the

water; Some special connectors are used to connect multiple boom sections (Dave et

al.2011). Figure 6 shows a fence boom (Hoang et al.2018).

Figure 6 Schematic of fence boom （Hoang et al.2018）

Curtain booms

Curtain booms have more circular flotation devices, and skirts are connected to

them. Curtain booms have large circular, foam filled chambers that remain over the

water and flexible skirts remain beneath the water; The diameters of the chambers

18
range between 100 to 500 mm and the lengths of the skirts range from 150 to 800 mm

(Dave et al.2011). Figure 7 shows the schematic of curtain booms (Hoang et

al.2018.). Besides foam filled chamber, curtain boom can also be inflatable.

Figure 7 Schematic of curtain boom (Hoang et al.2018)

Skimmers

Skimmers are always used together with booms. After booms have successfully

blocked the further spreading of spilling oil, skimming and/or suction are used by

skimmers to remove the spilling oil from the affected area, and spilling oil is

subsequently pumped into storage units on a vessel or at shorelines (Dhaka et

al.2021). Similar to booms, there are also a lot of types of skimmers based on their

different structures. There are three major types of skimmers. They are oleophilic

skimmers, suction skimmers, and weir skimmers.

Weir skimmers

Weir skimmers are composed of dams or enclosures which are located at the

interface of oil and water surface; lips of the weir skimmer are placed slightly below

the oil and water interface; due to the gravity, oil flows over the weir and is

19
selectively recovered; pumps are used to collect this mixture of water and oil and

transfer to storage tanks on vessels at the seashore (Dhaka et al.2021). After this step,

oil is either disposed or recycled depending on the condition of the oil (Dhaka et

al.2021). Figure 8 shows a schematic of weir skimmer.

Figure 8 Schematic view of weir skimmer（Fingas,2011）

Oleophilic skimmers

Oleophilic skimmers are made of oleophilic materials. Disc, drum, belt, brush,

and other shapes are some typical shapes of oleophilic skimmers. Due to the

properties of oleophilic materials, oil could be selectively adhered to the surface of

these materials when the skimmers are rotating on the water surface (Dhaka et

al.2021). The oil is then cleaned away from the oleophilic material either by

scrapping or by squeezing the material (Dhaka et al.2021). After this step, a sump is

used to collect them. Pumps or the action of gravity could transport treated oil into a

storage tank (Dhaka et al.2021). Figure 9 shows different kinds of oleophilic

skimmers.

20
 Figure 9 Different kinds of oleophilic skimmers (Hoang et al. 2018)

Suction skimmers

The working principle of suction skimmers is similar to the principle of vacuum

cleaners (Dhaka et al.2021). Vacuum pumps or air suction systems are used to suck

the spilling oil on the surface of the water directly (Dhaka et al.2021). After sucking

oil, spilling oil is transported into sumps or storage tanks (Dhaka et al.2021).

Figure 10 Side view and top view of suction skimmer (Fingas,2011)

21
Factors governing booms and skimmers

There are a lot of factors that affect the effectiveness of such method. They could

be classified as oil properties and behavior, environmental conditions, and operational

and logistical issues (Etkin et al.2020). These factors could be applied to all types of

booms and skimmers.

Slick Thickness
Oil properties and behavior play a significant role in effectiveness of mechanical

methods. The thickness of the oil slick could be approximately 0.1 mm on average

(Etkin et al.2020). A boom and skimmer system would collect approximately 100

barrels of oil per hour when the oil slick is about 0.1 mm thick (Etkin et al.2020). The

system would not be so effective when the slicks are much thinner than 0.1 mm

because not much oil would be picked up much oil during the operation (Etkin et

al.2020).

Viscosity
Viscosity is another important factor that could affect the effectiveness of boom

and skimmer system. Some kinds of oil might have high wax and gel content to make

oil non-flowing (Etkin et al.2020). High viscosity decreased the efficiency of

skimmers to collect spilling oil (Etkin et al.2020).

Current speed
Current speed is an important environmental factor that could affect the

effectiveness of mechanical methods. When the current speed is too high, which

reaches at greater than about 0.7 knots, oil will go under the booms at a high speed
22
(Etkin et al.2020). This failure is called entrainment. In addition, submergence failure

could also happen when flow velocity is too high (Fingas,2011.). When submergence

occurs, oil will flow over booms and skirts. Figure 11 and figure 12 demonstrate the

entrainment failure and submergence failure (Fingas,2011).

Figure 11 Demonstration of entrainment failure (Fingas,2011)

Figure 12 Demonstration of submergence failure (Fingas,2011)

The following diagram summarized the effectiveness of booms and skimmers

under different conditions of current speed (Figure 13) (Fingas,2004). The effectiveness

of skimmers and booms decreased as the current speed increased.

23
 Figure 13 Relationship between efficiency and current speed (Fingas,2004)

Wind speed
Wind speed will also challenge the use of booms and skimmers system. High wind

speed would make it unsafe to deploy the equipment altogether (Etkin et al.2020). In

addition, high wind speed will facilitate the spreading of spilling oil and make booms

difficult to collect them (Etkin et al.2020).

The following diagram summarized the effectiveness of booms and skimmers

under different conditions of wind speed (Figure 14) (Fingas,2004). The effectiveness

of skimmers and booms decreased as the wind speed increased.

24
 Figure 14 Relationship between efficiency and wind speed (Fingas,2004)

Wave height
Failure would also happen due to wave height factor. When wave height is greater

than the freeboard part of a boom, splashover may occur. When the wavelength to

height ratio is less than 10:1, splashover is more likely to happen (Fingas,2011). Figure

15 demonstrates splashover failure (Fingas,2011).

Figure 15 Demonstration of splashover failure (Fingas, 2011)

The following diagram summarized the effectiveness of booms and skimmers

under different conditions of wave height (Figure 16) (Fingas,2004). The effectiveness

of skimmers and booms decreased as the wave height increased.

25
 Figure 16 Relationship between efficiency and wave height (Fingas,2004)

Environmental impacts of booms and skimmers

The method is one of the most environmentally friendly methods as it only changes

the physical status of spilling oil. There is not too much environmental impact on the

surrounding environment including air and ocean water.

Recovery efficiency of booms and skimmers

There is not too much information on theoretical recovery efficiency on booms

and skimmers. However, there were a lot of reports on the recovery efficiency in real

world situations. The efficiencies were reported based on the total spilled volume. For

example, in Ixtoc I well oil spill, the total spill amount was 3,332,000 bbl of crude oil

and the efficiency of booms and skimmers was 5%; in Exxon Valdez oil spill, the total

spill amount was 261,900 bbl of crude oil and the efficiency of booms and skimmers

was 8.3% (Etkin et al.2020).

26
Cost of booms and skimmers

Based on the research, Allen and his colleagues reported the average cost on

booms and skimmers when the ratio of treated oil to total amount of oil reached 50 to

80 percent. The cost of mechanical method is $100 to $150 per barrel of oil (Allen et

al. 1993).

In Situ Burning

The components of crude oil varied. The major components of crude oil are

hydrocarbons, oxygen, nitrogen, Sulphur, and other trace metals (Hoang et al.2018).

Figure 17 shows the products of in situ burning (Stone et al.2020). Carbon monoxide

and some particulates are formed when incomplete combustion occurs. The following

shows the general equations of burning hydrocarbon, nitrogen, and sulfur components

in crude oil.

Burning hydrocarbons:

CxHy+(x+y/4) O2---xCO2+y/2H2O (Eq 1)

Burning Nitrogen:

Organic N+O2---NOx (Eq 2)

Burning Sulfur:

S+O2---SO2 (Eq 3)

27
 Figure 17 Burning residues by percentage (Stone et al.2020)
“In situ” is a Latin phrase which means “on site” or “in position”. The technology

is always used on the site of the oil spill. Among or the technologies to clean spilling

oil, in situ burning is one of the most simple and rapid methods (Dave et al.2011). The

equipment used are fire resistant booms and igniters. In addition, burning agents and

wicking agents are also necessary for this technology to sustain the combustion of oil.

Gasoline, light crude oils and numerous commercially available products are used as

burning agents. Straw, wood, glass beads and silica are used as wicking agents (Dave

et al.2011). There are also several different types of fire-resistant booms and igniters.

Fire-resistant booms

Two kinds of fire-resistant booms are used typically in the response of in situ

burning, they are Sandvik steel barrier and pyro boom.

Sandvik steel barriers

Sandvik steel barriers are one of the most efficient booms used in in situ burning.

The design of the barriers allows it to move freely and can also follow the motion of

waves. Booms are connected by bolt joints (Buist et al.1999). They also consist of

sheets of stainless steel supported by pontoons of welded stainless-steel cylinder (Buist

28
et al.1999).

Pyro booms
Pyro booms are fabric fence booms; they are supported by wire mesh and coated

with silicone rubber bonded to a fabric skirt coated with PVC; the ballasts of the boom

are chains in a pocket at the bottom of the boom; Flotation sections are series of stainless

hemispheres bolted together on the ocean surface; The floats are filled with high

temperature-resistant, closed cell foamed glass (Buist et al.1999).

Figure 18 Schematic of pyro booms (Buist et al.1999)

Igniters

Igniters are used to ignite the spilling oil. The main part of an igniter is a torch.

There are two methods to use igniters. They are surface-deployed igniters and aerially

deployed igniters.

Surface-deployed igniters

Surface-deployed igniters systems are used from a ship or from the ground. The

29
system consists of a marine flare attached to a container of light, liquid fuel (Goodman

et al.2014). In addition, diesel, gasoline or a mixture of these can also be used as fuel

and they are often gelled (Goodman et al.2014). They are initiated by using the striking

mechanism of the flare or by using a match or torch (Goodman et al.2014). The flare

breaches the container at the bottom and allows the fuel to spread (Goodman et al.2014).

The flare then ignites the fuel. At first stage, the fuel spread in order to initial fire that

provides sufficient heat to ignite the spilling oil (Goodman et al.2014). After this step,

oil will be burned due to the sufficient heat provided by the initial fire. Figure 19

showed a hand-held and improvised surface-deployed igniters (Goodman et al.2014).

Figure 19 Demonstration of surface-deployed igniters (Goodman et al.2014)

Aerially deployed igniters

Aerially deployed igniters have similar mechanisms as surface-deployed igniters.

Currently, there are two kinds of igniters system deployed aerially by helicopters or

hand thrown. They are dome igniters and Heli-torch igniters.

Dome igniter

The dome igniter has a size approximately 25cm * 15cm * 10cm and weights about

30
500g; The main parts of the system are fuel basket, solid propellant, thermal igniter

wire, gelled kerosene, metal square, mesh wire and 25cm-long fuse wire; The system

is a hand-thrown device. An electric ignition system consisting of a 12 V, spill-proof

battery with a gel electrolyte and a heater element is used to start the fuse wire; It only

takes 2 seconds to activate the igniter’s fuse wire (Buist et al.1999). After activation,

the 25cm-long safety fuse will have 45 seconds delay for throwing the igniter to targeted

oil slick. Once ignited, the solid propellant burns intensely for about 10 seconds at a

temperature higher than 1200 oC (Buist et al.1999). During this burn, gelled kerosene

begins to burn at temperature up to 700-800 oC and last about 10 minutes (Buist et

al.1999).

Figure 20 Structure of dome igniter (Buist et al.1999)

Heli-torch

The Heli-torch is a helicopter-deployable fuel igniter (Buist et al.1999). There are

three types of gelled-fuel capacities which are 110, 210 and 1100 L; Among these sizes,

210 L model has been tested most extensively on oil spills (Buist et al.1999). Figure 21

shows the structure of a helicopter deployed system. It contains a suspension adapter,

31
electrical cable, and support cable assembly. These components are used to drag the

Heli-torch and make it stable (Buist et al.1999).

Figure 21 shows a detailed structure of Heli-torch. Gelling mix is used to thicken

the gasoline that produces a smooth, viscous gel when mixed with liquid fuel (Buist et

al.1999). The gelling mix is normally poured to the entry port of the Heli-torch fuel

storage drum (Buist et al.1999). The gelled fuel mixture is lit with electrically fired

propane jets (Buist et al.1999). Then, the burning gel falls as a highly viscous stream

and exits through one or more nozzles. The viscous stream will break up into individual

globules before hitting the oil spilling site (Buist et al.1999).

Figure 21 Heli-torch structure (Buist et al.1999)

32
Factors governing in situ burning

This section will analyze the factors that govern in situ burning of spilling oil. Oil

slick thickness and flame are two key components that affect the efficiency of in situ

burning. Environmental conditions such as wind speed, current and temperature can

affect those components.

Oil slick thickness

One of the most important factors is the thickness of the oil slick. The oil should

be thick enough to ensure burning. It will act as insulation and keep the burning slick

surface at a high temperature by reducing heat loss to the ocean water (Buist et al.1999).

This layer of hot oil is known as “hot zone” (Buist et al.1999). As the oil slick thins

through burning, more heat passes through it. Then the temperature of the surface oil

will drop below its fire point at which time the burning stops (Buist et al.1999).

Wind speed and Current

Wind and current can be factors that govern oil slick thickness. Wind and current

can herd a slick against various kinds of booms discussed above, thus thickening the

oil for continued burning. When wind speed reaches 2 m/s, it is capable of herding oil

to thicknesses that will sustain the combustion (Buist et al. 1999). In this process,

current can also largely increase burning efficiency by herding oil together with wind

to increase the efficiency (Buist et al. 1999). Wind speed also affects the flame

spreading. If the fire does not spread to cover a large part of the surface of a slick, the

removal efficiency will be low (Buist et al. 1999). When the wind speed increased, the

downwind flame spreading increased.

33
Flame spreading
Flame spreading is another essential factor that affects in situ burning. As

discussed in the previous part, when flame spreading is low, the overall removal

efficiency is low (Buist et al.1999). In general, there are two ways a flame spreads

across a pool of liquid fuel. Firstly, the adjacent liquid oil can be warmed to its fire point

by radiant heating; Secondly, the hot liquid beneath the flame can also spread out over

the surrounding cold fuel (Buist et al.1999). In addition, when evaporation happens,

flame spreading velocity decreases and efficiency decreases. Additional heating of the

slick to raise the temperature of the surface of the slick is required (Buist et al. 1999).

Burning efficiency and combustion efficiency

In situ burning is assessed by two parameters: burning efficiency and combustion

efficiency. Burn efficiency is a volumetric measurement regarding the burn residue to

the volume of the initial oil (Stone et al.2020). Combustion efficiency is related to the

stoichiometric completeness of the conversion of hydrocarbons (Stone et al.2020).

Combustion efficiency depends on the oxygen level. When there is sufficient oxygen

supply, combustion efficiency will be high, and the produce of smoke will be reduced.

In situ burning has high elimination rate. On average, the range of removal for

most relatively fresh crude oils is approximately about 100 US gallons / day / square

foot (2.38 oil barrels / day / square foot) (Allen et al.1993). Experiments have shown

that a single 500-foot-long fire boom in a towed U configuration can sustain an

elimination rate of 500 gallons / minute (11.9 oil barrels / minute) (Allen et al.1993).

34
 In addition, in situ burning also has a high efficiency of burning. The volume of

oil removed depends on the original thickness of the oil. Oil is commonly burned to an

average thickness of about 2 to 3 millimeters (Allen et al.1993). Oil layers about 4

inches or 100 millimeters can result in an efficiency of removal of 98 to 99 percent

(Allen et al.1993). Table 3 summarized the residue thickness of different types of crude

oil.

Types of different oil Residue thickness

10-20mm unemulsified crude oil 1mm

50 mm unemulsified crude oil 3-5mm

Emulsified slicks Much greater than 5mm

Light and middle-distillate fuels 1mm

Table 3 Types of different oil and corresponding residue thickness (Allen et al.1993)

Cost of in situ burning

The cost of in situ burning is one of the lowest among all technologies. Based on

the use of fire-resistant boom in a towed U configuration, the average cost of in situ

burning is between $20 and $50 per barrel of oil when the burn efficiency reaches 95

percent. (Allen et al.1993).

Health of cleaning workers and Air Quality of in situ burning

Cleaning workers can expose to spilled and burned oil. There are mainly three

pathways: inhalation, skin absorption and ingestion. Inhalation is to breathe particulates,

unburned volatile organic compounds, and by-products of in situ burning. Skin

35
absorption is physical contact with spilled oil and its burn residues. Ingestion is a

process when a person incidentally consuming spilled oil or burned residue. In addition,

there will be symptoms if humans are exposed to spilled oil or burned residue.

Inhalation will cause breathing difficulties and increased dizziness, disorientation, or

headache (Barnea, n.d.). Ingestion can cause vomiting or diarrhea (Barnea, n.d.).

There are several types of emissions when oil is burned. These include smoke

plume, particulate matter, combustion gases, hydrocarbon incomplete burning, organic

compounds (Fingas, n.d.). Smoke plume, particulate matter and polyaromatic

hydrocarbons are the major compounds that can contribute to health concerns and air

pollution. Studies have been done on PM2.5 on in situ burning by the National Institute

of Environmental Health Sciences. It suggested that the highest 24-h average

concentrations of PM2.5 sometimes exceeded 5000 ug/m3 in the first 500 m downwind

of burning and reached 71 ug/m3 within a kilometer of some in situ burning and below

10 ug/m3 beyond 40 km (Pratt et al. 2020). The concentration has exceeded the safety

level. It is suggested 12 ug/m3 is a safe environment, when the level goes to or above

35 ug/m3 during a 24-hour period, the air is considered unhealthy and can cause health

issues (Indoor Air Hygiene Institute, n.d.).

Chemical dispersants

Chemical dispersants consist of surfactants, which are also known as surface

active agents (Dave et al.2011). They are dissolved in one or more solvents and

stabilizer (Dave et al.2011). Dispersants are able to break down the oil slick into smaller

36
oil droplets and transfer it into the water column where it undergoes rapid dilution and

can be easily degraded (Dave et al.2011).

Chemical dispersants work similarly to detergent soap that we use to clean grease

from dishes (Fiocco et al.1999). Chemical dispersants contain molecules with

hydrophilic, also known as water-seeking end and lipophilic, also known as oil-seeking

end (Fiocco et al.1999). The mechanism of oil dispersants is shown in figure 22 (Dave

et al.2011).

Step (a) shows dispersants applying to water surface; Step (b) shows that

dispersants molecules attaching to the oil; Step (c) shows dispersants breaking up the

oil slick. Lipophilic end is attaching to oil slick and hydrophilic group is attaching to

water and breaking them down to oil droplets.

Figure 22 Mechanism of oil dispersants （Dave et al. 2011）

Nowadays, a lot of commercially available chemical dispersants are used in oil

spill response. These include Slickgone NS, Neos AB3000, Corexit 9500, Corexit 8667,

Corexit 9600, SPC 1000TM, Finasol OSR 52 and other kinds of dispersants (Dave et

al.2011).

There are several ways to apply chemical dispersants to oil. They could be
37
deployed from ships and boats, helicopters, and fixed-wing aircraft. All dispersant spray

systems consist of a dispersant storage tank, a pump, and nozzles. Storage tank is used

to store chemical dispersants. Then pumps are used to transfer dispersants to spray arms,

and nozzles are used to convert these dispersants into a spray.

From ships and boats

Chemical dispersants are primarily deployed by aerial application from fixed-wing

planes or helicopters, boats and ships could also be used to deploy them (Fiocco et

al.1999). Ship spray arms are used on ships and boats. They are made as long as

possible. Large ships can have spray arms up to 12 m long and small boats have smaller

spray arms which are typically 5 to 6 m long (Fiocco et al.1999). Power for the

dispersant pump can be applied from ship’s electrical supply or from gasoline or diesel-

powered engines of the ships (Fiocco et al.1999).

From fixed-wing aircrafts

Dispersants can also be sprayed from fixed-wing aircrafts. These aircrafts are

evolved from small, single-engine crop-spraying aircraft (Fiocco et al.1999). Typically,

the capacity of these aircrafts is very small, usually carrying less than 1 tonne of

dispersant. Today, Douglas (DC) series aircrafts are used in dispersants spraying. For

example, DC-3, DC-4 and DC-6 are the popular aircrafts used in dispersants spraying.

The largest unit currently available is the Airborne Dispersant Delivery System (ADDS)

developed by Biegert Aviation (Fiocco et al.1999). This system can carry 5000 US

38
gallons of dispersants. The aircraft used in this system is the C-130 Hercules.

Depending on different aircrafts, spray arms could be on the wings or on the tail of the

aircraft (Fiocco et al.1999).

These spraying aircrafts have strict rules during spraying. For example, aircrafts

have strict rules on altitude, speed, and safety to ensure the effective and safe spraying

of chemical dispersants. Aircraft should be flown as low as possible. The precise

spraying parameters will differ with different aircraft types (Fiocco et al.1999). Table 4

summarizes these parameters for different types of aircrafts.

Aircrafts Speed (Knots) Altitude (Feet)

DC-3 100 15-30

Hercules 140 50-100

Table 4 The requirements for fixed wings aircrafts (Fiocco et al.1999)

Figure 23 Chemical dispersants spraying in the Deepwater Horizon response

(NOAA,2015)

From helicopters

Like fixed-wing aircraft, helicopters could also be used to spray chemical

dispersants. Helicopters are usually used in smaller scaled oil spills. A bucket is

39
underslung at the bottom of the helicopter. The size of the bucket depends on the

carrying capacity of the helicopters (Fiocco et al.1999). Spraying arms are used on

helicopters to spray the chemical dispersants. Helicopter spraying also has speed and

altitude requirement. Table 5 summarizes some typical helicopters used for spraying

chemical dispersants.

Aircrafts Speed (Knots) Altitude (feet) Carrying Capacity (tons)

MBB-105 25-50 30-50 1

S61-N 25-50 30-50 3

AS 322 Puma 25-50 30-50 3

Table 5 Requirements for helicopters (Fiocco et al.1999)

Factors governing chemical dispersants

Dispersants amount
Dispersants amount could affect the effectiveness of dispersion. The amount of

dispersants is represented by ratio of dispersant to oil (DOR) (1:x). Fingas et al. have

done experiments to explore the relationship between effectiveness of dispersion and

dispersants amount. In these experiments, 1:5 to 1:60 were used. Results were shown

in figure 24. As the results showed, the effectiveness rapidly falls with decreasing

dispersant amount; It also approaches to 0 at about 1:40 to 1:60 (Fingas et al.1991).

40
Figure 24 Relationship between effectiveness and ratio of dispersant to oil (Fingas et
al.1991)

Oil viscosity
Oil viscosity is an important factor that could govern the effectiveness of chemical

dispersants. With high viscosities, oil tends to be much less dispersible as delivery of

the surfactant to the oil-water interface becomes more difficult (Chapman et al.2007).

Oil is also affected by weathering; it will also increase the viscosity of the oil (Chapman

et al.2007). In addition, oil components can also determine the viscosity. For example,

the wax content could affect viscosity, and thus affect the effectiveness of chemical

dispersants.

Laboratory experiments have been done to explore the effects of oil viscosity on

chemical dispersants. Two kinds of oil IFO-180 and IFO-380 were used. The viscosity

of these two kinds of oil were 2000 cp and 7000 cp at 15oC (Colcomb et al.2005).

Dispersants A, B and C were used in the experiment. The temperature was 15oC in the
41
experiment. Due to confidential reasons, brand names of dispersants were not shown.

The results showed that IFO-380 was more difficult to disperse than IFO-180 because

of high viscosity. IFO-180 can be dispersed rapidly by two kinds of dispersants,

however, IFO-380 cannot be dispersed by any of the dispersants (Colcomb et al.2005).

Wind speed and current

Weather and sea conditions have played important roles in the dispersion

effectiveness. Mixing energy is always required for better dispersion. Laboratory

studies have been done to report the wind speeds needed for dispersion. It is reported

that wind speeds of at least 5 m/s are needed to generate sufficient energy for the mixing

of chemical dispersants and spilling oil (Chapman et al.2007). Dispersants are not so

effective in calm conditions. The reason is not enough energy will generate for the

mixing of chemical dispersants and oil. However, some researchers suggested that

when wind speeds do not reach 5 m/s or ocean is in calm condition, chemical

dispersants are effective when it is applied within 24 h of a spill (Colcomb et al.2005).

Temperature
Temperature can affect the performance of oil dispersants. Experiments have

shown that high temperature will reduce the viscosity of crude oil and thus improve the

effectiveness of oil dispersants（Chandrasekar et al.2006）. Experiment was done to

show the relationship between effectiveness of oil dispersants and temperature. Figure

25 shows the results of the experiment. The experiment was done by Emergencies

Science Division in Ottawa, Canada. The dispersant used was Corexit 9527 and crude

oil was Alberta Sweet Mixed Blend crude oil (Fingas et al.1991). As the result showed,

42
the effectiveness of oil dispersants is increasing rapidly with increasing temperatures.

The temperature refers to both the temperature of the oil and the seawater (Fingas et

al.1991).

Figure 25 Relationship between effectiveness and temperature (Fingas et al. 1991)

Salinity
Salinity is an important environmental factor that can affect the effectiveness of

chemical dispersants. Experiments are done with Alberta Sweet Mixed Blend (ASMB),

Norman Wells and Adgo crude oils and Corexit 9527 and Enersperse 700 chemical

dispersants were used (Fingas et al.1991). The experiment was divided into two rounds.

Different combinations of crude oil and chemical dispersants were used. In the first

round, four combinations were used. They were ASMB and Corexit, ASMB and

Enersperse 700, Norman Wells and Enersperse 700 and Adgo and Corexit. Results were

43
shown in Figure 26. In the second round, only ASMB was used with other chemical

dispersants. Results were shown in Figure 27. The results of the two rounds were

consistent. The effectiveness of chemical dispersants was at their best when salinity

was 40 to 45‰. The effectiveness was increasing rapidly when salinity is from 10‰

to 45‰. After 45‰, the effectiveness of chemical dispersants is decreasing. When

salinity is increasing, the solubility of dispersants in water is decreasing, it will result

in more surfactants being available to interact and mix with the oil (Chandrasekar et

al.2006).

Figure 26 Relationship between effectiveness and salinity in first experiment (Fingas

et al. 1991)

44
 Figure 27 Relationship between effectiveness and salinity in verification run (Fingas
et al. 1991)

Chemical Components
Saturate content is one of the components of crude oil which can affect the

effectiveness of chemical dispersants. The saturate content is the percentage of the oil

which constitutes hydrocarbon compounds with only singly-bonded carbon (Fingas et

al.1991). Various kinds of crude oil such as ADGO, Amauligak, Arabian Light, ASMB

and other crude oil were tested. In addition, Corexit, Enersperse and Dasic chemical

dispersants were used in the experiment. The results showed that there is a strong

relationship between the effectiveness of chemical dispersants. Figure 28 shows this

relationship (Fingas et al.1991). When the saturate content increased, the effectiveness

of dispersants increased rapidly. Other chemical contents in crude oil will also affect

45
the performance of dispersants such as aromatic content, asphaltene content and polar

compound. The results showed that when the percentage of aromatics increased, the

effectiveness of chemical dispersants decreased rapidly; when asphaltene content and

polar content increased, the effectiveness of chemical dispersants decreased rapidly

(Figure 29, Figure 30, Figure 31).

Figure 28 Relationship between effectiveness and saturate content (Fingas et al. 1991)

46
 Figure 29 Relationship between effectiveness and aromatics (Fingas et al. 1991)

Figure 30 Relationship between effectiveness and asphaltene content (Fingas et al.

47
 1991)

Figure 31 Relationship between effectiveness and polar compound content (Fingas et

al. 1991)

Effectiveness of chemical dispersants

The effectiveness of different chemical dispersants is different. In addition,

different kinds of crude oil and weather conditions will have different effectiveness.

Different experiments have reported various efficiency of chemical dispersants.

Experiments were done by using Corexit 9500 dispersant and Alaska North Slope and

Forties Blend crude oil were used (Davies et al.1998). The results showed that both

crude oils were dispersed completely and efficiently (Davies et al.1998). In this

experiment, two kinds of crude oil have different kinds of chemical components. There

is higher asphaltene content in Alaska North Slope crude oil, however, the results of

48
these two crude oils were the same. Thus, these researchers have concluded that the

studies that linked effectiveness of chemical dispersants and the chemical contents in

crude oil were not appropriate. However, this is still debatable.

Other researchers have reported different dispersed effectiveness of oil dispersants.

Davies et al. reported a 50 %-75% of NO.5 bunker oil (Davies et al.1998). Holakoo et

al. has reported a 90% dispersion effectiveness (Holakoo,2001). The difference in

dispersion effectiveness is largely due to different properties of certain oil. During the

Deepwater Horizon response, although there was heavy application of dispersants, over

1,300 miles of shoreline was still oiled (PWSRCAC, 2022).

Cost of chemical dispersants

The cost of chemical dispersants is another advantage. It is low compared to

booms and skimmers. Allen and his colleagues have reported the cost of dispersants

when the dispersant efficiency reached 50 to 70 percent. The cost is $50 to $100 per

barrel dispersed (Allen et al.1993).

Environmental impacts of chemical dispersants

Different kinds of oil dispersants were used, and different concentrations were

applied. There were 6 oil dispersants in experiments including Biorieco, Dispolen,

Emulgal, Inipol, Petrotech and Slickgone (Shafir et al.2007). There were 9 different

concentrations of dispersants used in the experiment. They were 0%, 0.5%, 1%, 5%,

10%, 25%,50%,75% and 100% (Shafir et al.2007). The coral species used was

49
S.Pistillata. Table 6 showed the results of the experiment one week after the

administration of nine graded solution from these tested dispersants (Sharfir et al.2007).

When the concentrations of dispersants were increasing, the survivorship of S.Pistillata

decreased rapidly, especially from 5% concentration to 10% concentration. In addition,

S.Pistillata all died when concentrations of all dispersants reached 25%.

Table 6 Relationship between survivorship of S.pistillata and concentration of

dispersants (Sharfir et al.2007)
During the responses of the Deepwater Horizon, Corexit 9500A chemical

dispersant was used. Laboratory experiments have been done on Corexit 9500A to test

the toxicity of the dispersant to marine microzooplankton. Four scenarios were involved

in the experiments: control, crude oil, dispersant and oil+dispersant. The concentrations

of crude oil and dispersant used in the 48-hour experiments were 1,5,10 uL-1 and 0.05,

0.24, 0.5 uL-1 (Almeda et al. 2014). As the results showed, when oil or dispersants were

added, the growth rate of microzooplankton decreased significantly and the mortality

rate increased rapidly in most experiments (Figure 32).

50
 Figure 32 Relationship between mortality and growth rates of microzooplankton
under different scenarios

Health Concern of chemical dispersants

Dispersants were carried out by aircraft and boat in the Deepwater Horizon oil

spill cleanup. Workers who handle and transport the dispersants were very easily

affected by these chemicals. Some workers were very sensitive to these chemicals.

Contacting with chemicals may cause disorders such as skin reddening, swelling, and

burning, follicular rashes, eye irritation, headaches, ataxia, dizziness, nausea, vomiting,

dizziness, cough, chest pain and respiratory distress. Statistics and surveys have been

done during and after the Deepwater Horizon oil spill on cleanup workers (Andrea et

al.2013). The results showed that 77% percent of patients have headaches, which was

the highest percentage and 8% with blindness which was the lowest (Figure 33).

51
 Figure 33 Percentages of patients with different symptoms (Andrea et al.2013)

Biological mechanisms

Invisible to the naked eye, there are 1030 cells in marine environment including

bacteria, archaea, and fungi (Das et al. 2010). They have played very important roles in

the global cycle of nutrients, matter, and energy in oceans. They have lived on this

planet for more than 3.5 billion years and are true master chemists that are capable of

carrying out the most diverse and sophisticated chemical reaction (Salazar et al.2017).

Archaea are one of the most abundant members of the marine plankton (Santoro

et al.2019). Once thought of as rare organisms found only in extreme temperature,

pressure, or salinity, archaea are now known in nearly every marine environment

(Santoro et al.2019). Archaea constitute a domain or kingdom of single-celled

microorganisms (Rezanka et al.2018). They are classified as prokaryotes. In other

words, they have no cell nucleus or any other membrane-bound organelles in their cells

(Rezanka et al.2018). They are found in environments like hot springs, salt lakes,
52
marshlands and oceans (Rezanka et al.2018).

Bacteria constitute a large domain of prokaryotic microorganisms (Paul,2006).

They are typically a few micrometers in length and vary in different shapes like spheres,

rods and spirals (Paul,2006). Bacteria could be found in soil, hot springs, radioactive

wastewater, Earth’s crust, bodies (Paul,2006).

Compared to archaea and bacteria, fungi appear to be rare in marine environments

(Richards et al. 2012). Fungi are classified as eukaryotic organisms that includes

microorganisms such as yeasts and molds (IUCN, 2021). According to Richards et al.

Fungi are key players in terrestrial environments (Richards et al. 2012). However, fungi

are still playing their roles in oil degrading in marine environment.

Fungi were reported that they could degrade n-alkanes and polycyclic aromatic

hydrocarbons by secreting extracellular enzymes (Poutasse et al. 2015). Nine bacterial

strains were found that they could degrade crude oil in polluted tropical stream in Lagos

and Nigeria (Adebusoye et al. 2007). A study in Amazonian Basin reported that some

archaea such as Halobacteriaceae, Desulfurococcaceae and Methanobacteriaceae

were involved in biodegradation of Brazilian crude oil within less than 48-days in

treatments (Campeao et al. 2017). Moreover, archaea are classified into 4 groups, which

are MGI, MGII, MGIII and MGIV (Santoro et al.2019). MGII and MGIII have the

potential to degrade high-molecular-weight compounds (Santoro et al. 2019).

Natural biodegradation occurred during the response of the Deepwater Horizon

Oil Spill. In addition, bioremediation was also a technology used to facilitate natural

biodegradation as a response to the oil spill. There are mainly two approaches to

53
bioremediation, namely bioaugmentation and biostimulation. Bioaugmentation is the

process to add oil-degrading microorganisms to the existing microbial population, and

biostimulation is the growth of indigenous oil degraders stimulated by the addition of

nutrients or other growth-limiting cosubstrates (Das et al. 2011). Moreover,

biodegradation could also happen naturally without human intervention.

Figure 34 shows the main principle of aerobic degradation. Firstly, when

hydrocarbons enter the system, they are attacked by oxygenases. Oxygenases are a

group of unique enzymes that catalyze oxygen fixation reactions (Hayaishi, 2013).

Secondly, peripheral degradation pathways convert organic pollutants into

intermediates of the central intermediary metabolism step by step. Finally,

biosynthesis of cell biomass occurs from the central precursor metabolites (Das et

al.2011). Most of the hydrocarbon pollutants are degraded into water, carbon dioxide

and oxygen. Depending on the chain length, enzyme systems are required to introduce

oxygen in the substrate to initiate biodegradation (Das et al.2011).

54
 Figure 34 General mechanisms of oil degradation by enzymes （Das et al.2011）
Alkane is one of the major components in crude oil. The following diagram shows

the degradation of alkane under aerobic condition (Figure 35). There are several

pathways of alkane degradation (Hassanshahian et al. 2013). [A] is monoterminal

oxidation, [B] is biterminal oxidation and [C] is subterminal oxidation. The reaction

involves the activity with monooxygenase, after that, a hydroxyl group was introduced

into the aliphatic chain (Hassanshahian et al. 2012).

55
 Figure 35 Mechanisms of alkane degradation (Hassanshahian et al. 2012)

Factors affecting microorganisms’ degradation

Temperature
Temperature is an important factor that affects. It has been found that the rate of

biodegradation generally decreases with the decreasing temperature (Das et al. 2011).

The highest degradation rates generally occur in the range of 30oC-40oC in soil

environments and 20oC-30oC in some freshwater environments and 15oC-20oC in

marine environments (Das et al.2011).

Oxygen level
As microorganisms’ degradation will happen more likely under aerobic

conditions, oxygen level is another factor that affected the microorganisms degrading.

Oxygen level is affected by the amount of oil spill. The aeration rate decreased with

more oil. As a result, the rate of degradation will decrease (Benka-Coker et al.1996).

56
Case Study

The observations and experiments have suggested that Gulf of Mexico marsh

sediments have considerable biodegradation potential and biodegradation was

confirmed by a combination of DNA, lipid, and isotopic approaches (Mahmoudi et al.

2013).

In this experiment, all samples were collected in Spartina alterniflora-

dominated salt marshes in Barataria Bay, Louisiana. Samples were collected from two

“impacted” sites and two “references” sites (Mahmoudi et al. 2013). The concentration

of PAH and alkane were measured. They were the main components of leaking oil of

Deepwater Horizon Oil Spill. Diagram a and b represented the concentration of PAH

and alkane, respectively (Figure 36). Examples were collected 5, 11, 18 months after

oil spill. From these diagrams, both PAH and alkane have highest concentration after 5

months of the spill. After 11 months, concentration values have reduced rapidly. After

18 months, concentration of PAH and alkane almost reduced to 0 mg/kg in 2 impacted

sites.

57
Figure 36 Time series of different components in studied areas (a: Total PAHs; b:Total
alkanes) (Mahmoudi et al. 2013)
Incorporation of carbon into microbial lipids and increasing abundance of

hydrocarbon-degrading species were the evidence of biodegradation (Mahmoudi et al.

2013). Isotopic mass balance approach was used to calculate Δ14CPLFA-rich. This value

measures the isotopic ratio of 14C content in lipids. Microbial uptake and incorporation

of petroleum carbon will reduce the 14C content of microbial membrane lipids, such as

Phospholipid-derived fatty acids (PLFAs) (Mahmoudi et al. 2013). Highly depleted

Δ14CPLFA-rich values observed at impacted sites 5 months after oil spill showed that

indigenous microbial communities were contributing to the loss of petroleum at

impacted sites (Mahmoudi et al. 2013). After 18 months of oil intrusion, Δ14CPLFA-rich

values were significantly less depleted since the contribution of petroleum carbon has

decreased (Mahmoudi et al. 2013). It was estimated that 86% and 78% of the carbon in

microbial PLFAs was derived from oil at impacted sites 1 and 2, respectively

(Mahmoudi et al. 2013).

Pyrosequencing technology was also used in this experiment. Operational

taxonomic unites (OTUs) were used to quantify the abundance of species. Statistical

analysis was used to show the contribution level of archaea, fungi and bacteria in oil

degradation. Nonmetric multidimensional scaling (NMDS) analysis based on Chi

Squared distance between sites were measured. Table 1 shows the results of these
58
analysis. P-values are significance levels between the observed pattern of species

taxonomic clustering for impacted sites and total alkane and PAH after 5 months. R2

values showed how closely are relative abundance of bacteria, archaea and fungi at

impacted sites clustered with references sites after 18 months.

Most OTU values P-values R2

Abundant (in %)

Phylum

Archaea Crenarchaeota 55.1 P>0.05 0.99

Bacteria Proteobacteria 65.4 P<0.05 0.87

Fungi Ascomycota 56.1 P>0.05 0.78

Table 7 Results of Deepwater Horizon Oil Spill Study (Mahmoudi et al. 2013)

Results

In the Deepwater Horizon oil spill experiment, archaea, bacteria and fungi have

all played their roles in oil degrading. For bacteria, Rhodobacterales and

Sphingomoadales (order of Proteobacteria) have been found in impacted sites 5 months

after oil intrusion into sediments which are dominant bacteria in degrading oil

(Mahmoudi et al. 2013). The taxonomic composition of impacted and reference sites

became more similar by 18 months after oil intrusion. P value after 5 months is smaller

than 0.05. The result is significant.

However, in this experiment and observation, the roles of archaea in hydrocarbon

degradation were not well understood (Mahmoudi et al. 2013). The p value of archaea
59
is also greater than 0.05 which means an insignificant result. Archaeal communities’

structure is more similar to each other rather than to the reference sites, regardless of

concentration of the pollutants (Mahmoudi et al. 2013).

In this study, fungi also played an important role in breaking down oil. After 5

months of oil intrusion, Dothideomycetes’s (class of Ascomycota) relative frequency of

OTUs has increased (Mahmoudi et al. 2013). This suggests that this group may be

playing a significant role in oil degrading. Dothideomycetes could produce oxidase

enzymes such as laccase and peroxidase. However, p value is greater than 0.05 for fungi

which means it is insignificant and requires future study.

Cost of biological mechanisms

The cost of biological mechanisms is low compared to other technologies used in

oil cleanup. From the research, the cost of bioremediation is (Orellana et al.2022) is

318.9 USD to 1952.4 USD per tonne (Orellana et al.2022). Converting to per oil barrel,

the cost is 43.3 USD to 266.4 USD. Moreover, biodegradation could also happen

indigenously without human intervention. The labor cost is typically lower than the cost

of other methods. It did not require constant needs of workers.

Environmental impacts of biological mechanisms

Biological ways are environmentally friendly. Natural biodegradation does not

damage the natural habitat as the process can happen naturally without human

intervention. Moreover, as no toxic chemicals will be added while bioremediation

60
applies, natural habitats will not be damaged.

Removal efficiency of biological mechanisms

The removal efficiency of biological ways can achieve nearly 100 percent.

However, it will take a very long time to achieve high efficiency. As the Deepwater

Horizon oil spills experiment showed, it took 18 months to remove all the spilling oil

in the site which is not always the best choice to remove spilling oil. Problems could

also be raised in bioaugmentation and biostimulation. It was reported that sometimes

there was no visible increase in biodegradation when bioaugmentation applies (Amber

et al.2012). For biostimulation, nutrients would be lost if there were more waves and

energy (Radermacher).

Discussion

As all the oil cleanup technologies are weather dependent, Allen has produced an

oil technologies guide based on wind speed, wind force, and wind-wave height with the

relationship to oil slick thickness as shown in figure 37 (Fingas et al.2014). As the

diagram shows, when the oil thickness is greater than 10-4 inches, less than 1 inch, and

when weather conditions meet certain requirements, mechanical cleanup and burning

will be used in oil cleanup. Otherwise, people will not intervene in the oil cleanup

processes except monitor and wait until the conditions meet the requirements.

61
 Figure 37 A guide to use the oil cleanup technologies （Fingas et al.2014）

In this section, the efficiency, cost, and level of environmental impact level will be

compared between these technologies. Some technologies and mechanisms only

change the phases of oil. Table 8 shows these technologies and corresponding phase

changes of oil. Thus, “efficiency” will be used in general instead of “removal

efficiency”. Table 9 shows the ranking of these technologies by efficiency, cost, and

environmental impact.

Technologies Phase changes

Booms and skimmers Recover oil from ocean surface

Chemical dispersants Disperse oil slick to small droplets

Table 8 Technologies and corresponding phase changes

62
 Criteria Ranking of criteria of technologies
from highest to lowest
Efficiency Biological mechanisms>in situ
burning>chemical dispersants>booms
and skimmers
Cost Booms and skimmers>chemical
dispersants>in situ burning>biological
mechanisms
Environmental impact In situ burning>chemical
dispersants>booms and skimmers>
biological mechanisms
Table 9 Ranking of criteria of technologies from highest to lowest
Efficiency and cost are not the only factors that decide the use of certain

technologies. The local environmental conditions are also major factors to be

considered. For example, there remains controversy over the use of chemical oil

dispersants because of their potential toxic effects (National Research Council,2014).

Only EPA pre-approved products that pass standardized product efficacy and toxicity

tests can be used during the oil spill response (National Research Council,2014). The

use of chemical dispersants in Alaska is debated although it has reached high

effectiveness. Prince William Sound Regional Citizens’ Advisory Council (PWSRCAC)

has summarized some reasons that chemical dispersants should not be used in Alaska.

Firstly, chemical dispersants only alter the fate and transport of spilled oil, but oil still

remains in the environment and thus may reduce the effectiveness of skimmers

(PWSRCAC, 2022). These remaining oil droplets may still impact shoreline areas and

thus damage the vulnerable ecosystem and organisms are not well understood

(PWSRCAC, 2022). In addition, the use of chemical dispersants is not successful

because of the cold-water regions (PWSRCAC, 2022). As analyzed previously. The

63
dispersed effectiveness increased with increasing temperature.

There are several secondary factors that led to the devastating consequences of the

Deepwater Horizon incident. They are explosions and fire on the Deepwater Horizon,

the rigs power supply and alarm and indication systems, procedures, and training

(National Research Council, 2012). Once the well control was lost, a large amount of

gaseous hydrocarbon was released onto the oil rig. Together with the wind velocity and

questionable venting selection, ignition was inevitable (National Research Council,

2012). The loss of power supply of rig’s dynamic positioning system, backup system

and the standby generator has reduced the ability to firefighting, keeping the position

right and overall situation control (National Research Council, 2012). The alarm and

indication system, procedures and training systems were insufficient to prevent the

incident (National Research Council, 2012). After the “kicks” happened, the blowout

preventer (BOP) also failed to prevent devastating consequences. Crew members

closed the upper annular preventer, however, the inflammable oil and gas continued to

flow toward the rig; The crews also closed the pipe ram; however, this is only a

temporary fix which did not prevent the “kicks” effectively. The crews have

misinterpreted the negative pressure test and considered the well as being properly

sealed at first (Hauge et al. 2012). Thus, more training was required in these situations.

Figure 38 shows the structure of the BOP (Affleck et al. 2021).

64
 Figure 38 BOP structure demonstration (Affleck et al.2021)

The Deepwater Horizon oil spill responses were not successful. It is not because

of the technologies themselves, but the irresponsibility of British Petroleum (BP) which

is responsible for the accident. There are three phases in crisis management models

which are pre-crisis phase, the response phase and the post-crisis phase (Wolf,2013).

Pre-crisis phase is about the prevention and preparation (Coombs,2007). Prevention

aims to seek to reduce known risks that could lead to a crisis; The possible actions can

involve implementing risk audits, safety measures and standards or a control system

(Coombs, 2007). Preparation involves creating the crisis management plan that should

be updated annually, selecting, and training the crisis management plan and conducting

exercises to test the crisis management plan and related personnels (Wolf,2013). The
65
response phase aims to mitigate the crisis and offer support to those affected by it

(Richardson,1994). The post-crisis phase begins when the organization or the firms

return to normal business and looks for ways to prepare for the next crisis

(Coombs,2007). BP was not doing well in the first two phases. During the phase of

prevention and preparation, the Congressional Investigations on energy and commerce

showed that BP had no contingency plans for catastrophic loss of well control, and BP

did not have planning, testing and maintenance either (Wolf,2013). During the response

phase, BP did not perform professionally. During this phase, BP took a very long time

to realize that the well itself was leaking. Moreover, BP has underestimated the daily

oil spills. The amount estimated by BP was only 1,000 barrels per day, however, the

real amount was 60,000 barrels (Wolf, 2013). Because of the lack of preparation and

prevention of the crisis, and the false performance in the response phase have caused

fatal consequences. As the introduction section showed, only a small percent of oil was

removed with human intervention.

Overall, oil spill accidents have been decreasing in recent years. Figure 39 shows

the number of oil spills greater than 7 tons each year from 1970 to 1979

(Ejeromedoghene et al.2020). The average number of spills decreased from 78.8 (1970

to 1979) to 6.2(2009 to 2018) (Ejeromedoghene et al.2020). Both technologies and laws

are helping reduce oil spills. By 2010, tankers are required to have a double hull instead

of a single hull (Sylves et al. 2012). Figure 40 shows the difference between single hull

and double hull structure (Decola,2009). When single-hulled tankers collided or

grounded, the hull was penetrated, and oil will spill directly into the ocean. With a

66
double-hulled tanker, the inner hull of the tanker will stay undamaged when collision

and grounding happen, and thus control the oil spill (Decola,2009).

Figure 39 Number of oil spills >7 tons from 1970 to 2019 (Ejeromedoghene et
al.2020)

Figure 40 Difference between single-hulled and double-hulled tanker (Decola,2009)

67
 Laws and regulations will also help minimize the risks of oil spills. Laws and

regulations were issued and amended over time to prevent future oil spills, especially

when large oil spills happened. After the Deepwater Horizon incident, the Bureau of

Safety and Environmental Enforcement (BSEE) has updated the laws on Drilling

Safety Rule in 2012 (Vizcarra, 2020). More specifically, it established new casing and

cementing requirements and required new casing and cementing integrity tests

(Vizcarra,2020). Moreover, it established the new well control training requirements

for deepwater operations (Vizcarra,2020). More importantly, “to ensure safety and the

protection of the human, marine, and coastal environments”, after an operator drills a

well, it must get BSEE’s approval before beginning production of the well

(Vizcarra,2020). Production Safety Regulations were also updated by 2016 which

revised the safety and pollution prevention equipment (SPPE) design, maintenance,

and repair requirements to make sure they will function in the most extreme

conditions they are exposed to (Vizcarra,2020).

Some suggestions have also been made after the Deepwater Horizon incident on

alarm and indicators system (National Research Council, 2012). Regulations should

require periodically checking of the status of alarms and indications. In addition,

regulations should be reviewed to ensure adequate redundancy in alarm systems.

Education and training of rig personnel is also required (National Research

Council,2012). Industry should also require that personnel aboard the rig achieve and

maintain a high degree of expertise in their assigned watch station (National Research

Council, 2012).

68
 Secondly, the Oil Pollution Act of 1990 and the National Contingency Plan of the

United States have played important roles. The Oil Pollution Act of 1990 was signed

by President G.H.W.Bush on August 18,1990 about one year after the Exxon Valdez

accident (Sylves et al.2012). Before 1989, legislators attempted to pass oil spill

reform measures, however, there was no sense of immediacy that prompted agreement

(Sylves et al.2012). After the Exxon Valdez accident, large pressures have been put on

legislators to streamline and strengthen federal oil pollution control laws (Sylves et

al.2012). Several major headers of the Oil Pollution Act of 1990 are listed below

(Sylves et al.2012):

A. Increase spillers’ liability many times over previous federal limits and
impose stiffer civil and criminal penalties. Liability could top $200 million
for very large tankers.

B. Require spillers to pay for cleaning up oil spills and compensate

parties injured economically by oil spills.

C. Continue to allow states to impose unlimited liability on shippers.

D. Require shippers to draft “worst case” oil spill response plans for quick
cleanup. Require that all oil tankers transiting U.S. waters be double-
hulled by 2010.

E. Stiffen anti-drug and anti-alcohol laws for ship operators by requiring

testing for certain workers and threatening substance abusers with
license revocation.

The National Oil and Hazardous Substances Pollution Contingency Plan (NCP) is

another important part. It became effective in 1968 in the response to the massive oil

69
spill from the oil tanker Torrey Canyon (Sylves et al.2012). The NCP has several major

sections focusing on the response to the oil spill. The NCP is a sophisticated system

which includes the responder training and expertise, equipment, logistics,

administrative needs, and funding systems and offers response guidance (Sylves et

al.2012). Subpart D of the law describes the operational response phases for oil removal.

The subpart D has 10 parts which are listed below (EPA,2015):

300.300 Phase I—Discovery or notification

300.305 Phase II—Preliminary assessment and initiation of action

300.310 Phase III—Containment, countermeasures, cleanup, and

disposal.

300.315 Phase IV—Documentation and cost recovery.

300.317 National response priorities.

300.320 General pattern of response.

300.322 Response to substantial threats to public health or welfare of the

United States

300.323 Spills of national significance.

300.324 Response to worst case discharges.

300.335 Funding.

70
Conclusion

Booms and skimmers, chemical dispersants, in situ burning and biological

mechanisms are the most used oil spill cleanup methods. The research has analyzed

how weather factors affect the performance of these technologies. Wind speed, current

speed and wave height have affected the performance of these technologies. Efficiency,

cost, and level of environmental impact were analyzed. Booms and skimmers rank the

lowest in efficiency; chemical dispersants and in situ burning rank the lowest on

environmental impact; biological mechanisms have the lowest cost.

However, people should not always depend on technologies, as analyzed before,

laws and regulations have played important roles. They minimize the risks of oil spills.

After large scaled oil spills, laws and regulations were updated and modified to

minimize the risks of similar events. As discussed in discussion section, after the

Deepwater Horizon incident, the updates on Drilling Safety Rule and Production Safety

Regulations have emphasized on the safety of operations and the requirements of the

design, maintenance, and repair of the safety and pollution prevention equipment. In

addition, some other laws and regulations such as the Oil Pollution Act of 1990 and the

National Oil and Hazardous Substances Pollution Contingency Plan (NCP) have played

important roles to minimize the risks of oil spills.

71
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