Former Texas Refinery Inspector, Neil Carman on:
Public health concerns of toxic air emissions:
Yuma Refinery - Draft Air Permit

Public health concerns of criteria and toxic air emissions:
ARIZONA CLEAN FUELS YUMA, L.L.C. draft air permit

Maximum Allowable Emissions Rates listed in state air permit for routine refinery operations:
Carbon Monoxide (CO) = 817 tons per year (tpy)
Nitrogen Oxides (NOx) = 396 tpy
Volatile Organic Compounds (VOCs) = 251 tpy
Sulfur Dioxide (SO2) = 251 tpy
Particulate Matter ten microns or less in aerodynamic diameter (PM10) = 176 tpy

Total Modeled Annual Criteria Emissions under draft permit = 1,891 tpy
Annual Permitted Criteria Emissions 1,891 tpy in pounds per year = 3,782,000 pounds per year

#1 Concern: No Emission limitations from many expected Startups, Shutdowns and Upsets appear to be included in the draft permit MAERT. Startups, Shutdowns and Upsets will produce added CO, NOx, VOCs, SO2, PM10, benzene and others but these emissions are not permitted since they are not listed in the draft permit issued by ADEQ. In essence, no instantaneous (pounds per hour) or annual pollution (tpy) limits have been included for dozens of expected events such as Startups, Shutdowns and Upsets emissions that occur each year. Without being included in the permit, these events and emissions are totally unregulated. Emissions in Startups, Shutdowns and Upsets alone may exceed 1,891 tpy of permitted toxins.

#2 Concern: Unenforceable conditions on Startups, Shutdowns and many types of Upsets. No time duration limits (hours), no pollution limits (volumes) and no repeat occurrence limits (number of events) have been specified on the air emissions from Startups, Shutdowns and Upsets in the draft ACF permit. The Sulfur Recovery Unit has a 15-minute limit in place. It means the ACF refinery is allowed an unlimited number of hours (8,760 per year) for Startups, Shutdowns and Upsets every year and is authorized an unlimited volume of emissions from these events. The number of repeat occurrences of Startups, Shutdowns and Upsets is unlimited. Without being included in the permit, these emission events are basically unregulated.

#3 Concern: Narrow air modeling analysis. No air dispersion modeling evaluation has been performed for expected emissions from Startups, Shutdowns and Upsets. These emissions include CO, NOx, VOCs, SO2, PM10, benzene, and others. The air modeling analysis is inadequate and does not demonstrate that the plant's emissions will be low enough to insure adequate protection of public health.

#4 Concern: Inadequate health effects analysis by ADEQ. No health effects reviews have been conducted for 100% of the refinery's emissions since no emission impacts were evaluated from Startups, Shutdowns and Upsets. Yet the draft permit mentions the potential for such events nearly 300 times from nearly the entire refinery. Health effects evaluation is inadequate and does not demonstrate that the plant's emissions will be low enough to insure adequate protection of public health. These emissions include CO, NOx, VOCs, SO2, PM10, benzene and others.

#5 Concern: Pollutants such as benzene are known human cancer-causing agents and there is no safe limit of human exposure to carcinogens. Based on ADEQ's technical review documents, the ACF refinery is expected to emit numerous carcinogens, probable carcinogens and suspected carcinogens at levels above minimum detection levels using available monitoring technology. The presence of detectable concentrations of such highly toxic pollutants indicates emissions will not be at safe levels in the environment around the plant.

#6 Concern: Synergistic and additive health effects analysis have not been performed for different combinations of harmful mixtures of any criteria or toxic pollutants expected to be released by the ACF refinery. Emissions from the refinery will not occur as single pollutants but in the form of complex toxic mixtures or soups for which no toxicological evaluation has been performed by ADEQ, ACF or ACF's consultants. People living in the area will be exposed to complex toxic mixtures.

#7 Concern: Health effects analysis have not been performed regarding children exposed to criteria or toxic pollutants expected to be released by the ACF refinery. Children are the most vulnerable to toxic exposures due to the following reasons:

1. developmental sensitivity of their immature systems.
2. higher rates of respiratory-metabolic activity meaning more pollution is breathed in per pound of body weight.
3. exposed more often by playing outside more than adults.
4. being primarily mouth breathers.
5. Children's airways are narrower than those of adults, thus enhancing the inflammatory effect of air pollution.
6. Children do not have a fully developed immune system, liver, or kidneys to help protect them from the damaging effects of many chemicals; Immature lungs are unable to remove or neutralize contaminants adequately, and developing brains and neural pathways are particularly vulnerable to toxins. In addition, some chemicals affect the endocrine system, potentially disturbing neural, reproductive, and immune development.
7. Airborne carcinogens and mutagens appear to have a greater effect on children, possibly because rapidly growing tissues are less differentiated and more "suggestible" than mature tissues.
8. Children exposed to carcinogens have a longer expected life span over which carcinogenic action may occur.

The American Academy of Pediatrics' Committee on Environmental Health has published an important new policy statement on "Ambient Air Pollution: Health Hazards to Children" which finds that there are adverse health effects at levels near or below the current standards for ozone, particulate matter, and nitrogen dioxide, and concludes that the 1997 NAAQS may not adequately protect children.

Specifically, the Policy Statement finds that the current annual and 24-hour NAAQS for PM2.5 and PM10 should be lowered to protect public health, based on recent scientific studies. In addition, the policy statement cites several studies demonstrating that ozone may be toxic at concentrations lower than the current 8-hour NAAQS, and suggests that the ozone standards may need to be revised if these studies are confirmed. The Statement makes further specific recommendations on need to set air quality standards with a margin of safety to protect against the potential effects of air pollution on the fetus, infant, and child.

Additional recommendations address the need for specific control strategies to reduce children's exposure to criteria air pollutants and toxic air pollutants, specifically mercury and diesel. The ACF refinery is expected to have both mercury and diesel emissions. The AAPC policy statement is available at: http://pediatrics.aappublications.org/cgi/content/full/114/6/1699

#8 Concern: ADEQ's Ambient Air Quality Guidelines (AAAQGs) are not state standards set in law and have not been subjected to external peer-review by independent toxicologists or public comments as to their adequacy or inadequacy in protecting public health. Being "guidelines," the ADEQ has complete discretion as to what concentration limits to set the AAAQGs at, when monitoring is required, and when, if ever, enforcement action is pursued due to exceedances. Typically such air quality "guidelines," are derived from the American Conference for Governmental Industrial Hygienists (ACGIH) handbook for setting TLVs in the workplace and it specifically recommends against using them to prescribe ambient air limits such ADEQ appears to do.

#9 Concern: The BACT analysis is incomplete since it has not been adequately performed to address all refinery emissions of CO, NOx, VOCs, SO2, PM10, benzene, and others occurring due to Startups, Shutdowns and Upsets.

#10 Concern: The draft permit does not appear to require reliable backup emergency electrical power systems to prevent upsets triggered by power dips, power surges, temporary power loss, or significant power failures during storms.

#11 Concern: The draft permit does not appear to require backup double or triple redundant electronic control systems to prevent upsets triggered by electronic glitches and computer malfunctions. If ACF is proposing to use such technology, the permit needs to reflect it.

#12 Concern: ADEQ has not required an ambient air monitoring system to be set up to confirm that refinery emissions are released at safe levels, except for a limited amount of H2S monitoring close to the refinery fence line. The draft permit does not address a community ambient air monitoring system. Oil refineries emit a toxic soup, a complex mixture of toxic substances and ACF will be emitting such toxins into the air on a daily basis. Air toxics to be monitored include but are not limited to Benzene, Benzo(a)pyrene, Biphenyl , 1,3-Butadiene, Carbon Disulfide, Carbonyl Sulfide, Cumene, Cyclohexane, Diethanolamine, Dioxin, Ethylene, Ethyl benzene, Mercury, Methyl Ethyl Ketone, Naphthalene, Phenol, PolyAromatic Hydrocarbons (PAHs), Propylene, 1,2,4-trimethylbenzene, Toluene, and Meta-,Para-, Ortho-Xylenes.

#13 Concern: The ACF will emit large volumes of numerous

1. cancer-causing chemicals,
2. chemicals causing birth defects in newborn children,
3. toxic substances causing neurological effects & damage,
4. substances causes reproductive effects such as sterility & dysfunction,
5. toxins that induce inheritable mutagenic effects altering DNA-genetics,
6. toxins producing respiratory problems,
7. developmental toxicants,
8. kidney toxicants,
9. gastrointestinal toxicants,
10. immunotoxicants,
11. cardiovascular toxicants,
12. endocrine toxicants,
13. skin toxicants, etc.

Neurological toxins: Cumene, Hydrogen sulfide (H2S), Mercury (Hg), Methanol, catalyst Molybdenum trioxide,
Carcinogenic toxins: Benzene, Benzo(a)pyrene, 1,3-Butadiene, catalyst Chromium compounds, Diethanolamine (DEA), Dioxin (TCDD), Hydrogen cyanide, catalyst Nickel compounds, Polycyclic Aromatic Hydrocarbons (PAHs-dozens of these compounds), Styrene, Tetrachloroethylene,
Reproductive toxins: Benzene, 1,3-Butadiene, Dioxin (TCDD), Hydrogen cyanide, catalyst Nickel compounds, Tetrachloroethylene, Toluene, (Ortho-, Meta-, Para-mixed isomers) Xylenes Birth defects toxins: Benzene, Biphenyl, 1,3-Butadiene, Dioxin (TCDD), Hydrogen cyanide, catalyst Nickel compounds, Phenol, Tetrachloroethylene, Toluene, (Ortho-, Meta-, Para-mixed isomers) Xylenes Mutagenic toxins (DNA damaging): Hydrogen cyanide, Styrene, Aromatic/benzene-containing toxins: Benzene, Biphenyl, Cresol (Ortho-, Meta-, Para-mixed isomers), Dioxin (TCDD), Ethylbenzene, Naphthalene, Phenol, Styrene, 1,2,4-trimethylbenzene, Toluene, (Ortho-, Meta-, Para-mixed isomers) Xylenes
Acute toxins: Ammonia, Carbon disulfide (CS2), Carbonyl sulfide (COS), Cresol (mixed isomers), Cyclohexane, Hydrogen cyanide, ethyl Ethyl Ketone (MEK), catalyst Molybdenum trioxide, Naphthalene, Propylene, Sulfur trioxide (SO3), Sulfuric acid (H2SO4), 1,2,4-trimethylbenzene,
Chronic toxins: Ammonia, Benzene, Biphenyl, Carbon disulfide (CS2), Carbonyl sulfide (COS), catalyst Chromium compounds, Cresol (mixed isomers), Cumene, Cyclohexane, Dioxin (TCDD), Ethylene, Ethylbenzene, catalyst Hydrochloric acid, Mercury (Hg), ethyl Ethyl Ketone (MEK), catalyst Molybdenum trioxide, Naphthalene, catalyst Nickel compounds, Phenol, Propylene, Styrene, Sulfur trioxide (SO3), Sulfuric acid (H2SO4), Tetrachloroethylene, 1,2,4-trimethylbenzene, (Ortho-, Meta-, Para-mixed isomers) Xylenes

KEY AIR TOXIC SUBSTANCES EMITTED FROM OIL REFINERIES:

Ammonia - AT, CT
Benzene - C, BD, R, CT - ***
Biphenyl - BD, CT - ***
1,3-Butadiene - C, BD, R, CT - ***
Carbon disulfide (CS2) - AT, CT - ***
Carbonyl sulfide (COS) - AT, CT - ***
Cumene - CT, N - ***
Cyclohexane - AT, CT
Diethanolamine (DEA) - C - ***
Dioxin (TCDD) - C, BD, R, CT - ***
Ethylene - CT
Ethylbenzene - BD, R, CT - ***
Hydrogen sulfide (H2S) - N, AT, CT
Mercury (Hg) - N - ***
Methyl Ethyl Ketone (MEK) - AT, CT - ***
Methyl Tertiary Butyl Ether (MTBE) - C, AT, CT - ***
Naphthalene - AT, CT - ***
Phenol - BD, AT - ***
Propylene - AT, CT
Styrene - C, M, CT - ***
Sulfur trioxide (SO3) - AT, CT
Sulfuric acid (H2SO4) - AT, CT - ***
1,2,4-trimethylbenzene - AT, CT - ***
Toluene - BD, R - ***
Xylenes - BD, R, CT - ***

AC = ACUTE TOXIN
BD = DEVELOPMENTAL TOXIN (causes birth defects)
C = CARCINOGEN
CT = CHRONIC TOXIN
M = HERITABLE MUTAGEN (causes genetic changes to DNA or genes)
N = NEUROTOXIN
R = REPRODUCTIVE TOXIN
***HAP = HAZARDOUS AIR POLLUTANT (list of 188 HAPs is from Title III of the 1990 Federal Clean Air Act Amendments signed into law November 15, 1990)

#14 Concern: The ACF refinery will experience, on a routine basis, a variety of upsets, malfunctions, and resulting excess emission events when toxic air pollution exceeds the permitted levels, or Maximum Allowable Emission Rates. For example, the draft 501 page permit uses the word "Upset" 9 times; "Malfunction" (singular form) is listed 108 times. "Malfunctions" (plural form) 38 times; and "Excess Emissions" 142 times. Total is 297 times.

Upset - listed 9 times in ACF's draft air permit (501 pages).
Malfunction - listed 108 times. Malfunctions - listed 38 times.
Excess Emissions - listed 142 times.

Upsets (9):
Most refinery units are vulnerable to upset conditions. Specifically listed are Amine Regeneration Unit, Sour Water Stripper, Sulfur Recovery Unit, Emergency Flares. Many more upset conditions are cited under Malfunction(s).

Malfunction (108) or Malfunctions (38) may occur in most plant process units:
Malfunctions Reporting & Record Keeping (7), Crude Distillation Unit (3), Gas Concentration Plant (0), Hydrocracker Unit (3), Naphtha Hydrotreater Unit (0), Catalytic Reforming Unit (6), Isomerization Unit (0), Distillate Hydrotreater Unit (3), Butane Conversion Unit (3), Benzene Reduction Unit (0), Delayed Coking Unit (0), Petroleum Coke Storage-Handling-Loading (0), Amine Regeneration Unit (0), Sour Water Stripper (1), Sulfur Recovery Unit (23), Hydrogen Plant (25), Storage Tanks/Tank Farm (12), Truck & Rail Car Loading Racks (4), Benzene Waste Operations (3), Wastewater Treatment Plant (22), Equipment Leaks (1), Emergency Flares (3), Steam Boilers (27), and Cooling Towers (0).

Excess emissions (142) are unpermitted and may be produced by most refinery process units: Excess Emissions Reporting & Record Keeping (30), Crude Distillation Unit (6), Gas Concentration Plant (10), Hydrocracker Unit (6), Naphtha Hydrotreater Unit (6), Catalytic Reforming Unit (6), Isomerization Unit (0), Distillate Hydrotreater Unit (6), Butane Conversion Unit (6), Benzene Reduction Unit (0), Delayed Coking Unit (6), Petroleum Coke Storage-Handling-Loading (0), Amine Regeneration Unit (11), Sour Water Stripper (5), Sulfur Recovery Unit (7), Hydrogen Plant (6), Storage Tanks/Tank Farm (7), Truck & Rail Car Loading Racks (9), Benzene Waste Operations (2), Wastewater Treatment Plant (7), Equipment Leaks (0), Emergency Flares (0), Steam Boilers (4), Cooling Towers (1), and Miscellaneous (2).

Fugitive Hydrocarbon Vapors from more than 52,700 Equipment Items Pieces of Refinery Equipment with Potentially Fugitive Organic Vapor Leaks in Gaseous and/or Liquid VOC Service = 52,706 components on pages 401-402 in draft permit. Organic vapors may contain benzene, toluene, xylene, ethylbenzene, 1,3-butadiene, and dozens of other toxic organic compounds in gasoline, diesel fuel, jet fuel, etc. 4,162 valves in gas/liquid service
15,594 valves in light liquid service
9,850 valves in heavy liquid service
3,254 connectors in gas/liquid service
12,493 connectors in light liquid service
7,037 connectors in heavy liquid service
190 pumps in light liquid service
113 pumps in heavy liquid service
13 compressors
Total = 52,706 equipment components in gas and/or liquid hydrocarbon service are all capable of leaking fugitive gases or liquids in ppm range. Fugitives estimated but not listed in permit.
55 STORAGE TANKS IN USE WILL LEAK FUGITIVE HYDROCARBON VAPORS

Certain Tanks with Potential for Fugitive Leaks in Liquid Service = 55 large tanks in draft permit CRUDE OIL AND PRODUCT STORAGE TANKS WITH MILLIONS OF GALLONS IN CAPACITY
"A" group product storage tanks = 8
"B" group product storage tanks = 27
"C" group crude oil storage tanks = 20

TOTAL PRODUCT/CRUDE TANKS = 55 All 55 Storage Tanks will leak a certain amount of fugitive hydrocarbon vapors into the air depending on the liquids present, the volumes and other factors.

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#15 Concern: Hydrogen Sulfide ambient monitoring

The refinery will install a Hydrogen Sulfide gas ambient air monitoring network around the facility's perimeter to determine if H2S is leaking at above or below the Arizona state standard of 0.03 ppm (30 parts per billion) over a thirty-minute period. The draft permit does not appear to specify how many H2S monitors are to be installed or how close they are to be, so there could be holes in the H2S monitoring network especially if a leak occurs from a process area or piece of equipment sited in between two monitors. It's possible that no H2S ambient air monitor would detect leaks from certain plant areas depending on how many or how few H2S monitors are eventually installed. If enough H2S monitors are installed, then detection of H2S leaks might be satisfactory if the monitors are always working properly, but they could shut down electronically during lightning strikes, thunderstorms, power surges, power failures, etc. when there could be electrical problems with the H2S monitors and H2S leaks in the refinery.

#16 Concern: Emergency Flares

Emergency Refinery Flares Number 1 and Number 2 - SMOKESTACKS

The requirement of "no visible emissions" allowed is a standard permit special condition for all refineries and petrochemical plant flares. Unfortunately, not a single refinery or petrochemical plant in the US can live up to the permit special condition of "no visible emissions" from the process flares or emergency flare stacks. It's expected that a "no visible emissions" prohibition on the two emergency flares will be violated on a regular basis during operator errors, computer-electronic glitches, refinery process malfunctions, equipment failures, upset conditions, power failures, power surges, lightning strikes, thunderstorms, and assorted breakdowns typical of such large facilities. The refinery is to be made with metal and electrical items subject to failure.

If all leaks, flaring and unaccounted emissions were included, the refinery's annual emissions could be significantly higher than the 1,891 tpy allowed the permit. The 1,891 tpy does not include emissions of chlorine, ammonia, carbon disulfide, carbonyl sulfide, sulfuric acid, sulfurous acid, sulfur trioxide, mercury, lead, and certain other toxic chemicals. Based on the 150,000 crude oil barrels refined/day, 1,891 tons per year equals 5.18 tons per day or 10,361.6 pounds per day. This calculates out to 0.069 or 0.070 pounds of air pollution per barrel.