Oil Refineries and 

Hazard Reduction
NEEDLESS RISK: 

OIL REFINERIES AND HAZARD REDUCTION

MEGHAN PURVIS

MARGARET HERMAN

U.S. PIRG EDUCATION FUND

AUGUST 2005
ACKNOWLEDGMENTS

Copyright 2005 U.S. PIRG Education Fund 

Cover photo of oil refinery obtained from the Hawaii State Department of Business, Economic 

Development & Tourism, at http://www.hawaii.gov/dbedt/ert/refinery.html. Note that this 

photo is for illustrative use only; this refinery does not use hydrofluoric acid. Photo of children 

playing courtesy of Denny Larson of the National Refinery Reform Campaign, 

www.refineryreform.org. This photo shows children from the Carver Terrace federal housing 

project playing in the shadow of the Premcor refinery in West Port Arthur, Texas. Photo of 

homes near an oil refinery obtained from EcoIQ.com Online Images. Photo of emergency 

medical technicians obtained from the City of Norfolk at 

www.norfolk.gov/NFR/images/emspic.JPG. 

The authors would like to acknowledge Alison Cassady of U.S. PIRG Education Fund for 

coordinating the research and distribution of this report, as well as her endless editorial support 

and cover design. 

In addition, we would like to thank Paul Orum, senior advisor to the Working Group on 

Community Right-to-Know, for his research leadership and editorial review. We would also like 

to thank the U.S. PIRG Education Fund interns for their help in collecting the data. 

The U.S. PIRG Education Fund’s Toxics and Environmental Health Program is grateful to the 

Bauman Foundation, the Beldon Fund, and individual contributors for their support. 

The authors alone are responsible for any factual errors. The recommendations are those of the 

U.S. PIRG Education Fund. The views expressed in this report are those of the authors and do 

not necessarily reflect the views of our funders or those who provided editorial review. 

The U.S. PIRG Education Fund is the research and public education center for the U.S. Public 

Interest Research Group (PIRG), the national advocacy office of the state PIRGs. The state 

PIRGs are a nationwide network of nonprofit, nonpartisan, state-based public interest advocacy 

organizations. The state PIRGs’ mission is to deliver persistent, result-oriented activism that

protects the environment, encourages a fair marketplace for consumers and fosters responsive, 

democratic government. 

For additional copies of this report, send $20 (including shipping) to: 

 U.S. PIRG Education Fund 

218 D Street, SE 

 Washington, DC 20003 

 202-546-9707 

 uspirg@pirg.org

www.uspirg.org 

For more information about the state PIRGs, visit our Web site at http://www.pirg.org. 
TABLE OF CONTENTS

EXECUTIVE SUMMARY .......................................................................................................................................4

CHEMICAL INSECURITY: HAZARDS LEAVE COMMUNITIES EXPOSED......................................6

HYDROFLUORIC ACID AND THE PETROLEUM INDUSTRY..............................................................8

HYDROFLUORIC ACID: A THREAT TO HEALTH AND SAFETY..............................................................8

USE OF HYDROFLUORIC ACID IN THE PETROLEUM INDUSTRY ..........................................................8

CHEMICAL ACCIDENTS INVOLVING HYDROFLUORIC ACID ................................................................9

HYDROFLUORIC ACID: A TERRORIST TARGET .....................................................................................10

REPORT FINDINGS: COMMUNITIES AT RISK.........................................................................................12

HOW POLICYMAKERS AND INDUSTRY SHOULD PROTECT COMMUNITIES .........................15

A PREVENTIVE APPROACH........................................................................................................................15

INHERENT SAFETY AT REFINERIES: ALTERNATIVES TO HYDROFLUORIC ACID .............16

PREVENT THE POSSIBILITY: SOLID ACID CATALYST............................................................................16

REDUCE THE SEVERITY: SULFURIC ACID AS AN OPTION...................................................................17

REDUCE THE PROBABILITY: HYDROFLUORIC ACID MODIFIERS.......................................................18

REDUCING CHEMICAL HAZARDS THROUGH POLICY MEASURES.............................................21

INADEQUACIES OF EXISTING POLICIES..................................................................................................21

THE RIGHT-TO-KNOW AS A SAFETY TOOL...........................................................................................22

PROTECTING COMMUNITIES THROUGH INHERENTLY SAFER TECHNOLOGY ...............................23

METHODOLOGY..................................................................................................................................................24

APPENDIX: OIL REFINERIES USING OR STORING HYDROFLUORIC ACID ON-SITE.........25

END NOTES ............................................................................................................................................................27
EXECUTIVE SUMMARY

Across the country, petroleum refineries, 

chemical plants and other industrial facilities 

use and store large amounts of hazardous

chemicals that could be released in the event 

of an accident or terrorist attack. Such 

releases could endanger thousands or even

millions of people who live in communities in 

close proximity to these facilities. According

to the Environmental Protection Agency 

(EPA), 106 facilities would each endanger at 

least one million people in the event of a 

worst-case chemical release. Another 3,000 

facilities would endanger at least 10,000 

people. Nearly 5,000 facilities store more 

than 100,000 pounds of at least one EPAclassified “extremely hazardous substance.” 

Many of these facilities, however, present an 

unnecessary risk to their surrounding 

communities. Industries often have multiple 

options for carrying out similar processes, and

some of these options are inherently safer

than others. Facilities that use fewer or

smaller quantities of hazardous chemicals, or 

even make changes to storage pressure or 

other processes, can eliminate the possibility 

of on-site chemical accidents and make 

themselves less appealing terrorist targets. 

Petroleum refineries stand as a stark example 

of the needless risk posed by such facilities in 

the event of an attack or accident as well as 

the opportunity to mitigate this risk by using

safer alternatives to toxic chemicals. 

 

Many petroleum refineries use hydrofluoric

acid in their processing, which poses a great 

public safety risk both because of its extreme 

toxicity to humans as well as its propensity to

form a toxic aerosol cloud when released. A 

catastrophic event at one of these facilities 

could cause a potentially lethal release of 

hydrofluoric acid, forming a stable aerosol 

cloud above the facility and surrounding 

neighborhoods. Exposure to hydrofluoric

acid results in devastating burns, and pain 

associated with the exposure may be delayed

for up to 24 hours. If the burn is not 

addressed, tissue destruction may continue for 

days. Inhalation of fumes can cause 

symptoms ranging from severe throat 

irritation to pulmonary edema. 

To estimate the number of Americans at

needless risk of exposure to hydrofluoric acid

in the event of a catastrophic accident or 

terrorist attack at a petroleum refinery, we 

examined the Risk Management Plans 

submitted by oil refineries to EPA. These 

plans estimate how far a chemical could travel 

off-site in the event of a release and report the 

number of people living within the 

“vulnerability zone,” the area potentially 

affected by the release. Based on this data, we 

found that petroleum refineries using 

hydrofluoric acid endanger millions of people. 

Specifically: 

• Of the 148 petroleum refineries in the 

United States, 50 use hydrofluoric acid in 

their processing or store it on-site. The 

remainder use safer alternatives, such as 

sulfuric acid. 

• These 50 refineries, using and storing 10.6 

million pounds of hydrofluoric acid, 

endanger more than 17 million people 

living in surrounding communities in 20 

different states. 

4 Needless Risk

• With 12 refineries using hydrofluoric acid, 

Texas has more than any state. Louisiana 

has five oil refineries that currently use 

hydrofluoric acid, and Montana has four. 
• Refineries using hydrofluoric acid in 

Pennsylvania endanger more than 4.4 

million people residing in their

vulnerability zones, according to 

conservative estimates. Refineries using 

hydrofluoric acid in both Illinois and New 

Jersey endanger more than 3.1 million 

people living within the vulnerability 

zones. 

• Seven petroleum refineries using 

hydrofluoric acid reported toxic release 

“worst-case” scenarios in which more 

than one million people could be affected. 

Furthermore, 15 refineries could place 

more than 500,000 people in harm’s way,

and 28 refineries could endanger more 

than 100,000 people in the event of a 

worst-case hydrofluoric acid release. 

• The companies operating refineries using 

hydrofluoric acid with the most people 

residing in their vulnerability zones 

include Sunoco, Valero Energy 

Corporation, Marathon Ashland

Petroleum, ConocoPhillips, CITGO, and 

ExxonMobil, each endangering at least 

two million people in total. 

• Many companies owning refineries using 

hydrofluoric acid also operate refineries

without that technology. ConocoPhillips, 

ExxonMobil, Valero Energy Corporation, 

and Marathon Ashland, for example, own 

refineries using hydrofluoric acid as well 

as refineries that use other technologies. 

Fortunately, hydrofluoric acid is not the only 

material oil refineries can use in their refining

processes. Many other refineries already use 

sulfuric acid, a safer alternative, in the 

alkylation process. This cost-effective and 

widely-used alternative diminishes the appeal

of refineries as a terrorist target and mitigates 

the public health and safety consequences of

an accident. In addition, a new technology, 

solid acid catalysts, will soon be available for 

widespread commercial use, offering an even

safer option than the use of sulfuric acid. 

Petroleum refineries are but one example of 

the facilities that pose an immediate risk to 

public health in the event of a terrorist attack 

or chemical accident. Refineries also are not 

the only example of facilities that could make 

cost-effective changes to manufacturing 

processes to reduce or eliminate the use of

hazardous chemicals. 

Needless Risk 5 

Unfortunately, most industrial facilities have 

not responded to the increased awareness of 

terrorism by switching to inherently safer 

technologies. Instead, industry organizations

such as the American Chemistry Council, the 

American Petroleum Institute, and the 

National Petrochemical and Refiners 

Association have emphasized increasing 

physical security at facilities. Hiring more 

guards, building higher fences, and placing 

more lights may all be part of a strong security 

plan, but this does not actually reduce the 

threat to the community. Switching chemicals 

and processes to something less volatile not 

only reduces the chemical hazard to the 

community, but also reduces the need for 

costly add-on security measures and the 

attractiveness of the facility as a target for 

attack. 
CHEMICAL INSECURITY: HAZARDS LEAVE 

COMMUNITIES EXPOSED

Across the United States, thousands of

industrial facilities use and store hazardous 

chemicals in large quantities that pose major 

risks to their neighbors. According to the 

Environmental Protection Agency (EPA), 106 

facilities would each endanger at least one 

million people in the event of a worst-case 

chemical release. Another 3,000 facilities 

would endanger at least 10,000 people.

Nearly 5,000 facilities store more than 100,000 

pounds of at least one EPA-classified 

“extremely hazardous substance.”1

Accidents at chemical and industrial facilities 

are common. Each year tens of thousands of

spills and gas leaks occur as a result of the

ongoing use of hazardous chemicals.2 As

recently as March 2005, an explosion at a BP 

oil refinery in Texas City, Texas killed 15 

employees. In Gulfport, Mississippi in 

February 2003, a cloud of toxic ammonia 

leaked from a chemical plant after an intruder 

broke into a fenced compound, attempting to 

steal the chemical to make illegal drugs. The 

toxic cloud led to the evacuation of seven 

hotels and the closure of Gulfport-Biloxi 

International Airport and a 10-mile stretch of 

Interstate 10 for seven hours.3

Since September 11, 2001, it has become 

increasingly apparent that these facilities pose 

a more sinister threat, as they may become the 

target of a terrorist attack. A report by the 

Army Surgeon General ranked an attack on a 

chemical plant second only to a widespread

biological attack in magnitude of the hazard to

the public.4 On February 12, 2003, the

National Infrastructure Protection Center

warned, “Al Qa’ida operatives...may attempt 

to launch conventional attacks against the 

U.S. nuclear/chemical-industrial infrastructure 

to cause contamination, disruption, and

terror.”5

Even before September 11, 2001, the Agency 

for Toxic Substances and Disease Registry 

(ATSDR) addressed the weak security at 

chemical facilities. In 1999, ATSDR published 

a study of chemical site security at two key 

chemical communities – the Kanawha Valley 

in West Virginia and Las Vegas, Nevada. The 

study found the industry poorly prepared for 

terrorist attacks, noting that industrial 

chemicals provide terrorists with “effective 

and readily accessible materials to develop 

improvised explosives, incendiaries and 

poisons.”6

Across the country, select facilities have made 

major progress by switching to safer 

chemicals and processes that pose less of a 

threat to surrounding communities in the 

event of a major chemical release. Soon after 

September 11th, for example, the Blue Plains 

Sewage Treatment Plant in Washington, DC

switched from using and storing chlorine and 

sulfur dioxide on-site to using sodium 

hypochlorite bleach in its processes. For 

weeks after September 11th, workers at Blue 

Plains removed up to 900 tons of liquid 

chlorine and sulfur dioxide. Whereas chlorine 

gas from the Blue Plains facility could have 

enveloped downtown Washington, DC, 

Anacostia, Reagan National Airport, and

Alexandria in a toxic cloud, sodium 

hypochlorite bleach is far more benign if 

accidentally released.7

6 Needless Risk

Unfortunately, too few other chemical

facilities have followed the lead of the Blue 

Plains facility, changing the processes and 

chemicals they use to make their facilities

inherently safer. Instead, industry groups 
have emphasized increasing physical security 

at facilities, such as guards and fences. The 

American Chemistry Council, the chemical 

industry’s lobbying organization, has issued 

site security guidelines for its member

companies and requires these companies take 

part in its Responsible Care program in order 

to continue membership in the organization.

This set of guidelines, however, focuses 

mainly on site security and does not include 

minimum standards that facilities must follow. 

For example, it does not require that facilities 

provide for protection against an armed 

intruder. In addition, Responsible Care does 

not require that facilities use inherently safer

technology to reduce the threat these facilities 

pose to surrounding communities. The 

industry does not even require members to set 

public goals and timelines to reduce chemical

dangers. 

Hiring more guards, building higher fences, 

and placing more lights may all be part of a 

good security plan, but this does not actually 

reduce the threat to the community.

Switching chemicals and processes to

something less volatile not only reduces the 

chemical hazard to the community, but also 

reduces the cost of physical security and the 

attractiveness of the facility as a target for 

attack. 

Furthermore, some in industry and the 

government have proposed limiting the 

public’s access to information on the potential

impact of a major chemical release on public 

health and safety. Limitations have been

placed on the information any individual can

obtain to protect themselves and their families 

from chemical releases at neighboring 

facilities. Instead of safeguarding these 

facilities from terrorists, these efforts merely 

deny public accountability measures that

encourage industry reform. 

Needless Risk 7 
HYDROFLUORIC ACID AND THE PETROLEUM INDUSTRY

Petroleum refineries stand as a stark example 

of the safety hazards posed by using toxic 

chemicals in the manufacturing process and 

the opportunities to switch to safer 

alternatives. 

Petroleum refineries are responsible for nearly 

11% of all of the high-risk processes in EPA’s 

Risk Management Program, the agency’s

primary chemical accident prevention

program established under the 1990 Clean Air 

Act Amendments.8

 Most notably, many of

these refineries use hydrofluoric acid, also 

known as hydrogen fluoride, as a catalyst to 

produce an additive to gasoline. This additive 

is then used to increase the octane levels in 

gasoline, which addresses the problem of

engine “knocking.” Currently, 148 petroleum

refineries operate in the United States, 50 of 

which use hydrofluoric acid as a catalyst to 

produce alkylate.9

HYDROFLUORIC ACID: A THREAT TO 

HEALTH AND SAFETY 

Highly toxic, hydrofluoric acid has many acute 

consequences for human health, as well as the 

ability “to kill people on the spot,” according 

to Jonathan Ward, director of toxicology at 

the University of Texas.10 Even slight contact 

with hydrofluoric acid may cause a variety of

acute symptoms, including skin burns and 

deep tissue burns, which may not be felt for 

up to 24 hours after exposure. In addition, 

hydrofluoric acid exposure commonly causes

eye irritation and can lead to permanent 

damage. If inhaled, the acid can cause 

irritation of the nose, throat, and lungs, 

causing coughing and dyspnea, or shortness 

of breath. Severe exposure can cause 

cyanosis, an indicator of hypoxemia, lung 

injury and a build up of fluid in the lungs, 

known as pulmonary edema.11 

Once hydrofluoric acid penetrates body tissue, 

it can react with the calcium and magnesium

in the blood stream, causing abnormally low 

calcium concentrations and a condition 

known as hypocalcaemia.

12 

Case studies have shown hydrofluoric acid to 

be fast acting, reporting instances of 

respiratory irritation in less than one minute 

after acute inhalation of 122 parts per million

(ppm).13 The Occupational Safety and Health 

Administration estimates that the lowest lethal 

concentrations range from 50-250 ppm for a 

five-minute exposure.14

USE OF HYDROFLUORIC ACID IN THE 

PETROLEUM INDUSTRY

Petroleum refiners use hydrofluoric acid as a 

catalyst in the alkylation process. With tighter 

standards on fuel emissions, alkylate has

become a key additive in gasoline because it

offers a high octane with very low sulfur and 

nitrogen content. 

Alkylation is the chemical process by which

high-octane gasoline is made. Light, gaseous

hydrocarbons, made up of compounds like 

propylene and butylenes, feed into a reactor, 

where contact with the acid catalyst results in 

a reaction that produces a heavy mixture of

hydrocarbons, along with excess heat, which 

must be removed. It is the liquid portion of 

this mixture that is known as alkylate, and it is

responsible for the anti-knocking property of

unleaded gasoline.15 Lastly, because some of 

the acid catalyst leaves the reaction chamber 

along with the alkylate, further treatment to

neutralize the acid is required as well in order 

to prevent corrosion further down the 

production line. 

8 Needless Risk
CHEMICAL ACCIDENTS INVOLVING 

HYDROFLUORIC ACID

Hydrofluoric acid has a boiling point of 67o F 

(19.4o C) at atmospheric pressure, and most 

reactions take place at about 100o F (37.8o C) 

in petroleum refineries. Therefore, the acid

will vaporize whenever the container is

penetrated.16 Furthermore, when the outside 

temperature is 67o F or greater, the 

containment unit housing hydrofluoric acid 

becomes pressurized because of the acid’s 

high volatility. Therefore, if hydrofluoric acid 

is released from containment, under certain 

atmospheric conditions it will form a stable 

aerosol cloud. 

Amoco, Mobil, Allied Chemical and DuPont 

tested the possibility of a release of 

hydrofluoric acid from one of their refineries 

then under construction in a Nevada desert in 

1986. Under conditions similar to those in an 

alkylation unit, lethal concentrations of 

hydrofluoric acid aerosol were present up to 

five miles (8 km) from the release points, at 

levels much higher than anticipated.17 The

amount of hydrofluoric acid released in the 

test was relatively small—1,000 gallons in two 

minutes.18

Hydrofluoric acid refineries have long had a 

history of accidental releases that prove the 

potentially devastating effects of a release 

caused by simple human error. The National

Response Center recorded more than 400 

incidents at refineries and other facilities 

involving hydrofluoric acid or hydrogen 

fluoride from 1990 to 2005.19 Simple 

malfunctions, ruptured valves or pipes, or 

valves accidentally opened often cause 

significant leaks that can harm both the 

people and the environment surrounding the 

refinery. 

• On October 30, 1987, a crane at 

Marathon Oil’s Texas City refinery 

dropped its load on a storage tank, 

rupturing a pipe and releasing 30,000 

pounds of hydrofluoric acid, the largest 

known release. The resulting vapor cloud 

sent 1,037 people to the hospital suffering 

from respiratory problems and skin rashes 

and forced 3,000 residents out of their 

homes for three days. “There were 

houses right up against the fence,” said 

Ronald Koopman of Lawrence 

Livermore. “The only thing that saved

people was that the [hydrofluoric acid]

plume shot 200 feet up in the air, and it 

went about 900 meters downwind before 

it actually came down into the 

neighborhood. If it had squirted out 

sideways, it would have killed hundreds, if 

not thousands.”20

• On March 2, 2003, 13 electricians working 

at the Marathon Ashland oil refinery in St. 

Paul Park, Minnesota were hospitalized

after being exposed to hydrofluoric acid. 

They had been hired to repair damage to 

the facility caused by a fire a few days

earlier. While working, a pump leaked 

one cup of hydrocarbons with trace 

amounts of hydrofluoric acid, which 

immediately vaporized and entered their

lungs.21

• An accidental hydrofluoric acid release in 

1991 killed two workers and injured five 

others at Southwestern Refining Co. in 

Texas.22

• Between 1995 and 1997, four separate 

one-pound releases of hydrofluoric acid at 

the Sunoco refinery in Philadelphia 

injured one worker in each accident.

23

Needless Risk 9 

• On October 2, 2001, 150 pounds of 

hydrofluoric acid in low concentration 

leaked within the Valero refinery in 

Paulsboro, New Jersey. Because the wind 

was blowing toward neighboring 

Greenwich Township, a nearby 

elementary school was forced to secure all
the children and staff in the gym by 

sealing the doors and windows with duct 

tape and plastic.24

• On March 19, 1988, at the Sun Co. 

refinery in Tulsa, Oklahoma, an accidental 

release of 210 pounds of hydrofluoric acid 

sent a cloud of hydrofluoric acid drifting 

five miles through downtown. Had the 

accident occurred on a weekday, more 

people would have been injured. One 

resident, living in the downtown area,

said, “I didn’t realize it was hazardous 

until I could see it leave orange particles 

everywhere...And then my eyes burned, 

my throat burned and my head ached.”25

• On March 23, 2005, an explosion at a BP 

oil refinery in Texas killed 15 employees

and injured more than 100. This was the 

third major accident in a year at this

facility. Although it did not involve a 

release of hydrofluoric acid, the presence 

of this chemical on-site was a major cause 

for concern.26

HYDROFLUORIC ACID: A TERRORIST 

TARGET

According to Neil Livingstone, board 

chairman of Global Options, a security firm in 

Washington, DC, hydrofluoric acid is a

“known quantity to some terrorists,” 

particularly those from oil-producing 

countries where hydrofluoric acid is 

commonly used.27 Terrorist attacks over the 

past 10 years have consistently targeted

petroleum facilities throughout the world 

because of their vulnerability, value to 

economies, and high volumes of toxic 

chemicals stored onsite. A few examples of 

coordinated attacks on petroleum facilities 

over the past 10 years include: 

• During the Croatian war, Serbian armies 

attacked a natural gas refinery in eastern

Slovenia that stored ethane, propane, and 

butane with rockets and cluster bombs.

28

• Serbian forces attacked large fuel storage 

tanks along the highway from Belgrade to

the outskirts of Zagreb and started large 

fires at Osijek, Sisak, and Karlovak.29

• A refinery in Sisak, which produced

liquefied petroleum gas, fuel, petroleum

coke, and solvents, was attacked with

thousands of Serbian artillery rounds, 

which hit 38 petroleum storage tanks. If 

these attacks had destroyed existing stored 

chemical containers, lethal concentrations 

of chemicals would have covered a wide 

area.30

• In October 2001, a group of Tamil Sea 

Tigers attacked and set ablaze the oil 

tanker MV Silk Pride. It was carrying 225 

tons of low-sulfur diesel, 160 tons of 

kerosene oil, and 275 tons of auto diesel.31

An organized attack on a U.S. oil refinery,

similar to the attack on the Sisak refinery by 

Serbian forces, would be nearly impossible for 

security guards to prevent. 

10 Needless Risk 

Furthermore, it is relatively simple for 

individuals to gain access to plants with the 

level of security common at refineries. As 

recently as January 2002, a robber carrying a

shotgun made his way into a CITGO facility 

in Texas. CITGO was one of the companies

that claimed to have dramatically increased

security measures after September 11, 2001.32 

In addition, activists and reporters have 

breached security at refineries and chemical

facilities across the country. Greenpeace 

activists entered Dow Chemical’s Plaquemine, 

Louisiana facility in February 2001 through an 

unlocked gate and gained access to the control 

panel that regulates wastewater discharges 

into the Mississippi River.33 A reporter in

Pennsylvania skirted inadequate security at 

more than 30 chemical facilities and found 
that he “could walk or drive right up to tanks, 

pipes and control rooms considered key 

targets for terrorists.”34

Assuming that on-site security was able to 

prevent all unauthorized access to a refinery 

and water mitigation systemsa were installed 

throughout the refinery, it would still not be 

difficult to release hydrofluoric acid into 

surrounding communities. According to 

Carol Coy, a California regulator whose 

agency pushed for an end to hydrofluoric acid 

use in southern California, saboteurs could 

deactivate the mitigation systems simply by 

shutting off the electricity.35 Furthermore,

munitions fired from an offsite location could 

puncture the storage tanks holding 

hydrofluoric acid. 

National security experts recognize that a

terrorist attack on chemical facilities and 

refineries is more likely than an attack with a 

conventional chemical weapon. Creating 

chemical weapons is a complex and expensive 

process, whereas industrial facilities provide

relatively easy access to large amounts of

chemicals from which a significant chemical

release could harm considerable numbers of 

people. In a Senate committee hearing on 

June 15, 2005, even the Department of 

Homeland Security (DHS) expressed concern

about the consequences of a terrorist attack

on a chemical facility.36 Robert Stephan, an 

undersecretary in the DHS, noted that, as an

aspect of America’s “critical infrastructure,”

chemical facilities indeed represent a 

dangerous terrorist target. In addition, 

chemical facilities have many easy access

points, making facility security more difficult. 

According to Stephan’s testimony: 

 a Water mitigation systems are designed to cool nearby

liquid petroleum gas containing vessels and columns to

insure their structural integrity and to reduce hydrogen 

fluoride vapors if a leak were to occur. For water

mitigation systems to effectively reduce hydrogen 

fluoride vapors in the event of a leak, sensors to detect

the leak must be installed. 

“DHS has identified five areas as the 

focus of our primary preparedness work 

with the industry: access and access

control, operational security, process

control, facility systems operations, and 

local first responder and external response 

and recovery coordination. These 

preparedness planning variables must be 

refined with reference to potential 

methods of attack. These include perhaps 

most importantly: insider threats or 

sabotage; cyber attack; and attacks using 

explosives or other weaponry.”37

Amy Smithson, director of the Chemical and

Biological Weapons Non-Proliferation Project 

at the Henry L. Stimson Center, testified to 

this in a House of Representatives committee 

hearing: 

Needless Risk 11 

“Although assembling from scratch an 

unconventional weapons capability that 

could cause mass casualties is not that 

elementary, there are tangible routes

whereby terrorists could inflict 

considerable harm with chemical and

biological substances. One shortcut 

involves foul play with industrial 

chemicals...Logic dictates that if the 

same result [mass casualties from a 

chemical release] can be achieved 

through a less arduous route, terrorists 

intent on causing mass casualties with 

chemicals would probably engineer the 

intentional release of industrial chemicals 

rather than wrestle with the complexities

of making large quantities of the classic 

chemical warfare agents.”38
REPORT FINDINGS: COMMUNITIES AT RISK

Under the Clean Air Act’s chemical accident

prevention requirements, industrial plants that 

use large volumes of certain toxic materials 

must file accident prevention plans (Risk

Management Plans) with EPA that include 

worst-case accident scenarios. These estimate 

how far a chemical could travel off-site and 

still maintain toxic concentrations in certain 

weather conditions and report the number of 

people living within that distance, named the 

“vulnerability zone.”b We examined the most 

recent Risk Management Plans for the 50

petroleum refineries in the United States using 

hydrofluoric acid in their processing or 

storing it on-site. These 50 refineries 

comprise one-third of the 148 refineries 

operating in the U.S.; meaning, two-thirds of 

all refineries use technology other than

hydrofluoric acid. 

These 50 refineries, using and storing 10.6 

million pounds of hydrofluoric acid, endanger 

more than 17 million people living in

surrounding communities in 20 states (Table 

1). See the Appendix for a list of all 50 

refineries using hydrofluoric acid in the U.S. 

Texas is home to the most hydrofluoric acid 

refineries, with 12; Louisiana is second with 

five facilities; and Montana is third with four 

facilities. These states are not home to the 

refineries that collectively endanger the most 

people, however; often a single refinery can 

endanger millions. Just two refineries using 

hydrofluoric acid in Pennsylvania endanger

more than 4.4 million people residing in their 

vulnerability zones, according to conservative 

estimates. In New Jersey, a single refinery 

using hydrofluoric acid endangers more than 

 b It is important to note that not all people living within 

a vulnerability zone would be affected by a single 

chemical release; those living downwind during a 

chemical release are most likely to be affected. 

3.1 million people living within the 

vulnerability zone. Three Illinois-based

refineries also endanger 3.1 million people 

living within the vulnerability zones. 

Table 1. Oil Refineries by State and Population at Risk 

in Each State in Event of Worst-Case Release of 

Hydrofluoric (HF) Acid 

State

# of Oil

Refineries

# of Refineries 

Using HF Acid 

Population 

Endangered By

HF Release 

AL 3 0 -

AK 6 0 -

AR 2 0 -

CA 21 2 360,000

CO 2 0 -

DE 1 0 -

GA 1 0 -

HI 2 0 -

IL 4 3 3,183,000

IN 2 1 8,000

KS 3 3 63,800

KY 2 1 300,000

LA 17 5 1,436,411

MI 1 0 -

MN 2 1 2,200,000

MS 4 0 -

MT 4 4 183,704

NV 1 0 -

NJ 6 1 3,170,000

NM 3 2 18,829

ND 1 1 68,013

OH 4 1 940,000

OK 5 3 113,388

OR 1 0 -

PA 5 2 4,400,000

TN 1 1 791,888

TX 26 12 1,930,805

UT 5 3 680,000

VA 1 0 -

WA 5 1 120,000

WV 1 0 -

WI 1 1 180,000

WY 5 2 63,067

Total 148 50 17,040,905c

Data on number of oil refineries by state obtained from Energy Information

Administration.39 Data on oil refineries using hydrofluoric acid and the population at risk

obtained from company Risk Management Plans (see methodology for more details). 

 

12 Needless Risk 

c This is not the aggregate total of the state totals, as it

takes into account overlapping vulnerability zones 

between states. As such, this is a conservative estimate. 
Table 2. Ten Refineries Endangering the Most People in 

Event of Worst-Case Release of Hydrofluoric Acid 

Facility Name Location 

Sunoco Philadelphia Refinery Philadelphia, PA 

Valero Refining Co. Paulsboro, NJ

PDV Midwest Refining (CITGO) Lemont, IL 

ConocoPhillips Trainer Refinery Trainer, PA

Marathon Ashland Petroleum, MN Refining Div. St. Paul Park, MN 

Chalmette Refining Chalmette, LA

Murphy Oil USA, Inc. Meraux Refinery Meraux, LA 

ExxonMobil Oil Corporation Joliet Refinery Channahon, IL

Marathon Ashland Petroleum, Ohio Refining Div. Canton, OH

ConocoPhillips Alliance Refinery Belle Chasse, LA 

Data on oil refineries using hydrofluoric acid obtained from company Risk Management Plans (see methodology for 

more details).

In some cases, however, the vulnerability 

zones of two or more refineries overlap, 

posing an even greater danger to people who

live and work within the overlapping areas. In 

Philadelphia, for example, the vulnerability 

zones of two refineries overlap across the 

Delaware River, encompassing the airport, 

sports stadiums, and many neighborhoods.40 

In Corpus Christi, Texas, four refineries using 

hydrofluoric acid are located near each other;

similarly, three refineries using hydrofluoric

acid are situated close together near New 

Orleans, Louisiana. 

Single refineries can endanger thousands or 

millions of people. Seven petroleum 

refineries with hydrofluoric acid alkylation 

facilities reported toxic release “worst-case”

scenarios in which more than one million 

people could be affected. Furthermore, 15 

refineries could place more than 500,000 

people in harm’s way, and 28 refineries could

endanger more than 100,000 people in the 

event of a worst-case hydrofluoric acid

release. 

The 10 facilities putting the most people at 

risk in the event of a worst-case release of

hydrofluoric acid are found in Illinois, 

Louisiana, Minnesota, New Jersey, Ohio, and

Pennsylvania (Table 2). 

Many parent companies put millions of 

people at risk from the hydrofluoric acid they 

use and store at their refineries. The 

companies with the most people residing in 

the vulnerability zones of refineries using 

hydrofluoric acid include Sunoco, Valero 

Energy Corporation, Marathon Ashland

Petroleum, ConocoPhillips, CITGO, and 

ExxonMobil (Table 3). These companies 

each put at least two million people at risk. 

Table 3. Parent Companies With at Least One 

Million People Living in Vulnerability Zones of 

Their Refineries Using Hydrofluoric Acid 

Parent Company 

Population at 

Risk

Sunoco, Inc. 4,400,000 

Valero Energy Corporation 4,366,193 

Marathon Ashland Petroleum 4,132,993 

ConocoPhillips 3,532,763

CITGO 3,415,420 

ExxonMobil 2,393,847

Murphy Oil Corporation 1,236,000 

Premcor Inc. 1,121,888 

Data on oil refineries using hydrofluoric acid and the population at risk

obtained from company Risk Management Plans (see methodology for more 

details).

Needless Risk 13 

Many companies that utilize the dangerous 

hydrofluoric acid technology also use 

refineries without that technology. 
ConocoPhillips, ExxonMobil, Valero Energy 

Corporaton, and Marathon Ashland, for 

example, own refineries that use hydrofluoric 

acid as well as refineries that use other

technologies. 

• ConocoPhillips owns six refineries that 

report to EPA’s Risk Management 

Program for their use of hydrofluoric 

acid, but runs 12 refineries in the United 

States. The other six facilities

presumably use a safer technology than 

hydrofluoric acid. 

• Valero Energy Corporation owns seven 

refineries in the United States that use 

hydrofluoric acid and five others that do 

not use that technology. One Valero 

refinery in Wilmington, California has

responded to concerned residents and is 

switching from hydrofluoric acid to a 

safer technology.

41

• ExxonMobil owns or co-owns four 

refineries that use hydrofluoric acid and 

three other refineries in the United

States that do not. 

• Marathon Ashland owns six 

hydrofluoric acid refineries in the U.S. 

and one refinery that does not use that 

technology. 

Companies owning facilities that use different 

types of chemicals in their alkylation

processes illustrate not only that alternative 

processes are possible to implement, but that

some companies have knowledge of safer

alternatives and choose not to implement 

them. 

14 Needless Risk 
HOW POLICYMAKERS AND INDUSTRY SHOULD PROTECT 

COMMUNITIES

A PREVENTIVE APPROACH

The actions of American industry—and 

American regulatory policy—have historically 

focused on preparing for or managing 

chemical accidents and releases rather than

preventing them. The continuing legacy of 

chemical accidents and un-addressed 

vulnerabilities in the United States is evidence 

that this strategy has failed to protect public 

safety. Furthermore, the events of September

11th make plain the need for preventive action. 

Safety valves may mitigate the effects of an

accidental release, and employee training may 

reduce the chances of an accident, but neither 

can protect public safety if a terrorist parks a 

truck bomb at a chemical plant or refinery. 

Designed to protect only against accidental

releases, many accident mitigation

technologies could be foiled by a deliberate 

saboteur. 

Reducing or eliminating chemical hazards 

offers the best strategy to fully protect 

American communities from both accidents

and terrorist attacks involving industrial 

chemicals. Hazard reduction means making a 

chemical process inherently safer by eliminating

the use of highly toxic, volatile, or flammable 

chemicals or using chemicals in safer

quantities or conditions. The concept of

inherent safety leads to a hierarchy to guide 

decisions on the use and management of

chemicals: 

First, reduce or eliminate the possibility of 

a chemical release by choosing inherently 

safer materials and technologies. 

Second, reduce the probability of a

chemical release through secondary 

prevention measures such as safety valves and 

double-walled vessels. In preventing 

terrorism, increasing site security is an 

additional secondary prevention measure 

(although inadequate in the context of 

modern terrorists’ tactics). 

Third, reduce the potential severity of the 

impacts of a chemical release through 

mitigation measures (containment dikes, 

sprinkler systems) or emergency response 

plans.42

Again, the first option—inherent safety—

provides the best response to the threat of 

chemical releases caused by acts of terrorism 

because it eliminates the potential hazard.

Add-on security and mitigation measures

could make minor contributions toward

preventing an act of terrorism, but traditional 

tools of terrorists—truck bombs, suicide 

bombers, and now airplanes—would likely

render such measures useless. Site security 

measures could prevent a terrorist from 

entering the grounds of a facility, but in the 

embassy bombings in Africa, the trucks 

containing bombs were parked near, not 

inside, facility grounds. Increasing physical 

security would have been of little help. 

Needless Risk 15 
INHERENT SAFETY AT REFINERIES: ALTERNATIVES TO 

HYDROFLUORIC ACID

Three options are available to petroleum 

refineries using hydrofluoric acid as a catalyst 

for alkylates in order to make this process 

inherently safer. 

• Change the alkylation process to use a 

solid acid catalyst; 

• Convert the hydrofluoric acid alkylation 

unit into a sulfuric acid unit; or 

• Add modifiers to the hydrofluoric acid 

that decrease the gaseous nature of 

hydrofluoric acid and install mitigation 

systems. 

PREVENT THE POSSIBILITY: SOLID ACID 

CATALYST 

The best option available to oil refineries is 

switching from using hydrofluoric acid to a 

solid acid catalyst, which completely 

eliminates the need to use either hydrofluoric 

acid or sulfuric acid to produce alkylate.

Industry experts report that a variety of solid 

acid catalysts will be available for use in 

alkylation facilities within the next four years. 

Critics, however, insist this technology has 

been available since the late 1990s, and simple 

industry inertia has kept solid acid catalysts 

from becoming the popular choice for

refinery alkylation processes.

43 

Solid acid catalysts have tremendous

environmental and safety advantages over 

both hydrofluoric acid and sulfuric acid 

because they are neither corrosive nor 

particularly hazardous to people or the 

environment. Furthermore, in the event that 

the container housing the catalyst is breached,

no further damage would result. Using a solid 

acid catalyst provides many benefits, including 

reduced waste disposal costs and hazards, 

possibility to expand capacity at a lowered

capital cost, and less corrosion of the 

equipment, resulting in lower maintenance 

costs.44

Considerable research is being conducted on

solid acid catalysts, and three main options 

currently exist: Albemarle Corp./ABB 

Lummus Global/Fortum Oil’s AlkyCleanTM, 

UOP’s AlkyleneTM, and Exelus Inc.’s 

ExSactTM. 

AlkyCleanTM’s demonstration phase at 

Fortum’s facilities in Porvoo, Finland was 

completed in January 2005 and is currently 

commercially available. According to the 

manufacturers, the operating and capital costs 

of the AlkyCleanTM process rival those of the 

liquid acid catalyst processes and produce an 

alkylate of similar high quality.45 

This solid acid catalyst also can replace 

existing hydrofluoric acid or sulfuric acid

alkylation units, reusing the existing feedstock

pretreatment and product distillation/recycle 

facilities. Converting to a solid acid catalyst 

would save the facility money over a sulfuric 

acid plant because this technology does not 

require refrigeration for the reaction to take 

place. Furthermore, there is no need to

remove acid from the finished product, 

thereby eliminating yet another step in the 

process.46 

16 Needless Risk 

UOP’s AlkyleneTM operates similarly, with the 

primary difference between the two available 

processes consisting of how the solid acid is

regenerated. The biggest difference is that

AlkyleneTM does not have the energy savings 

associated with AlkyCleanTM. Furthermore, 

the feedstock does have to be treated to
remove impurities. Yet, even with these 

differences, AlkyleneTM is still very cost 

competitive with hydrofluoric and sulfuric 

acid facilities.47 Recent industry publications 

report this technology has “overall economics

superior to sulfuric acid technology.”48

AlkyleneTM also has recently become 

commercially available, though there is limited 

interest so far in the United States and Europe 

given the need to construct new solid acid 

units.49 In February 2005, however, the Baku 

Heydar Aliyev Refinery of Azerbaijan awarded 

UOP a contract for the design of a new highoctane gas facility, which included, among 

other technologies, the world’s first

AlkyleneTM unit. Production is estimated to

start by 2008.50

Exelus Inc. also has a new solid acid catalyst

technology (ExSactTM) that is currently in its

six to nine month demonstration phase that 

precedes commercialization. This technology 

not only includes a stable and active catalyst,

but also a fixed-bed reactor that enhances the 

efficiency of the reaction and reduces the 

cost.51 According to a representative of 

Exelus Inc, U.S. petrochemical companies,

not refineries, have shown interest in this

technology; oil refineries in Norway and

Eastern Europe have demonstrated interest.52

All three of these alkylation processes cost 

significantly less than sulfuric acid alkylation 

units and virtually the same as hydrofluoric 

acid units. Manufacturers expect the market 

for solid acid catalyst technology to increase 

significantly as oil refinery alkylation units age 

and have to be replaced. The mounting costs 

of physical site security also add an incentive 

for refineries to select alternatives to 

dangerous hydrofluoric acid. 

REDUCE THE SEVERITY: SULFURIC ACID AS 

AN OPTION

Sulfuric acid is often used in the alkylation 

process instead of hydrofluoric acid because 

when released, it will not readily form a toxic 

aerosol cloud. Instead, sulfuric acid is 

released as a liquid form, making it much 

easier to contain and prevent exposure to 

those offsite. As a result, sulfuric acid does 

not pose as much as a threat to life outside of

the facility. 

 

Converting a hydrofluoric acid alkylation unit

into a sulfuric acid alkylation unit requires

several equipment changes. First, a sulfuric 

acid alkylation unit requires a refrigeration 

process.d

 Second, if the hydrofluoric acid 

facility contains the metal monel, it must be 

replaced because it reacts with sulfuric acid. 

Finally, an acid regeneration facility also 

should be constructed onsite so as to decrease 

the need to frequently transport sulfuric acid, 

which poses the risk of offsite consequences. 

The fundamental difference between using 

hydrofluoric acid and sulfuric acid in the 

production of alkylate is in how the acid is 

regenerated, once the acid becomes too

contaminated with impurities. Hydrofluoric 

acid can be distilled to remove impurities. 

However, sulfuric acid must go through a

series of steps that first break down the acid

into sulfur dioxide and then mix the sulfur 

dioxide with water to create regenerated

sulfuric acid.53 Sulfuric acid catalysts 

inevitably cost about fifty cents per barrel of 

alkylate more than hydrofluoric acid catalysts 

because of the elaborate regeneration process 

that sulfuric acid requires.54

Although sulfuric acid is less hazardous than 

hydrofluoric acid, direct exposure to sulfuric 

acid can cause many detrimental health effects 

at concentrated levels, such as burns or severe 

irritation to the eyes, skin, and respiratory 

 

Needless Risk 17 

d The catalytic reaction using hydrofluoric acid takes

place around 100o F, which only necessitates the use of

water cooling towers to maintain an optimum reaction

temperature. The reaction to produce alkylate using

sulfuric acid is optimized at 45o-50o F (7o-10o C), 

requiring refrigeration to maintain the optimum 

reaction temperature.
tract if concentrated fumes are inhaled.

Because sulfuric acid is often regenerated

offsite, there is a risk of an accident involving 

sulfuric acid during transportation. Once 

onsite, however, it can be regenerated

indefinitely if the refinery builds a 

regeneration facility. 

Two options exist to switch the alkylation

process from hydrofluoric acid to sulfuric 

acid: using a conversion system or building a 

new sulfuric acid alkylation unit. One system

for switching from hydrofluoric acid to 

sulfuric acid is the AlkysafeTM 

conversion/expansion process, offered by 

STRATCO®. AlkysafeTM reuses both the 

reaction and distillation sections of the

alkylation facility.e

 Due to the short 

downtime and the amount of equipment that

is reused, STRATCO claims that AlkysafeTM 

is cost-competitive with mitigation systems

being installed on hydrofluoric acid alkylation 

units. These mitigation systems, on average, 

will cost a refinery between $20 million and 

$30 million, with costs reaching at most $50 

million.55

The cost of building a sulfuric acid alkylation 

unit varies according to the amount of alkylate 

the refinery produces each day. As a general

rule, a new alkylation unit will cost about 

$5,000 per barrel of alkylate produced, per

day. Therefore, a new alkylation unit capable 

of producing 10,000 barrels of alkylate per day 

would cost about $50 million. STRATCO’s 

AlkysafeTM process is estimated to cost onehalf to two-thirds the cost of installing a new 

sulfuric acid alkylation unit.56

ExxonMobil also offers a sulfuric acid

alkylation process that can replace 

hydrofluoric acid alkylation systems, although 

the cost of the process is higher than using 

the STRATCO designs. However, this 

 e The distillation section of the alkylation unit 

neutralizes any acid leaving the reaction chamber with

the alkylate. 

process also would be competitive with

building a new hydrofluoric acid alkylation 

unit.57 It is currently in use in approximately 

12 refineries.58

REDUCE THE PROBABILITY:

HYDROFLUORIC ACID MODIFIERS

The final option available to decrease the 

threat of a hydrofluoric acid release is to 

invest in alkylation modifiers and install active 

mitigation units, such as water spray systems.

This option, however, does not remove the 

possibility of a terrorist threat, and an 

adversary could thwart mitigation systems. 

Modified hydrofluoric acid reduces the ability 

of the acid to form an aerosol cloud by a 

certain percentage, thereby mitigating the 

impact the toxic cloud will have on the 

surrounding community. UOP and Texaco 

estimate the cost of modifying a hydrofluoric 

acid alkylation refinery using Alkad, a passive 

mitigation system, at $7 million. This 

estimate, however, does not include the cost 

of active mitigation systems, which would be

necessary in order to truly reduce the potential

severity of a release.59 Mitigation systems

cost, on average, between $20 million and $30 

million to install.60

ConocoPhillips and ExxonMobil have devised 

their own alkylation modifier under the name 

ReVAP, which has the ability to reduce 

hydrofluoric acid aerosol formation when 

leaked by 60% to 90%. ReVAP is currently 

licensed at five refineries, including the 

Woods Cross Refinery in Utah and the 

Torrance Refinery in California. 61 

18 Needless Risk 

In 2003, public pressure succeeded in 

persuading the Valero Energy Corporation to 

switch to modified hydrofluoric acid at its 

Wilmington, California refinery, near Los 

Angeles. Since an explosion that caused an 

accidental release of hydrofluoric acid at a 

neighboring Torrance refinery in 1987, the 

local community and government have
pushed to shut down two refineries that used

hydrofluoric acid and required a third facility 

to change to modified hydrofluoric acid. The 

community was able to negotiate an

agreement with the South Coast Air Quality 

Management District with regards to the 

Valero facility; Valero decided on 

ConocoPhillips’ ReVap technology and will 

pay a fine up to $1 million if the renovation is 

not complete by the end of 2005. The change 

is expected to cost Valero about $30 

million.62,63 

Since both modification systems cannot 

completely reduce the threat of a hydrofluoric 

acid release, active mitigation units also must 

be installed. Active mitigation for 

hydrofluoric acid requires sensors to detect a

hydrofluoric acid release; acid pumps to 

quickly move the acid to remote locations and 

decrease the amount of acid that is released;

and water spray systems that knock the acid to

the ground and prevent it from affecting 

surrounding communities. If the sensors are 

working properly and detect a leak

immediately, water spray systems can knock

up to 90% of the hydrofluoric acid to the 

ground; however, tests have shown that it

requires at least 40 volumes of water for each

volume of hydrofluoric acid released. 

Effective water spray systems often include 

water spray curtains and remotely operated

water cannons.

64 

Needless Risk 19 
TABLE 4. COMPARISON OF INHERENTLY SAFER TECHNOLOGIES FOR PETROLEUM 

REFINERIES USING HYDROFLUORIC ACID

Sulfuric Acid Solid Acid Catalyst HF modifier 

How Catalyst

Regenerated 

Decomposed into sulfur 

dioxide, then regenerated by

mixing with water vapor 

Frequent regeneration 

with dissolved hydrogen 

every two to four weeks.

Distilled 

Required 

Facility 

Modification 

Some versions require a new 

refrigeration facility and design 

change and modifications of 

current equipment; other

versions cannot be fitted to 

existing alkylation processes. 

AlkyleneTM and 

ExSactTM require 

entirely new alkylation 

facilities, while 

AlkyCleanTM only 

requires a new

regeneration system. 

Additional separation 

equipment needed to

remove leaching acid from

alkylate. 

Advantage over 

HF Alkylation

Unit 

Will not form an aerosol cloud 

and will not pose a threat to 

life outside the facility. 

No corrosive acid can

leave the reaction 

chamber. No threat of a 

chemical spill to anyone. 

Decrease HF aerosol 

formation from 60% to 

90% in the event of a leak, 

depending on version 

used. 

Additional 

Mitigation 

Systems 

Needed 

None None Active mitigation systems 

needed.

Safety 

Concerns 

Acid spill during transport to 

the refinery and to the 

regeneration facility if the 

regeneration facility is not part 

of the refinery. 

None Active mitigation systems 

can fail. 

Cost of 

Conversion 

Varies depending on the daily 

output required. Estimated to 

cost between $2,500 to $3,333

per barrel of alkylate produced 

per day for one version,

$5,000 per barrel for another. 

Cost competitive with 

installing a new

hydrofluoric acid unit, 

less than installing a 

sulfuric acid alkylation

unit. 

Valero is paying an 

estimated $30 million to 

convert its Wilmington, 

CA refinery; most 

modifiers cost $7 million 

plus the cost of active 

mitigation systems. 

20 Needless Risk 
REDUCING CHEMICAL HAZARDS THROUGH POLICY 

MEASURES

The possibility that terrorists could turn 

American industry into weapons that threaten 

Americans’ safety provides policy-makers with

a clear imperative to revise existing policy on 

lethal chemical releases. Furthermore, more 

action is needed than simply increasing 

physical security at chemical facilities; more 

physical security measures do not offset the 

possibility of terrorists taking extreme 

measures to orchestrate a chemical release. 

INADEQUACIES OF EXISTING POLICIES

Industry Cannot Be Left to Voluntary Measures 

Since September 11, 2001, our nation has

tightened security in a variety of venues.

Airports and airlines have numerous new 

regulations they must follow; airplanes have 

routinely patrolled our water supply; our 

government has even established an entire 

new governmental department, the 

Department of Homeland Security. Despite 

the repeated admission by government 

officials that the chemical industry poses a

significant security threat, however, no federal 

regulations exist that require oil refineries or 

any chemical facility to reduce their hazards

when they are able to do so. 

Instead, some facilities subscribe to a 

voluntary industry program known as 

Responsible Care. Responsible Care is an 

initiative developed by the Chemical

Manufacturers Association (CMA), now the 

American Chemistry Council (ACC), in 1988 

to respond to the public’s lack of confidence 

in the chemical industry. The CMA needed to

act to address the poor public image or “end 

up in worse shape than the atomic industry,” 

according to John Johnstone, a former 

chairman of CMA.65 Fifteen years later, the 

ACC requires all member companies to 

comply with this voluntary initiative to

improve security. Responsible Care, however, 

only requires facilities to install physical 

security and does not address preventing 

accidents or terrorist attacks by requiring 

companies to switch to safer technology. 

A former member of the Security Committee 

of the American Chemistry Council, as well as

a former Security Manager for Georgia-Pacific 

Company, has addressed just how inadequate 

these voluntary guidelines are. In a June 2005 

hearing in the House Subcommittee on

Economic Security, Infrastructure Protection,

and Cybersecurity, Sal DePasquale said, “it

may be argued that inner city liquor stores are 

better protected than are the facilities that 

manufacture and use highly toxic and lethal

chemicals.” Despite industry’s claims of

effective self regulation, he continued, “if the 

industry will not issue substantive standards, it 

cannot say that it is self regulating. It is simply 

a contradiction in terms.”66

Furthermore, ACC is made up of only around 

160 of the largest chemical companies, 

meaning that, according to Department of 

Homeland Security statistics, 20% of chemical

companies in the United States do not fall 

under any sort of voluntary chemical security 

standards.67 

The Emergency Planning and Community Right-toKnow Act 

Needless Risk 21 

After the 1984 Union Carbide chemical

disaster in Bhopal, India, which killed 

thousands of people, grassroots pressure 

convinced Congress to pass the Emergency 

Planning and Community Right-to-Know Act 

(EPCRA). This act established a network of 
Local Emergency Planning Committees

(LEPCs) and required facilities to disclose a 

baseline of important information on 

chemical risks, including the amount of

hazardous materials stored at particular 

facilities. 

Despite some positive results of EPCRA, 

including the creation of the Toxics Release 

Inventory and a general decline in toxic 

releases, this law did not address the need to

prevent chemical releases before they happen.

Instead, it only addressed the need to prepare 

for and respond to them. The LEPCs lack 

the authority to mandate hazard reduction,

and many are inactive.68

The Clean Air Act and Risk Management Planning 

Program 

In response to an explosion at a Phillips

chemical facility in Texas that killed 23 

workers in 1989, Congress took further action 

by adding amendments to the Clean Air Act 

in section 112(r). These amendments

established the Risk Management Planning 

(RMP) program that requires industry to 

develop a hazard assessment that covers 

various release scenarios, off-site 

consequences, and a five-year accident history;

a prevention program that manages

procedural areas such as training and safety 

audits; and an emergency response program. 

Therefore, the Risk Management Planning 

program addresses the management of 

chemical risks, but not their prevention. If 

the RMP program were fully implemented as

EPA originally intended, the worst-case 

scenario estimates of off-site impacts of

chemical releases would be available in a

national database and could help reduce 

chemical hazards, much as the Toxics Release 

Inventory has. Although originally available

to the public online, the RMP plans have been

removed from public view and are now 

difficult for individuals to obtain. 

The case study of the voluntary changes at the 

Valero refinery in California shows that when 

a community is aware of the threat a local 

refinery poses to its safety, public pressure 

may successfully persuade the facility to 

change its chemicals and processes in order to

reduce the threat. In order for the RMP 

program to be successful, risk management 

plans must be readily available to the public. 

EPCRA and RMP Too Specific to Address Threat 

In addition to the limitations addressed above,

both EPCRA and the RMP program were not 

designed to address the threat of a terrorist 

attack at a chemical facility, and consequently 

pertain only to certain chemicals, industries, 

and facilities using quantities of chemicals 

above certain thresholds. 

Smaller quantities of chemicals are easier to

manage onsite and therefore pose less of a 

concern for accidental releases. Terrorists, 

however, could specifically target smaller 

quantities of chemicals and still cause 

significant harm. For example, a single oneton cylinder of chlorine gas can fall below 

thresholds for the RMP program. The 

quantity of chlorine gas in this cylinder, 

however, could result in toxic concentrations 

nearly two miles off-site. 

THE RIGHT-TO-KNOW AS A SAFETY TOOL

The federal government should not limit the 

public’d access to information about chemical

use and releases in the effort to prevent 

chemical terrorism. 

22 Needless Risk 

Ensuring a community’s right-to-know about 

chemicals used, stored and released has long 

been a useful tool in protecting public safety 

from toxic hazards. In Massachusetts, for 

example, companies are required to assess and 

disclose all chemicals used by their facilities as 

well as complete toxics use reduction plans.

Simply by completing these plans, and not 

necessarily even implementing them, 
Massachusetts companies have reduced their 

overall use of toxic chemicals by 40%, the 

waste generated by 70%, and their

environmental releases by 92% between 1990 

and 2003. At the same time, production

increased 23% at these facilities.69 

 

New Jersey has seen similar success with its 

Pollution Prevention Act, which requires 

companies to assess and report chemical use. 

As a result of these reporting requirements 

and the Toxic Catastrophe Prevention Act,

hundreds of drinking water facilities and 

sewage treatment facilities have stopped using 

chlorine gas. 

Based on these examples, it is likely that if a 

petroleum refinery completed an assessment 

of available inherently safer technologies, and

was required to disclose the findings to the 

public, it would be compelled to switch to a

safer technology. 

PROTECTING COMMUNITIES THROUGH 

INHERENTLY SAFER TECHNOLOGY

The most effective means of protecting 

American communities from the consequence 

of an act of chemical terrorism is to require

facilities to implement inherently safer 

technologies. 

In the case of hydrofluoric acid in alkylation 

units, inherently safer technology exists and is 

proven to work. Facilities should change their 

chemicals and processes to a safer technology 

as soon as possible, and new facilities should 

be built using the safest technology available. 

Policymakers could require refineries to 

change their processes or to conduct a

technology options analysis.70 A technology 

options analysis is a way to address a range of 

industries and require them to make a 

concerted effort to identify inherently safer 

options in their chemical uses and processes.

Furthermore, a technology options analysis 

provides an opportunity for facilities to adopt 

technologies with acceptable cost and

appropriate performance characteristics and

to explain why technologically feasible options

were not selected. These technology options

analyses should be made public, while 

protecting legitimate confidential business

information, in order to inform communities 

of safety measures at nearby facilities as well 

as to disseminate information on innovative 

technologies. 

Needless Risk 23 

Oil refineries using hydrofluoric acid on site 

pose an unnecessary risk to surrounding 

communities. By requiring facilities to switch 

to inherently safer technologies, as well as

requiring them to publicly disclose plans to 

protect surrounding communities, oil 

refineries could greatly reduce their risk. As 

oil refineries are not the only facilities that 

pose unnecessary risk to surrounding 

communities, these same policy changes 

should apply to a variety of industries and 

facilities. Future policy must focus on 

significantly reducing or eliminating the 

potential harm posed by terrorist attacks on

industrial facilities, instead of focusing on 

physical security and the unachievable task of 

mitigating the consequences of a major 

chemical release. 
METHODOLOGY

The vulnerability zone data in this report were 

collected from Risk Management Planning 

reports obtained at public reading rooms 

operated by the Environmental Protection

Agency in Washington DC, in compliance 

with all rules that currently govern the 

collection of such data. We collected this data

in June and July 2005. 

Facilities had to report their latest Risk 

Management Plans to EPA starting in June 

1999 with revised reports due no less often

then every five years. The data used in this

report are current as of December 2004. 

Facilities are required to file RMPs if they 

store hazardous chemicals listed in section 

112(r) of the Clean Air Act above a threshold 

level used in regulated processes. These 

facilities span a broad spectrum of industries, 

including chemical manufacturers, petroleum 

refineries, agricultural wholesalers, drinking 

water and wastewater treatment systems, 

electric utilities, and others. 

To estimate the total number of people living 

in the vulnerability zones in each state and

nationally, we reviewed the geographic 

location of each facility, as oil refineries are 

often grouped together only a few miles apart.

In order to avoid double counting, we 

assumed if the vulnerability zones of two or 

more facilities overlapped that they 

overlapped entirely. In these instances, we 

included the highest at-risk population from 

the facilities in our calculations. 

As a result, the reported totals are a

conservative estimate of the total population

at risk in each state. In addition, the totals do 

not reflect the fact that many individuals are 

at a heightened risk because they live within

the vulnerability zone of two or more oil 

refineries using hydrofluoric acid. 

24 Needless Risk 
APPENDIX: OIL REFINERIES USING OR STORING 

HYDROFLUORIC ACID ON-SITE

Needless Risk 25 

State Facility Name City Parent Company 

CA ExxonMobil Torrance Refinery Torrance ExxonMobil 

CA Ultramar Inc. d/b/a Valero Wilmington Refinery Wilmington Valero Energy Corporation 

IL ExxonMobil Oil Corporation Joliet Refinery Channahon ExxonMobil 

IL PDV Midwest Refining, LLC Lemont CITGO 

IL Marathon Ashland Petroleum LLC IRD Robinson Marathon Ashland Petroleum LLC 

IN Countrymark Cooperative, Inc. Mt. Vernon Countrymark Cooperative, Inc. 

KS Coffeyville Resources Refining & Marketing Coffeyville Coffeyville Resources, LLC 

KS Frontier El Dorado Refining Company El Dorado Frontier Oil Corporation 

KS National Cooperative Refinery Association McPherson Cenex 

KY Catlettsburg Refining, LLC Catlettsburg Marathon Ashland Petroleum LLC 

LA ConocoPhillips Company Alliance Refinery Belle Chasse ConocoPhillips 

LA Chalmette Refining, L.L.C. Chalmette 

Chalmette Refining, L.L.C

(ExxonMobil and Petroleos de 

Venezuela S.A.) 

LA 

Marathon Ashland Petroleum, LA Refining 

Division Garyville Marathon Ashland Petroleum LLC 

LA Murphy Oil USA, Inc. Meraux Refinery Meraux Murphy Oil Corporation 

LA Placid Refining Co. L.L.C. -Port Allen Refinery Port Allen Placid Refining Co./Petro-Hunt 

MN Marathon Ashland Petroleum, MN Refining Div. St. Paul Park Marathon Ashland Petroleum LLC 

MT ConocoPhillips Billings Refinery Billings ConocoPhillips 

MT Montana Refining Company Great Falls Holly Corporation 

MT CHS Inc. - Laurel Refinery Laurel Cenex 

MT ExxonMobil Billings Refinery near Billings ExxonMobil 

ND Tesoro Mandan Refinery Mandan Tesoro Corporation 

NJ Valero Refining Co. - New Jersey Paulsboro Valero Energy Corporation 

NM Navajo Refining Company Artesia Holly Corporation 

NM Ciniza Refinery Jamestown Giant Industries 

OH Ohio Refining Division Canton Marathon Ashland Petroleum LLC 

OK TPI Petroleum Inc. Ardmore Valero Energy Corporation

OK ConocoPhillips Refinery - Ponca City, Oklahoma Ponca City ConocoPhillips 

OK Wynnewood Refining Company Wynnewood Gary-Williams Energy Corporation

PA Sunoco Philadelphia Refinery Philadelphia Sunoco, Inc. 

PA Trainer Refinery Trainer ConocoPhillips 

TN The Premcor Refining Group Inc. Memphis Premcor Inc. 

TX Alon USA Big Spring Refinery Big Spring Alon USA LP 

TX Borger Refinery and NGL Center Borger ConocoPhillips

TX Flint Hills Resources, L.P. - CC West Refinery Corpus Christi Koch Industries 

TX Valero Refining Co. - Texas, L.P. - West Plant Corpus Christi Valero Energy Corporation 

TX CITGO Corpus Christi Refinery East Plant Corpus Christi CITGO 

TX Valero Refining Co - Texas, L.P. - East Plant Corpus Christi Valero Energy Corporation 
State Facility Name City Parent Company 

TX Crown Central Petroleum, Houston Refinery Pasadena Crown Central LLC 

TX Premcor Port Arthur Refinery Port Arthur Premcor Inc. 

TX Marathon Ashland Petroleum Texas Refining Texas City Marathon Ashland Petroleum LLC 

TX BP America, BP Texas City Site Texas City BP 

TX Valero Refining - Texas, L.P. Texas City Valero Energy Corporation 

TX Diamond Shamrock Refinery - Three Rivers Three Rivers Valero Energy Corporation 

UT Big West Oil LLC North Salt Lake Flying J, Inc. 

UT ChevronTexaco Salt Lake Refinery Salt Lake City ChevronTexaco Corporation

UT Woods Cross Refinery Woods Cross Holly Corporation 

WA ConocoPhillips Company Ferndale ConocoPhillips 

WI Murphy Oil USA Superior Refinery Superior Murphy Oil Corporation 

WY Frontier Refining Inc. Cheyenne Frontier Oil Corporation 

WY Wyoming Refining Company Newcastle Hermes Consolidated 

26 Needless Risk 
END NOTES

 1 Congressional Research Service, RMP Facilities in the United States as of May 2005, released by Representative

Edward J. Markey, July 6, 2005. 2 U.S. EPA, Assessment of the Incentives Created by Public Disclosure of Off-Site Consequence Analysis Information for Reduction in 

the Risk of Accidental Releases, April 18, 2000: 2. 3 “Ammonia leaks rousts tourists from Gulf hotels,” Sun Herald, February 23, 2003. 4 The Army Surgeon General found chemical plant terrorism to be second only to a major bioterror event. See Eric 

Pianin, “Study Assesses Risk of Attack on Chemical Plant,” Washington Post, March 12, 2002. 5 National Infrastructure Protection Center, “Homeland Security Information Update,” February 12, 2003. 6 Agency for Toxic Substances and Disease Registry, “Industrial Chemicals and Terrorism: Human Health Treat 

Analysis Mitigation and Prevention,” 1999. 7 Carol D. Leonnig and Spence S. Hsu, “Fearing Attack, Blue Plains Ceases Toxic Chemical Use,” Washington Post, 

November 10, 2001. 8 James Belke, U.S. Environmental Protection Agency, “Chemical accident risks in U.S. industry – A preliminary

analysis of accident risk data from U.S. hazardous chemical facilities,” September 25, 2000. Available at 

http://www.epa.gov/swercepp/pubs/stockholmpaper.pdf. 9 Energy Information Administration, Annual Refinery Report, “Petroleum Supply Annual 2004, Volume 1, Table 

36. Number and Capacity of Operable Petroleum Refineries by PAD District and State as of January 1, 2005.” 10 Adam Fifield, “In the Shadow of Danger: The Chemical Plant Peril How Safe, How Secure?” Philadelphia Inquirer, 

April 20, 2003. 

11 “Hydrofluoric Acid: Chemical Safety Information,” Environment Health and Safety at University of North 

Carolina. Available at http://ehs.unc.edu/pdf/HydrofluoricAcid.pdf. 12 Bruce Scott, “Alkylation Process Hazards Management: Does it Matter Which Acid You Use?” Presented at the 

1991 Alkylation Seminar. May 1991. 13 Agency for Toxic Substances and Disease Registry, “Toxicological Profile for Fluorides, Hydrogen Fluoride, and 

Fluorine.” Available at http://www.atsdr.cdc.gov/toxprofiles/tp11.html. 14 “Occupational Safety and Health Guideline for Hydrofluoric Acid,” 

http://www.osha.gov/SLTC/healthguidelines/hydrogenfluoride/recognition.html. 15 “Alkylation.” Encyclopedia Britannica Online, 2005. 16 Bruce Scott. “Alkylation Process Hazards Management: Does it Matter Which Acid You Use?” Presented at the 

1991 Alkylation Seminar. May 1991. 17 DuPont fact sheet, “H2SO4 vs. HF.” Available online at

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23 Adam Fifield, “In the Shadow of Danger: The Chemical Plant Peril How Safe, How Secure?” Philadelphia Inquirer, 

April 20, 2003. 

24 Adam Fifield, “In the Shadow of Danger: The Chemical Plant Peril How Safe, How Secure?” Philadelphia Inquirer, 

April 20, 2003. 

25 Don Steward and Sandi McDaniel, “Danger Adrift: Chaos reigned after Sun Co. Spill,” Tulsa Tribune, April 28, 

1988. 

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Needless Risk 27 

31 Theodore Karasik, “Toxic Warfare,” RAND Project Air Force, 2002. 
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Technologies White Paper, Leveraging Resources and Targeting Performance.” Available at 

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http://www.uop.com/objects/NPRASpr2003HFAlky.pdf. 49 Personal communication with Peg Stein, UOP LLC, June 29, 2005. 50 “Baku Heydar Aliyev Refinery selects UOP technologies for high-octane gas project,” American International 

Automobile Dealers, February 7, 2005, at www.showroommagazine.com. 51 Exelus, “Exelus Solid Acid Catalyst Technology – ExSact,” Accessed July 14, 2005 at 

http://www.exelusinc.com/exsact.shtml. 52 Exelus, “Exelus Solid Acid Catalyst Technology – ExSact,” Accessed July 14, 2005 at 

http://www.exelusinc.com/exsact.shtml. 53 Enviro-Chem, “Spent Acid Regeneration: Sulfuric Acid,” accessed July 14, 2005 at http://www.envirochem.com/plant-tech/3rdtier/spentacidtop.html. 54 Personal communication with Randy Peterson, Alkylation Division at STRATCO, July 21, 2003. 55 Randall Peterson, STRATCO, The STRATCO® AlkysafeTM Process: Low Cost Conversion/Expansion From HF To 

H2SO4 Alkylation,” Available online at http://www.stratco.dupont.com/alk/pdf/STRATCOAlkysafeProcess.pdf. 56 Personal communication with Randy Peterson, Alkylation Division at STRATCO, July 21, 2003. 57 Steven Ackerman, Girish K. Chitnis, and David S. McCaffery, Jr. “ExxonMobil Sulfuric Acid Alkylation 

Process.” Presented at the 5th International Topical Conference on Refinery Processing. March 10-14, 2002 58 ExxonMobil, “Sulfuric Acid Alkylation: Light Ends Upgrading Technology,” accessed July 14, 2005 at 

http://www.prod.exxonmobil.com/refiningtechnologies/fuels/mn_sulfuric.html. 59 Pam Pryor, “Alkylation Current Events,” paper presented at the 2001 Alkylation Seminar in Scottsdale, Arizona, 

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28 Needless Risk 

61 ConocoPhillips Technology Solutions, “ReVap in Action,” Accessed July 14, 2005 at 

http://www.coptechnologysolutions.com/alkylation/revap/revap_action/index.htm. 
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1991 Alkylation Seminar, May 1991. 65 John Holusha, “Chemical Makers Identify a New Hazard,” New York Times, August 12, 1991. 66 Sal DePasquale, Testimony before the House Homeland Security Committee hearing, June 15, 2005. 67 Testimony of Martin Durbin of the American Chemistry Council, Senate Committee on Homeland Security and 

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Needless Risk 29 

70 ConocoPhillips Technology Solutions, “ReVap in Action,” Accessed July 14, 2005 at 

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