.

-


Dioxins and Refineries:
Analysis in the San Francisco Bay Area.
August 2000
Introduction.
In a June 21, 2000 television interview a Bay Area oil refinery official summarized his indus-
. try's position on why it is not taking action to prevent its ongoing releases of dioxins. saying
that: "[O]ver 95 percent of the dioxin that goes out in our effluent to the Bay comes from
sources outside of our control."
Dioxins cause serious threats to public health. Bay Area communities and most Bay A.rea elect-
_ed officials seek dioxins elimination wherever possible, suggesting that oil refiners should do
their part to stop the pollution. However, public officials charged with protecting environmental
health from refinery pollution have declined to require- or even to investigate- pollution pre-
vention for dioxins and refineries. The San Francisco Bay Regional Water Quality Control
Board explains this inaction by siding with the industry argument. The Water Board says
refineries cause so little of this pollution that most of the dioxins contamination in refineries is
caused by residential wood fires and vehicle use by people in the community.
In fact, no government health agency has ever made a thorough assessment of all the rekases of
dioxins caused by petroleum refineries.
Dioxins and Refineries reports the first comprehensive assessment of the total amount of dioxins
released from all petroleum refinery sources. It reveals oil refining as an important source of
dioxins in the Bay Area. It shows that existing government analyses drastically underestimate
refinery releases of dioxins. As an immediate matter. it sets forth specific steps for cost-effec-
tive elimination of dioxins in refineries.
Communities for a Better Environment ( CBE) Report No. 2000-2



Author:
Dioxins and Refineries:
Analysis in the San Francisco Bay Area.
Communities for a Better Environment (CBE)
CBE Report No. 2000-2. August 10, 2000.
Supporting analysis:
Greg Karras, Senior Scientist
Azibuike Akaba, Staff Scientist
Anne Simon, Senior Attorney
Karen Susag, Community Health Advocate
Sue Tuddenham, Intern
This report was made possible by thousands of CBE's members, friends and
supporters, and by the generous support of the Richard and Rhoda Goldman
Fund, Jenifer Altman Foundation, Patagonia Environmental Grants Program,
Mari Mayeda and Albert Kutchins, through the San Francisco Foundation, and
of the V-Fund through the Tides Foundation.
In addition, many environmental scientists, researchers, community members
and other experts reviewed, guided and substantially improved the research,
analysis and communication of the information. CBE is solely responsible for
the report's content.
Thank you all!
Founded in 1978, Communities for a Better Environment (CBE) is an
environmental health and justice organization that works with urban
communities directly affected by industrial pollution. CBE provides
organizing skills and legal, technical and scientific resources that
assist these communities in taking control of the decisions that affect
their quality of life. We believe that fundamental change comes from the
grass roots up, and that environmental solutions can only be sustained in
concert with social and economic justice.
Currently CBE's staff are:
- Organizing community members and developing their leadership skills to
reduce exposure to environmental hazards.
- Training community members who live in heavily industrial areas to use
low-cost and highly accurate air monitoring devices.
- Fighting for the elimination of dioxin releases into the San Francisco
Bay and promoting community Right-To- Know about dioxin emissions by
industries.
- Using legal strategies to affect policy change and enforce environmental
health protection laws and rules .
Oakland Office
1611 Telegraph Ave., Suite 450
Oakland, CA 94612
510/ 302-0430
Huntington Park Office
5610 Pacific Blvd., Suite 203
Huntington Park, CA 90255
323/ 826-9771



CONTENTS:
Introduction
Contents
Purpose, scope and terms
Approach
Findings
Discussion
Recommendations
Part 1. Multiple sources of preventable dioxin pollution in oil refineries
Confirmed sources:
Reforming catalyst regeneration
Cracking catalyst regeneration
Oil- and waste-fired process heaters and boilers
Contamination of diesel fuel in refineries
Contamination of motor oil in refineries
Suspected sources:
Flares, coking, desalting, distillation and other processes
Contamination of petroleum coke and other products
Process upsets and uncontrolled fires
Contaminated solid waste disposal
page 1
page 2
page 3
page 4
page 5
page 8
page 11
page 12
page 12
page 16
Part 2. Measurement of the dioxins release rate from all Bay Area oil refinery sources page 17
Analysis of dioxins release measurement data quality: page 17
Error and bias related to choice of analytical methods
Error and bias related to test frequency and disclosure
Error and bias when there is no testing of a known or suspected source
Error and bias related to sampling of release pathways
Analysis of source-specific measurements: page 23
Reforming catalyst regeneration
Cracking catalyst regeneration
Oil- and waste-fired process heaters and boilers
Contamination of refined products in refineries
Contamination of effluent in refineries
Other (suspected) refinery sources
Minimum and maximum bounds of total Bay Area oil refining dioxins release page 27
Part 3. Measurements linking dioxins in the Bay Area environment to refinery sources page 28
Analysis of dioxins pollution gradients in sediment, water and fish
Analysis of dioxins profiles at refinery sources and in environmental samples
Comparison of releases with fallout to Bay Area refineries from other sources
Literature cited
2
page 28
page 33
page 35
page 38
Purpose, Scope and Terms.
Dioxins are a group of industrial byproducts and among the most toxic chemicals known. Pre-
industrial dioxin pollution was virtually nonexistent. Today people throughout the general popu-
lation have dioxins in their tissues at or near concentrations that cause a high risk of cancer, and
may cause diabetes, endometriosis and other effects.l,2,3,4 Studies of humans suggest that diox-
ins exposures in the womb and through breast feeding cause effects on learning and the immune
system in 10-20% of children .1 ,2,3.4
Citing high exposure for people who rely on San Francisco Bay fish for food, the U.S.
Environmental Protection Agency overruled the California Regional Water Quality Control
Board in 1999 to designate dioxins pollution as a "high priority" cause of water quality stan-
dards violations throughout the Bay.
5
Nearly ten years earlier, California established a policy
that directs the Water Board to eliminate dioxins discharges to the Bay by the year 2000.
6
The term "dioxins" in this report includes the polychlorinated dibenzo-p-dioxins and diben-
zofurans with chlorine atoms in the 2,3,7 and 8 positions ("CDDs" and "CDFs"), and polychlo-
rinated biphenyls (PCBs) that exhibit dioxin-like toxicity. Refinery releases are reported as the
combined toxicity of these chemicals (including dioxin-like PCBs) using the World Health
Organization consensus (TEQDFP-WH0
98
).
16
When measurements include only CDD/Fs the
combined toxicity of these dioxins is noted as TEQ
0
F (the "P" is left out of the subscript).
Individual dioxins are named using abbreviations (for example: OCDD, OCDF, and PCB-126).
When a larger group of chemicals that includes some dioxins is discussed, the larger group is
referred to by a different term, such as "total CDD/Fs" or "PCB homologue groups."
Petroleum refining is among the world's largest industries, yet the first published evidence
that oil refining is a dioxins source came only 12 years ago, 7 31 years after dioxin was found to
cause health problems in 1957.
4
As recently as November 1999 EPA admitted that it does not
know the total amount of dioxins released by refineries.
8
Importantly, more data exist on refin-
ery dioxin pollution in the Bay Area than in any other region of the country.
Underestimating pollution is a recurrent environmental problem. For example, until late
1990 the Water Board agreed with oil company managers' claims that refineries are not signifi-
cant sources of toxic selenium pollution in S.F. Bay.9 However, the Water Board later admitted
that refineries appeared to be the "predominant" source of this pollution 1 o until citizen suits
forced clean ups.
11
The Water Board also agreed with refinery management claims that dioxins
do not violate water quality standards in the Bay
1
2 before EPA overruled this claim in 1999.
Today, oil industry and Water Board managers assert the hypothesis that refineries are insignifi-
cant sources of dioxins to S.F. Bay, and claim refineries are dioxin "sinks" that remove more
dioxins from the environment than they release.\3.14 Water Board staff say that a focus on refin-
ery dioxin pollution is "really a distraction and a diversion from solving the problem,"
14
and the
Water Board has increased the amount of dioxins it allows to be released.
1
5
This case study attempts a comprehensive review of existing information on petroleum refin-
ery dioxins pollution in the S.F. Bay Area. It allows the first thorough public review of the
hypothesis that refineries are "insignificant" dioxins sources. It attempts to quantify releases
from refineries themselves. This analysis is specific to the Bay Area, where there are relatively
more refinery dioxins data, but it can be used by communities near refineries everywhere.
3






Approach .
In general, there are four ways to investigate a pollution source: 1) by measuring
how pollution is caused and prevented at the source; 2) by measuring the pollution released
from the source and from other similar sources; 3) by measuring the flow of pollution from the
source into the environment where this pollution accumulates; and 4) by measuring health
effects caused by the pollution source in humans and other organisms. The first three types of
measurements are used here to investigate dioxins released from Bay Area petroleum refineries.
Part I investigates the ways in which dioxins are created and released by refineries, and how
this can be prevented. This pollution prevention engineering analysis is useful in answering the
central question of how to improve health protection. It also tells us whether refinery activities
are sources creating dioxins, or merely pathways carrying them from some other source.
Part 2 investigates measurements of the amounts of dioxins released from all refinery sources.
It builds on the engineering analysis in part 1 and uncovers the amount of dioxins refineries
release to the environment through all pollution pathways, based on a detailed analysis of what
is - and is not - known from existing measurements of each refinery source. This analysis is
useful because despite public debate over the significance of this pollution, there is no govern-
ment estimate today of overall releases of dioxins from all refinery sources.
Part 3 analyzes measurements in the environment to investigate the extent to which environmen-
tal accumulations of dioxins can be traced to refinery sources. It builds on CBE's comprehen-
sive inventory of Bay Area sources of dioxins. When other sources are accounted fm;, one can
get a more complete picture of the pollution gradients stretching from refineries into the envi-
ronment. It analyzes new information on how dioxins might (in some cases) be traced to their
source using the "profile" of the relative amounts of specific dioxin compounds. Information
explored here links releases to environmental exposures, and provides a "check" on the source
measurements of pollution amounts in part 2.
A discussion of findings and recommendations looks at the data as a whole and puts the new
findings in perspective based on what is known now, what we can learn quickly, and what can
be done now to improve environmental health protection from refinery dioxin pollution.
Readers should note that despite important new data, few data exist to describe exactly
"how much" dioxin is released from most sources. This analysis benefits from a comprehensive
assessment of Bay Area data on all dioxins, sources in refineries, and release pathways from
refineries into the environment. Further, it looks at releases of these persistent, trans-generation
taxies from the more relevant perspective of long-term release, allowing more data to be consid-
ered. Nevertheless, poor monitoring has led to many gaps in scientific information. In order to
interpret the incomplete data accurately, this analysis takes the approach of estimating that Bay
Area refineries as a group release more than a minimum amount of dioxin pollution, and less
than a larger maximum amount of this pollution.
These region-wide refining estimates should not be applied to an individual source: this could
overestimate or underestimate the amount of dioxins released, and the measurement accura-
cy, depending upon the source. Data and analysis methods are detailed in parts 1, 2 and 3.
4
Findings.
Multiple sources create oil refineries' releases of dioxins.
Six San Francisco Bay Area oil refineries use many process units that create dioxins.
Reformers, crackers, and oil-fired heaters and boilers that process a total of more than 25 mil-
lion gallons of petrochemicals each day in Bay Area refineries are confirmed sources of dioxins.
This is based on measurements of CDD/Fs in the initial releases from these processes at Bay
Area refineries, and the presence of chlorine inputs and process conditions that create dioxins in
these processes. Measurements of PCBs homologue groups also confirm the creation and
release of newly-formed PCBs in Bay Area refineries' reforming and oil-fired processes.
In addition to these known sources, there is suggestive evidence that flares, cokers, desalters,
distillation towers, and/or uncontrolled fires in refineries create and release dioxins, although no
tests of these suspected sources for dioxins have been reported publicly.
Releases of dioxins from refineries are confirmed by direct measurements of smoke stacks,
waste water discharges, and rain storm runoff discharges at Bay Area refineries and by direct
measurements of newly-refined diesel fuel and motor oil at southern California refineries.
Newly-refined diesel also contains chlorine, which could cause more dioxins to form in vehi-
cles. Although the diesel pollution pathway to the environment is through vehicle exhaust pipes,
it is important to recognize the refinery source because - regardless of how much of the dioxins
emitting from the tailpipe form in the refinery and how much form in the vehicle - getting the
dioxins and the chlorine out at the refinery may be the most practical way to stop this pollution.
Refineries are poorly monitored for releases of dioxins.
Despite relatively better monitoring of dioxins at S.F. Bay Area oil refineries than at refineries
elsewhere, many refinery sources, pollution pathways to the environment, chemicals in the
"dioxins" group, and pollution-causing events have not been measured at Bay Area refineries.
Direct measurements for dioxins are not reported in releases from flares, cokers, desalters, distil-
lation towers, or uncontrolled fires at any Bay Area refinery. None of the major Bay Area
refineries reports measurements of dioxins from every one of the confirmed source types it uses.
No Bay Area refinery reports these measurements for most of its smoke stacks, or for any of the
diesel, motor oil and other products it refines. Despite direct measurements confirming release
of PCB homologue groups that contain dioxin-like PCBs, no Bay Area refinery reports direct
measurements that isolate dioxin-like PCBs from other PCBs it releases. Further, most of the
measurements that have been done were not planned to be sensitive enough to fully quantify
many of the individual CDD/F chemicals above analytical detection limits.
Finally, even monitored releases are measured only a small fraction (one-ten thousandth) of the
time that the releases are occurring, and these tests are announced in advance, raising the possi-
bility that only the low end of the highly variable releases from refineries is measured directly.
Because of this poor monitoring, the true rate of dioxins release from refineries is only known
within a wide range (of minimum to maximum release).
5






Bay Area oil refineries release more than 1.8 billion picograms of dioxins per
day, and up to a maximum of 171 billion picograms of dioxins/day, on average.
This is measured as the toxicity of CDD/Fs and dioxin-like PCBs (TEQDFP-WH0
98
).
The minimum rate of dioxins release (1.8 billion pg/day) is based on direct measurements of
confirmed refinery sources and release pathways, and the minimum plausible amount of
CDD/Fs and dioxin-like PCB compounds that were present but not fully quantified in confirmed
releases due to analytical problems. However, Bay Area refineries actually release an amount as
low as this minimum amount of dioxins only if all the following conditions exist:
- none of the many suspected, but unconfirmed sources in refineries release dioxins;
- dioxins known to be released that are not fully quantified in releases due to analytical prob-
lems are released at only the lowest rate that measurements show is possible;
- on-road diesel is the only refined product causing environmental release of dioxins; and
- releases are not larger during refinery fires or when refiners know "they are not being tested.
While it is possible that all these conditions exist in reality, the detailed analysis in this report
shows that the probability of this is very low.
It is equally possible (and equally unlikely) that all of the opposite conditions exist: one or
more suspected refinery sources release dioxins; dioxins present but not fully quantified in
releases are released at only the highest rate existing measurements indicate is possible; other
refined products release dioxins; and releases are much larger when refineries are not tested. If
all these conditions exist, refineries could release up to a maximum of 171 billion pg/day of
dioxins TEQ.
Of course, the most likely situation is that some of these conditions exist (for example, an
unconfirmed source releases dioxins), and some other conditions exist in between the minimum
and maximum possible extremes (for example, dioxins below detection are released at rates
between the lowest and highest possible rates defined by analytical detection limits).
Thus, Bay Area oil refineries release more than 1.8 billion pg/day and less than 171 billion
pg/day of dioxins TEQ, and their true release rate is likely to be closer to the middle than the
extremes of this 1.8 - 171 billion pg/day range.
Environmental measurements support the finding that Bay Area refineries
release more than 1.8 billion picograms per day of dioxins toxicity.
Average concentrations of dioxins (TEQDFP-WH0
98
) in San Francisco Bay fish are 30 to 250
times larger than those in fish from a comparable location in northern California that should
receive similar amounts of dioxins from distant sources. The greater fish contamination in the
Bay Area suggests that there are important Bay Area sources of dioxins.
The average concentration of CDD/Fs (TEQ
0
F-WH0
98
) in aquatic sediment of a Bay Area
refinery discharge canal is 20 to 140 times larger than the concentrations of TEQDFP-WH0
98
in
the northern reach of the S.F. Bay/Delta and two of its tributary rivers, and 600 times larger than
the concentrations of TEQ
0
F-WH0
98
in sediment of two of its other tributary rivers. The rela-
tive levels of different individual CDD/F chemicals in the refinery's canal sediment and one of
its process releases (the "profiles" of dioxins within each homologue group) are similar, support-
ing the conclusion that refinery caused the accumulation of dioxins in its discharge canal.
6
Maximum concentrations of CDD/Fs (TEQ
0
F-WH0
94
) in changing rain storm runoff are up to
70 times greater at refineries than at sites 15 to 25 kilometers from refineries and other industrial
sources of dioxins, and these maximum levels taper off for at least six miles from the sources.
Further, particulate pollution follows this same pollution gradient from refineries: This is impor-
tant because dioxins often attach to particulate pollutants from refineries and other sources, and
this enhances their fallout near sources and their movement into this storm water runoff.
Finally, a disproportionate number of runoff tests at refineries have high dioxins levels that can-
not be explained by the suspended solids levels in the runoff: This provides another indication
that refinery sources are contributing to the dioxins gradient observed in the runoff.
All these measurements indicate a gradient of pollution with higher levels of dioxins near
refineries and other industrial sources, and gradually decreasing levels as the pollution disperses
far into the Bay Area environment. These measurements show that oil refineries contribute
important amounts of the dioxins found in the Bay Area environment.
The pollution gradient in runoff is also of interest with respect to another type of dioxins release.
According to the Bay Area Air Quality Management District, residential wood burning releases
as much dioxins as any Bay Area source: an estimated 2.2 billion pg/day of TEQ
0
F-WH0
94
.1
4
However, the levels of dioxins at runoff sites near residential wood burning but far from indus-
trial sources are among the lowest found in the Bay Area, and these sites are at the low end of
the pollution gradient, while refineries are at the high end of the pollution gradient. This indi-
cates that refinery releases could not be significantly smaller than residential wood burning
releases (2.2 billion pg/day), and it suggests that refinery releases are larger.
The comparison in Figure ES-1 shows that the minimum refinery release discussed above is at
least 30 times the amount of dioxins from other sources that is estimated to fall out to a land
area of the size used by Bay Area refineries. This is consistent with the much greater dioxins
levels in sediment and runoff at refineries than those at sites far from industrial sources.
Environmental measurements support the source measurements that indicate Bay Area refineries
release more than 1.8 billion pg/day of dioxins TEQ. Indeed, if refinery releases were much
smaller than those from residential fireplaces (estimated at 2.2 billion pg/day) and much less
than 30 times fallout from other sources, the 20-600 times greater concentrations of dioxins
TEQ found at refineries than at other Bay Area sites would be very difficult to explain.
Oil refineries can prevent dioxin pollution now.
Chlorinated dioxins cannot be created without chlorine. Refiners can block the chemical reac-
tions that create dioxins by removing chlorine from their processes. They can also trace the
chlorine entering their processes to its sources and prevent chlorine from entering the processes.
One small refiner in the South Bay community of Newark has committed to do this - and thus
virtually eliminate dioxins from a process heater- within two years. Dioxins have no industrial
use, and chlorine has no use in cracking or heater or boiler processes. Thus, dioxins can be
eliminated in these refinery processes immediately.
Refiners do use chlorine to regenerate reforming catalyst; but even here, the creation of dioxins
can be eliminated by a concerted effort to find and install methods that protect, clean and repair
this catalyst without burning chlorine. Thus, at every process that is a known source of dioxins
and in every Bay Area oil refinery, steps can be taken today to eliminate the creation of dioxins.
7






Discussion .
This report shows that preventable sources in Bay
Area oil refineries release at least as much dioxins
as the biggest pollution sources cited by regional
government officials, and contribute significantly to
health threats affecting subsistence anglers.
It also highlights a health concern for the general
food supply, when one begins to consider the toxi-
cological significance of more than 1.8 billion
pg/day of dioxins toxicity release from Bay Area
refineries, and where some of it may be going. One
picogram of dioxin exposure per day can cause a
person to exceed the lowest lifetime cancer risk
threshold considered "acceptable" by public health
officials. Most dioxins released will end up in soil
and sediment rather than in our food, but prevailing
winds from the Pacific Ocean could carry signifi-
cant amounts of dioxins emitted by Bay Area
refineries to parts of California that EPA says are
among the major U.S. food producing regions.
4
This pollution should be prevented starting now .
This analysis suggests refineries release amounts of
dioxins significantly within the extremes of the 1.8-
171 billion pg/day range shown in Figure ES-1.
Nevertheless, given the size and scope of this indus-
try, its release rate needs to be known better. If the
industry's releases nationwide approach the median
of this range, refineries may cause more release of
dioxins than all but one source estimated by EPA.
4
One might speculate that releases approach the geo-
metric mean of this range (and refineries are the sixth
largest source) but in any case, such speculation real-
ly only highlights a need to monitor refineries.
A program to organize monitoring of dioxins in the
confirmed and suspected refinery sources and
release pathways is needed now. This should be
done before Toxics Release Inventory reports on
dioxins8 are released nationwide next year.
Figure ES-1 shows that even the minimum amount
of dioxins released by Bay Area oil refineries is
165 times greater than that estimated by the San
Francisco Bay Regional Water Quality Control
Board, and 13 times greater than that estimated by
8
Figure ES-1. Lower and upper bounds of
dioxins release from Bay Area oil refineries
(pg/day other estimates,
and fallout on refineries from other sources.
171
billion
pglday
or less

(Scale compressed)
tt
1.82
billion
pglday
or more
Key
II
D
D

t
Lower bound of amount
Upper bound of amount
Estimates by others
Arrows point to
increasing likelihood
of true release rate
Bay Area Refineries Refineries Fallout on
refineriesa (Bay Area (Water Bay Area
AQMD)b Board)C refineriesd
NOTES: aThis analysis. bBAAQMD refinery (refonning)
estimate from reference 34. CRWQCB refinery (effluent)
estimate from reference 53. dEstimated from national data
in reference 4. refinery acreage, and methods in part 3.
the Bay Area Air Quality Management District. The maximum possible release found by this
analysis exceeds these regional health officials' estimates of refinery release rates by
1,200-15,000 times. The Water Board's estimate that Bay Area refineries release an amount of
dioxins equal to 11 million pg/day is documented in its February 1998 staff report entitled
Dioxins in the Bay Environment, and in its May 25, 1999 and June 21, 2000 staff reports regard-
ing the Tosco Avon Refinery.t3,14,53 The Air District's estimate that these refineries release an
amount of dioxins equal to 137 million pg/day is documented in its March 27, 1996 staff report
entitled Air emissions of dioxins in the Bay Area environment.3
4
However, these Water Board and Air District analyses exclude many considerations that prove
important based on the evidence in this report:
- The Air District estimate does not report any amount of release from known refinery sources
in cracking and oil-fired processes, or from suspected sources in flares, cokers, distillation
units, desalters or fires. The Water Board analyses rely on this Air District estimate.
- The Water Board and Air District estimates do not report any amount of refinery release via
storm water runoff, refinery products, or fugitive emissions from fires.
- The Water Board and Air District estimates do not report dioxin-like PCBs releases.
- The Water Board estimate does not report any release of CDD/Fs known to be created and
released by refineries when the chemicals are below detection limits due to poor monitoring.
- Refinery releases of dioxins are tested only a small fraction (one-ten thousandth) of the time,
release rates can change by hundreds of times, and advance warning of tests may result in
sampling when releases are low. However, the Air District and Water Board estimates
assume refineries never release more dioxins when they are not looking (testing the releases).
The cumulative error caused by excluding many refinery sources, release pathways, dioxins, and
measurements of greater release explains how the Water Board and Air District have drastically
underestimated oil refinery releases of dioxins.
Amounts of dioxins in the environment near Bay Area refineries provide a second important
measurement of this pollution, confirming the refinery release rate from source measurements.
The analysis in this report finds links between refineries and pollution in fish, sediment, and
runoff, that were missed by public health officials' earlier assessments.
In fish, a 30-250 times greater concentration of dioxins is linked to Bay Area sources by consid-
ering a key site-specific factor, and comparing Bay Area fish with other fish near the Pacific
Ocean. These fish are more comparable due to the lower rate of dioxins fallout near the Pacific.
In contrast, the Water Board's February 1998 staff report
5
3 does not account for this ocean influ-
ence, compares S.F. Bay fish with fish from U.S. waters far from the Pacific that receive fallout
from many land-based sources to windward, and fails to find the clear difference revealed here.
In sediment, a 20-600 times greater concentration of dioxins is linked to refinery sources by
considering environmental processes that affect dioxins. Dioxins build up in sediment near
sources for a long time, and move back into the water only slowly. The report accounts for this,
comparing dioxins in sediment with long-term releases. In contrast, in its June 21, 2000 and June
16, 1999 staff presentation reports 14 the Water Board agrees that the dioxins buildup in sediment
could cause discharges from a refinery canal for years, then contradicts itself by claiming that dis-
charge from the refinery's canal during a five-month plant shutdown was from another source.
9






Environmental processes also shift the mix
(the "profile") of dioxins so that sediment has
higher levels of dioxins with more chlorine
atoms, and lower levels of dioxins with less
chlorines, as compared to sources. The report
accounts for this factor, and finds that the
"profile" of dioxins in sediment of the refin-
ery discharge canal is (not surprisingly) simi-
lar to that of the refinery source. In contrast,
the Water Board's May 25, 1999 staff reportl3
does not account for this factor, and fails to
notice this similarity in the profiles.
In storm runoff, dioxins, particulate pollution
associated with dioxins, and changes in the
ratio of dioxins to particulates are each linked
to refinery sources when one accounts for all
the nearby industrial sources of this pollution.
Figure ES-2 shows the location of sources,
illustrating how runoff far from refineries
might be near other sources of dioxins.
Figure ES-3 shows that when the distance
from all these sources is accounted for,
refineries (gray bars) are shown to influence
all three pollution-related factors. As shown
in the Figure, this analysis reveals pollution
gradients starting from maximum dioxins and
suspended solids levels at refineries, and
instances of high dioxins at refineries even
when suspended solids levels are moderate.
Thus, refineries influence a pollution gradient
with 70 times greater maximum runoff levels
that taper off for miles into the environment.
In contrast, the Water Board's June 21, 2000
staff reportl3 compares runoff between only
two types of sites: refineries and all others
(even if other sources are nearby). This does
not account for the effects of other industrial
sources. Thus, the Water Board has missed
refinery effects on this pollution gradient.
Most important, this report reveals immediate
steps that can eliminate creation of dioxins in
refineries by blocking chlorine inputs. This
will stop this pollution via all routes - includ-
ing stack and tailpipe discharge to the Bay.
Therefore, it is within the Water Board's man-
date to address all discharges to water.
Figure ES-2. Oil refineries and other industrial
dioxin sources identified in the S.F. Bay Area.
Source key:
oil refineries

incinerators
0
scrap
furnaces

chemical
drum
furnaces
0
foundries
0
other
industries

NOTES: Data from references 2 and 47.
0
Figure ES-3. Dioxins and suspended solids in Bay Area
runoff v. distance from industrial sources.
7o
~
so
40
Jo
20
IO
- Runoff sample at refineries
I Runoff sample at
other sites
7o
~ ~
~
so!-'
...:.
4 ~
-5
Jo]
...
.!!
20-11
"' .s
Io ~
Q
NOTES: 47 s:unples with CDD/F and solids doUI; from references 2. 47. 97 ond 98.
10
RECOMMENDATIONS:
1. The San Francisco Bay Regional Water Quality Control Board, State Water Resources
Control Board and U.S. Environmental Protection Agency should reverse their deci-
sions to allow ongoing dioxin pollution by Bay Area oil refineries. The agencies should:
Reverse the June 21, 2000 decision to weaken the effluent limit on dioxins discharge by
the Tosco Avon Refinery. The Regional Board based this decision on its drastic under-
estimate of refinery dioxin pollution, but it did not raise this reason in its proposal until
after its comment deadline, and it did not accept written comments thereafter.
Revise the permit allowing dioxins discharge by the Chevron Richmond Refinery to S.F.
Bay, which expired by its own terms in 1997, to require dioxins elimination.
Conduct a basin planning process with formal public debate on how Federal require-
ments for total maximum "loads" of all dioxins release to S.F. Bay can best meet the
existing State policy goal to eliminate dioxins discharge to the Bay by the year 2000.
2. The Regional Board, State Board and EPA should require pollution prevention audits
of all root sources creating dioxins at the Chevron, Tosco, Equilon (formerly Shell), and
Valero (formerly Exxon) refineries in the Bay Area, and fund experts hired and directed
by the community and workers to ensure independently verifiable results. Within two
years audits should identify, test and effect options that:



Protect reforming catalyst or repair and clean it without incinerating chlorine .
Identify, trace and prevent chlorine inputs to cracking processes .
Identify, trace and prevent chlorine inputs to oil/waste-fired process heaters/boilers.
Identify, trace and prevent or remove chlorine inputs to other refinery processes .
3. The Regional and State water boards, State Air Resources Board and EPA should
design a monitoring program that is capable of confirming oil refinery dioxins release
rates within 25% of the true rates, and implement this program so that dioxins reports
to the Toxics Release Inventory, which are required for the first time in 2001, will pro-
vide useful information. This program should include:




Identification, direct measurement, and ongoing monitoring of all sources of dioxins .
Monitoring of all dioxins (CDD/Fs and PCBs) and all release pathways from refineries .
Adequate sensitivity (design for quantitation) and greatly increased sample frequency .
Comprehensive measurement of dioxins release during and after upsets and fires .
4. To improve health protection against refinery dioxin pollution, the public needs to take
action. Community members joining with CBE can demand actions by our public offi-
cials and engage refinery managers who still refuse to cooperate in open investigations
of ways to eliminate dioxins at the source. Elected officials should organize and con-
duct hearings to investigate the ongoing problems in public health officials' responses to
oil refinery dioxin pollution, and hold the Water Board, Air District and EPA account-
able for actions to prevent this pollution and protect our health.
11






Part 1. Multiple sources of preventable dioxin pollution in oil refineries .
From years of direct measurements in laboratories, industrial processes and the environment it is
now known that the primary cause of dioxins pollution involves the introduction of chlorine into
various high-energy (usually high-heat) industrial processes. Sources of chlorine in the high-
heat processes of petroleum refineries cause some of this dioxin pollution.
U.S. refineries process approximately 5.5 billion barrels- 700 million metric tons assuming 45
API crude - of crude petroleum annually. This production rate far exceeds that of any other
industry believed to cause major dioxins releases.
2
-
17
.18 One of the three largest oil refining cen-
ters on the U.S. west coast surrounds San Francisco Bay and refines nearly 300 million barrels
per year.I7.I9 Major refineries are run by San Francisco-based Chevron Corp. in the community
of Richmond, Tosco (in Avon and Rodeo), Equilon (Martinez), and Valero (Benicia). A sixth
plant run by Evergreen Oil, Inc. in Newark (near Hayward) is classified as a "lube" refinery.
Generally, refiners remove unwanted chemicals, distill the crude, "crack" the distillate into
smaller fuel-size molecules, "reform" the shapes of these molecules to boost octane, and sell the
fuels, lubricants, and side products such as petroleum coke that result. These steps are done by
applying massive amounts of energy in dozens of different hot process units (distillation towers.
catalytic crackers, reformers, etc.). Part of the output stream from many process units is fed
back into other processes. This is why refineries look like a maze of interconnected pipes- and
why putting chlorine into one refining process can lead to dioxins formation in other processes.
CONFIRMED SOURCES:
Catalytic reforming boosts fuel octane by reshaping
petrochemical molecules. Six reformers process
170,000 barrels/day at the Chevron, Tosco, Equilon
(formerly Shell) and Valero (formerly Exxon) plants.
The reforming reaction is aided by a catalyst that con-
tains platinum and/or rhenium. The catalyst becomes
less effective with carbon deposits and wear. The
refiner cleans the catalyst in a "regeneration" process
that involves incinerating the carbon deposits.
The chlorine source for dioxins formation in this
process is the addition of chlorine to aid during clean-
ing and reactivation of the catalyst. When dioxins
were discovered in refinery sludge in 1988, this was
the first refinery process tested for dioxins.?
Tests of waste water directly exiting reformer catalyst
regenerators find high concentrations of 17 CDD/Fs
from reformers at the Chevron, Tosco (Avon and
Rodeo) and Valero refineries.
2
0.2I Three days of stack
tests at the Tosco Avon No.3 Reformer measured
high levels of CDD/Fs and high levels of newly-
formed PCBs.
22
(See tables 1 and 2.)
12
I. Reformer stack tests (Tosco Avon Refinery)
picogrnmslharrcl reformed Day I Day 2 Dayj
2,3,7, K-TCDD 7 12 22
1,2,3,7.K-PcCDD <)(, 202 -'j2
1.2.3.4,7 .K-HxCDD <JS 245 5+1
1.2,3.6,7.8-HxCDD 251 521 1377
1.2.3.7,K,<J-HxCDD 161 322 9.!X
1.2.3.4.6.7.K-HpCDD 702 1563 5391
OCDD 471 974 2895
2.3,7,K-TCDF 266 -143 ~ 7
1.2.3.7.K-PcCDF 525 1010 2822
2,3.4.7 ,8-PcCDF 62 1 12Stl .t0 54
1.2.3,4,7,K-HxCDF IIX)I 2573 8 ~ 1
1.2.3,6.7.8-HxCDF 76 1 1 ~ 3 1 63K7
2.3,4,6,7.K-HxCDF 616 136ll ssa9
1.2,3,7.8.9-HxCDF IlK 245 738
1.1.3.4.6,7,8-HpCDF !W4 ~ 0 1 8 29.l.IS
1.1.3.4,7,8,<J-HpCOF 342 M3 !SOS
OCDF 929 2229 6387
Mnnochloro-PCBs 2636 2867 4163
Dichlorn-PCBs (m5 675(1 7837
Trichlorn-PCBs 120.5(1 139.52 17 123
Tetra-CBs 11 .552 15130 !!514
Pc-CBs IIS.S2 17123 2.10)\l
Hx-CBs 101'!3 1513() 1'.157(1
Hp-CBs 16(,7() :6274 .l81i86
Ocla-CBs li\131 115.52 21563
Nonachlom-CBs 1.572 2K61 SSS9
Dccachloro-CBs 2777 S\IS IS IS
NOTES: Data from reference 22.
The mechanism that creates dioxins starts when chlo-
rine is added. Some of the chlorine reacts with the
hot carbon atoms and compounds in the reaction
chamber and its exhaust piping to form dioxins.
Dioxin formation is catalyzed by combustion-induced
changes in oxygen chemistry, by metals, and by the
ash/soot/carbon buildup (which on a micro-scale has
a high surface area that aids the reactions). Carbon
skeletons of the CDD, CDF and PCB molecules form
by slightly differing trace chemistries, and chlorine
atoms attach to these molecules. These side-reactions
take seconds in the primary reactor and the down-
stream sections of the process_2,7,23-30
In other words, the chemistry that governs the kinds
and amounts of dioxins formed is dynamic and com-
plex, but it is clear that because chlorine is put into
this process that burns waste carbon off metal cata-
lyst, dioxins form in the process and emit into the
environment. These chlorinated dioxins cannot form,
however, if the chlorine source to these reactions is
blocked.
Immediate next steps toward zero dioxin: Dioxins
have no useful purpose in refining. Since a primary
chlorine source causing dioxins creation in reformers
is already identified, an immediate next step
involves blocking the chlorine source to the chemi-
cal side-reaction that creates dioxins. Options to
protect reforming catalyst, or repair and clean it
without putting chlorine into an incineration process,
can be tested for their effectiveness starting today.
Steps toward zero dioxin in refinery reformers are
summarized in Figure 1.
2. Reformer water tests (3 Bay Area refineries)
picogramslliler
Chevron Tosco Tosco
Richmond A\on Rodeo
2,3,7,8-TCDD 170 BD 22
1,2,3,7,8-PeCDD 730 BD 85
1.2,3,4,7,8-HxCDD 740 8700 90
1,1,3,6,7,8-HxCDD 910 15700 90
I .2.3.7 ,8,9-HxCDD 440 16900 190
1,2,3,4,6,7 ,8-HpCOD 2640 55900 890
OCDD 11 70 63400 1400
2,3,7,8-TCDF 3350 5300 150
1,2,3.7,8-PeCDF 9150 -14000 120
2,3,4,7,8-PeCDF 4600 111 500 180
1,2,3,4,7,8-HxCDF 14700 128500 340
I ,2,3,6, 7 .8-HxCDF 5800 131000 240
2,3,4,6, 7 ,8-HxCDF 1320 2.5000 190
1,2,3,7,8,9-HxCDF 1700 177000 230
1,2,3,4,6,7,8-HpCDF 17100 599000 970
1.2,3.4.7,8,9-HpCDF 7500 566000 520
OCDF 10250 279500 1900
NOTES: Average BD=below detecuon
limit. Data from reference 20.
I. Reforming Unit Pollution Prevention.
Spent Reformer Catalyst
_t_
Remove carbon buildup &
regenerate metal catalyst
without forming dioxin
"'
'
Process gases for recovery I
disposal without liquid (dry
"
process)
NOTES: Figure from reference 2.
#1: How to regener-
ate catalyst without
chlorinated solvents?
#2: How to confirm
dioxin elimination &
safety of new option?
Catalytic cracking breaks large petroleum molecules into smaller, fuel-sized molecules in
order to make more gasoline, diesel and jet fuel out of each barrel of cnide oil. Including cat-
alytic hydrocracking, at least seven crackers process more than 500,000 barrels/day at the
Chevron, Tosco, Equilon, and Valero refineries.l7-J9 This process uses a silica-alumina catalyst
that is cleaned of carbon deposits by incineration in cracking catalyst regenerators.
In the first dioxins tests of this process ever reported, dioxins were detected in three tests of
stack exhaust from the Chevron Richmond Refinery catalyst regenerator.
2
3
2
See Table 3.
Measurements confirm chlorine in partially refined materials fed into cracking processes.
2

31
Incinerating cracking catalyst with this chlorine creates dioxins in side-reactions that are cat-
alyzed by high surface area and metals of the silica-alumina catalyst, the carbon deposited on
(and burned from) the catalyst and the process unit interior structures_2.23-30.3
3
13






Immediate next steps toward zero dioxin: The dioxin-
forming reactions in this process can be blocked by get-
ting the chlorine out of the cracker feed stream. Chlorine
can be removed from oil before processing (see oil-fired
heaters below). Since methods to measure chlorine in oil
are readily available,
31
testing in refineries can trace
cracker chlorine inputs to their sources and prevent chlo-
rine inputs to all refining processes. (See Figure 2.)
2. Cracking Unit Pollution Prevention.
Spent Crucker C;ualyst
'
Remove carbon buildup
from silica-alumina catalyst
without forming dioxin
1'-
y
Block the chlorine source to
the dioxin-forming reaction
in the process
NOTES: Figure from reference 2.
#1: Chlorine soun:es
can be traced by in-
plant testing.
#2: Chlorine can be
removed from inputs,
before dioxins fonn.
Oil- and waste-fired process heaters and boilers
provide some of the enormous amount of heat used in oil
refining, and can also reduce the amount of "leftover"
material that refiners must pay to dispose of as liquid or
solid wastes. Generally, all refineries bum some of the
fuels they are refining, ranging from No. 2 fuel oil
(diesel) to tank-bottom sludge. A cumulative total of
more than 2.6 million barrels/day of crude and partially
refined oil is put through heated distillation, cracking,
coking, reforming, hydrotreating and other processes in
the Bay Area.
17
A conservative estimate (that only 1.5-
6% of this cumulative throughput is burned with natural
gas and other energy to heat the rest) puts oil burning by
Bay Area refineries at 40,000-160,000 barrels/day.
The chlorine source for dioxins formation in this process
is the same as that for catalytic cracking, except that
some refinery residuals contain relatively high chlorine
content due to process chemistry or contamination.31,35
Oil-fired boilers and heaters are known dioxins sources
from testing elsewhere.
2
Table 4 shows results from
three tests that found dioxins and PCBs in stack exhaust
from an oil-fired process heater at the Evergreen Oil. Inc.
used oil refinery in Newark.
3
6 An old stack test at the
Shell (Martinez) CO boilers failed to detect dioxins
(though the Air District presumed it is a source).3
4
14
3 Cracker stack tests (Chevron Refinery)
picogrnms per second Test I Test 2 Tcst3
2.3,7,8-TCOO 80!110) 80( 130) 80(96)
I ,2,3,7.8-0eCDO 80{110) 80(801 80(42)
1,2.3.4.7,8-HxCOO 8[)(130) 80(95) 80(81)
1,2,3 ,6,7 ,8-HxCOD 80(120) 80(98) 80(76)
1.2.3.7.8,9-HxCDD 80(110) 80<88) 80(72)
1.2.3,4,6,7,8-HpCDD 190 80(57) 80(140)
OCOD 2200 530 1300
2,3,7,8-TCOF 80(12) 80(82) 80(86)
1.2.3,7,8-PeCDF 8[)(85) 80(61) 80(68)
2.3,4,7,8-PeCDF 80(75) 80(55) 80(64)
I ,2,3,4,7 ,8-HxCDF 80(89) 80(39) 80(54)
1.2.3,6,7,8-HxCOF 80(75) 80(33) 80(42)
2.3.4.6.7.8-HxCOF 80(92) 80(41) 80(51)
1.2.3,7.8,9-HxCOF 80(100) 8'0 (45) 80(60)
1.2.3,4,6,7,8-HpCOF 80(75) 80(45) 80(51)
1.2.3.4,7,8,9-HpCOF 80(75) 80(65) 80(81)
OCOF 430 80(29) 80(2HO}
:-IOTES: 80=below detectton hnut (detecuon hnut). PC8s
results (80) not shown. Data from reference 32.
4. Oil-fired heater stack tests (Evergreen Oil)
picograms/test Test I Test2 Test3
2.3,7.8-TCOO 14.0 11.0 13.0
1.2.3,7.8-PeCOO 80(3.6) 3.7 80(3.6)
1,2.3.4.7,8-HxCOO 12.0 12.0 12.0
1.2.3.6,7.8-HxCOO B0(2.S) 3.1 80(2.9)
1.2.3.7.8.9-HxCOO 80(7. 1) 4.1 8'0(3.6)
1.2.3,4,6. 7 .8-HpCOO 7. 1 13.0 6.8
OCOO 13.0 20.0 14.0
2.3,7,8-TCOF 40.0 24.0 29.0
1,2.3,7,8-PeCOF 80(1 7) 60( 15) 8 0 (1 4)
2.3,4.7,8-PeCDF 9.6 11.0 9.1
1.2,3.4, 7.8-HxCOF 8.6 12.0 8.4
1,2,3,6, 7,8-HxCDF 4.8 6.2 4.4
2.3.4.6.7,8-HxCOF 80(4.1) 4.6 80{4.21
1,2,3.7.8,9-HxCOF 16.0 14.0 13.0
1,2,3.4.6.7 ,8-HpCDF 80(61 80(11) 80(7.11
1.2.3.4. 7,8,9-HpCOF BO(S.Ol 80(5.3) 80(5.0)
OCOF 7.8 8.1 8.4
Monoch1oro-PC8s (2. 1000) (9000) (31000)
Oichloro-PCBs (35000) (20000) (24000)
Trichloro-PCBs (460001 (23000) l50000)
Tetra-CBs (150001 030001 ( Hi0001
Pe-CBs (17000) (380001 (180001
Hx-CBs ( 190001 150000 (200001
HJ>-CBs ( 190001 110000 (20000)
Octa-CBs (48000) (260001 (24000)
Nonachlor<rCBs (3 1000) (270001 !31000)
Decach1or<rCBs 4 ~ 0 0 0 ) (370001 (43000)
NOTES: BD=below sample-specific detection limit
(detection limit for test). Data from reference 36.
The mechanism of dioxin formation in oil-fired boilers and process heaters is generally similar
to that in other combustion or incineration sources, as described above.
2

23
-
30
However, the rela-
tive amounts of CDDs, CDFs and PCBs produced may differ from these other sources due to
differences in the material burned, the substances that catalyze dioxins formation, and combus-
tion conditions. The mix of dioxins produced by oil/waste-fired boilers tested elsewhere differs
from the mix of dioxins produced by incinerators.
4
Immediate next steps toward zero dioxin:
Dioxins formation in this process can be
blocked by getting the chlorine out of the mate-
rial burned. In fact, the steps to virtually elimi-
nate dioxins from this process source are start-
ing now at one Bay Area refinery. In a March,
2000 settlement agreement with CBE, the
Evergreen Oil Inc. refinery committed to
remove at least 99% of chlorine from the feed
burned in its process heater within two years.
Evergreen will measure the effect of its process
change and the data will be independently veri-
fiable. In the event that the process change is
not effective, Evergreen will use a different
energy source for heat.37 See Figure 3.
3. Oil-fired Heater/boiler Pollution Prevention.
Material burned to heat process
t
Block the chlorine source to
the dioxin-forming reaction
in the process
..
Verify the effectiveness of
process/production system
change with direct testing
f'.
#1: Get chlorine out
of oil through pre-
vention or removal.
#2: Use other zero-
chlorine energy
source to heat the
process if necessary.
Contamination of diesel fuel in refineries is a contributing source to dioxins release from
motor vehicles and a pathway by which dioxins created in refineries enter the environment. On
average, from December 1999 through June 2000 California refineries processed 1,680,000 bar-
rels/day of crude and, in addition to other products, produced 290,000 bbl/day of distillates, of
which 170,000 bbl/day was diesel for on-road use. IS Bay Area refineries process an average of
779,400 bbl/day of crude.I7,19 Thus, based on proportionate production Bay Area refineries pro-
duce an estimated 80,000 bbl/day of on-road diesel and 136,000 bbl/day of total distillates.
Tests of diesel taken directly from southern California refineries found CDD/F TEQ in on-road
and off-road diesel at concentrations ranging from 0.07 to 300 picograms per liter (detection
limit problems contribute to the range).38 These diesel fuels were sampled before use in any
vehicle: thus; dioxins measured in the fuel were not created by combustion in vehicles. Instead,
diesel and the partially refined oil it is made from accumulate some of the dioxins formed in
refining processes that produce it. Indeed, this accumulation is expected, because dioxins have
high affinity for lipids (fats and oils) and extremely low volatility and solubility in water.
The known sources of chlorine for the dioxins found in diesel are described for reforming,
cracking and oil-fired processes above. In addition, diesel as it leaves the refinery contains
chlorine and other dioxin precursors from refinery processes.31.3
8
Dioxin releases are measured
from diesel vehicles.2.3
4
.38,39.40.41 Dioxins formation in the vehicle is widely suspected, but it is
also possible that dioxins "present in the fuel may be detected in the exhaust because some of
the fuel is not burned during combustion."38 In either case, refinery sources of dioxins, chlo-
rine and dioxins precursors are preventable sources of dioxins released from vehicle tailpipes.
Contamination of motor oil in refineries is shown by a test of new oil that found one dioxin
compound at 2000 picograms per liter, 38 and occurs by similar mechanisms as those for diesel.
15






SUSPECTED SOURCES:
Flares, coking, desalting, distillation and other processes that were not tested for dioxins
run a total throughput of 1.9 million barrels of crude and partially refined petroleum in the Bay
Area daily. These processes appear to create conditions that favor dioxin formation: chlorine
inputs (in partially refined materials as shown for cracking and oil-fired processes above); car-
bon precursors in the feed; soot or ash that catalyzes formation; and combustion or high heat.
Tests that detected dibenzofuran as a combustion product of oil-field flaring strongly suggest
that CDFs can be created from refinery flares.
4
2 Findings that reformer materials containing
chlorine may enter cokers,
4
and that dioxins are present in a Bay Area refinery's coke pile
4
3 fur-
ther suggest that coking may form and emit dioxins. The desalting process uses technology sim-
ilar to that used in chlorine production from brine, which is a known dioxins source.
2
Finally,
distillation subjects large quantities of material to temperatures that favor dioxins formation:
incomplete desalting might introduce chlorine to crude distillation; and other distillation
processes are susceptible to the same chlorine sources that affect the cracking and oil-fired
process sources discussed above.
Catalytic cracking catalyst regeneration was an undiscovered dioxins source until this source
was tested for the first time - as recently as 1997 - at the Chevron Richmond Refinery. Taken
together, the evidence strongly suggests that additional dioxins sources may exist in refineries.
This likelihood can be confirmed or ruled out only by further investigation.
Contamination of petroleum coke and other products with dioxins has not been confirmed
by testing of these refined materials, yet this contamination is likely. Dioxins are found in the
refined products that have been tested,38 and in runoff from a refinery coke pile.
43
The combus-
tion of petroleum coke after it leaves the refinery (in Bay Area power plants, metal foundries
and smelters, and a cement kiln) is associated with dioxins release.
2
3
4
The extremely low
volatility and water solubility of dioxins can result in their accumulation in coke and ash just as
they accumulate in diesel and motor oil. Ash from other combustion sources is known to con-
tain dioxins,
44
and refinery furnace ash may be used in clinker by cement kilns - which release
dioxins. Dioxins are probably released from refineries in petroleum coke and furnace ash .
. Process upsets and uncontrolled fires that result from such upsets have obvious potential to
generate dioxins from the chlorine and petrochemicals that are present with metals and other
dioxin formation catalysts throughout refineries. Dioxins formation is confirmed in combustion
of oil (see above), and during fires in buildings.2.4.3
4
At least 19 major incidents involving
uncontrolled fires occurred in Contra Costa County oil refineries between March 1989 and April
1997.
45
.46 In 1999 major fires killed workers at the Avon plant and damaged the Chevron refin-
ery's cracker. Yet despite the clear potential for dioxins creation in some of these major events,
no properly designed testing of Bay Area refinery fires for dioxins has been conducted.
Contaminated solid waste disposal almost certainly transports dioxins from refineries, how-
ever, EPA has excluded disposal of dioxins in landfills from its estimate of release to the envi-
ronment.4 EPA's approach is open to criticism because landfills sometimes leak, and as EPA
admits, dioxins emit from landfills to the air.
4
.34 While supporting this valid criticism, this
analysis uses a release estimate that excludes landfill releases in order to avoid the potential for
inaccuracies as communities compare the results reported here with EPA's estimates.
16
Part 2. Measurement of the dioxins release rate from refinery sources.
RELEASE MEASUREMENT DATA QUALITY:
Error and bias related to choice of analytical
methods: The quality of dioxins data is often limited
by two analytical choices: one about the volume of
sample collected; and one about the dioxins to analyze.
Some effects of small sample volume are shown in
Table 5. For example, Bay Area refinery effluent tests
that collected one liter samples failed to detect TCDD
at levels below about one picogram per liter, but tests
elsewhere that collected more than 1,000 liters of water
per sample measured TCDD at concentrations more
than a thousand times smaller. The smaller sample
volumes collected in these refinery tests did not allow
for concentrating enough dioxins for the lab instrument
to detect and quantify.51,52 In air samples, tests at a
Bay Area refinery failed to detect TCDD below about
one pg per cubic meter of emission, but tests that col-
lected more air detected 50 times smaller levels.
Figure 4 shows the potential for error caused by the
choice of small sample volume. In a typical test of a
refinery's final effluent discharge to San Francisco
Bay, the amount of CDD/Fs toxicity that could be pre-
sent at the detection limits of the analysis is 50 times
the amount detected by this analysis. In stack tests of
a Bay Area refinery cracker, the amount of TEQ that
could be present at the detection limits of the analysis
is 370 times the amount detected. In diesel as it leaves
refineries (before use as a fuel), the amount of TEQ
that could be present at the detection limits of the
analysis is 900 times the amount detected.
When a chemical is measured below the detection limit
of the sample-specific analysis, this test really only
measured this chemical at a concentration between
zero and the sample-specific detection limit. The exact
level is not measured. Assuming the true level is zero
could underestimate this release, but assuming it equals
the detection limit could overestimate this release.
Unless other data suggest that releases approximate
half the detection limit, this analysis reports the
amounts of undetected dioxins in the test as the labora-
tory reports them: at a level between zero and the sam-
ple-specific detection limit of the analysis.
17
5. Effect of sample volume collected on sensitivity
of the analysis: examples for 2,3,7,8-TCDD.
Sample Amount Detection
volume detected limit
WATER TESTS Li ters pg!L pg!L
Tosco effluent l - 1.3
Baltic Sea 1.500-2.200 0.00025 o.ooos
AIR TESTS Cubic m t ~ r s pgfm3 pgtm3
Chevron stack 112-162 - 1.16
So. Cal. ambient 350-540 0.021 0.022
NOTES: average of sample-specific results; average
detection limits exceed amounts detected due to higher
detection limits for some samples. m3=cubic meter.
pg=picogram. L=liter. Data from references 32.48.49.50
4. Effect of sample v9lume collected on the
possible dioxins release that is not measured:
examples from measurements of refineries.
TEQ
detected
0.13 pg!L
6.55 pg/L
Possible
TEQ
released
Typical refinery effluent test: 88% of CDD/Fs
below detection due to small sample volume.
TEQ
detected
0.78 pg/second
289 pg/second
Possible
TEQ
released
Refinery cracker stack tests: 90% of CDD/Fs
below detection due to small sample volume.
TEQ
detected
0.07 pg!L
65.6 pg/L
Possible
TEQ
released
Test of Cal. reformulated diesel directly from
refineries: 94% of CDD/Fs below detection.
NOTES: Data from references 32.38.48.






A second problem stems from the choice to measure PCBs homologue groups (PCBs with the
same number of chlorine atoms), but not to measure individual dioxin-like PCBs. Refmeries
create relatively large amounts of newly-formed PCBs, and some of these are dioxin-like PCBs.
Assuming none of these PCBs are dioxin-like will underestimate TEQ
0
FP released, and assum-
ing all these PCBs are dioxin-like will overestimate releases. A better measurement is needed.
Laboratory and field studies confirm the formation
and release of dioxin-like PCBs from incinerators,
cement kilns, and other sources.2,44,54,56,57
Refinery sources create similar conditions for for-
mation of dioxin-like PCBs as incinerators and
cement kilns_7.22-
2
5 This is reflected in the similar
mix of specific CDD/Fs that is measured in these
source types. Figure 5 shows that in all three
sources: HpCDD and especially OCDD dominate
among CDDs; 1,2,3,4,6,7,8-HpCDF dominates
among HpCDFs; 1,2,3,7,8,9-HxCDF is very low;
other HxCDFs exceed HxCDDs; PeCDFs exceed
PeCDD; and TCDF exceeds TCDD.
In addition to these clear similarities, however, the
refinery source produces more PeCDFs, HxCDFs,
and HpCDFs than the other sources. Conditions
favoring formation of CDFs also favor formation of
PCBs.23-25 This suggests that refineries may create
more dioxin-like PCBs than these other sources.
In Figure 6, total PCB concentrations at a Bay Area
refinery and a municipal waste incinerator located
elsewhere are compared. This homologue compari-
son shows a clear increase in the amount of PCBs
relative to CDD/Fs from the refinery. PeCBs
include the most toxic dioxin-like PCB and make up
13% of the total CDD/Fs and PCBs from the refin-
ery source but only 3% of this total from the incin-
erator. HxCBs, which include the second most toxic
dioxin-like PCB, make up 11% of the total from the
refinery source versus 3% from the incinerator.
Existing measurements show dioxin-like PCBs
range from 5-25% of total TEQ in municipal incin-
erators, and 60% of the total TEQ in cement kiln
emissions.
2
44,5
4
,56,57 Greater PCBs and CDFs mea-
sured at the refinery source suggest PCBs are more
of the total TEQ from refineries than incinerators.
This analysis reports the dioxin-like portion of PCBs
releases from refineries as I 0-60% of total TEQ.
18
5. Congener profiles: refineries and other sources
Individual CDD or CDF/total CDD+CDF
O.ll2 0.04 0.06 0.08 0. 1 0.12
2.3.7.8-TCDD
Refinery reformers
1.2.3.7.8-PeCDD
0 Municipal incinerators
1.2.3.4.7 .8-HxCDD
1.2.3.6.7.8-HxCDD
D Cement kilns
1.2.3.7 .8.9-HxCDD
1.2.3.4.7.8.9-HpCDF
:-;oTES: Data from references and 55.
6. Total PCBs profiles: refinery and incinerator
PCB homologue/total CDD+CDF+PCB'
MonoCBs
DiCBs
TriCBs
TCBs
PeCBsb
HxCBsc
HpCBs
OCBs
Nona CBs
DecaCB
0 0.05 0.1 0.15 0.2 0.25

Refi nery


reformer
-------'
Municipal
0
incinerator
----'
-'
.....

Each PCBs group (mono-chlorinated.
etc.) is divided by the sum of total COOs, CDFs.
:llld PCBs. CDD/F portion of profile not shown.
blncludes PCB-126. clncludes PCB-169.
Dam from references 22 and 54.
Error and bias related to test frequency and disclosure: On average, the Bay Area
refinery source releases that are tested at all are tested only a small fraction (one-ten thousandth)
of the time that the releases are occurring. See Table 6. This is true despite relatively better
dioxins testing of Bay Area refinery releases than those elsewhere.
6. Timing of refinery dioxins releases and release testing in the Bay Area, June 1990-June 2000.
Tested Cumulative Testsb Test Cumulative Portion of
sources release-days
0
typeC test-days time tested
Effluent 6 21900.0 :!00 grab 0. 139 0.000006
Storm runoff 5 912.5 31 mix 0.354 0.000388
Air emission 4 14600.0 12 composite 4.000 0.000274
Refined products - 0
-
Totals 37412.5 4.493 0.000120
NOTES: acumulative days of release per source pathway over 10 years. Rain runoff set at 5% per year.
b Actual test number may be lower. Includes some water tests of combined refinery and non-refinery releases.58
CGrab samples set at I minute duration; composite samples set at 8 hours: one runoff sample was a composite.
Data from references 17,19,22,32,34,36,48,57,58.
A large variability exists in the concentration of dioxins in emissions. (See Table 7 .) Dioxins
release increased by 6.8 times in three consecutive days of testing at one Bay Area reformer.
22
At the Chevron cracker, stack emissions detected on all three test days changed by four times.
32
These tests on a few days show that releases at single sources change dramatically from day to
day, but they do not capture the full range of refinery release amounts.
On a burn rate basis, releases vary by 20,000 times in two sets of tests at the Shell and
Evergreen boiler/heater stacks.2,32,36,59 Emissions varied by 3,000 times between two sets of
tests done on two reformer stacks at refineries in Avon and Bakersfield_4,22,55 Tests of other
sources confirm similar hundred-fold to thousand-fold changes in dioxins emission rates.
2
4-Z9,
44
7. Variability in rate of dioxins release at refinery sources, and similar sources
Change in
Measurements compared
dioxins release
6.8 times
Stack tests of a Bay Area reformer on three consecutive days22
4 times Detected emission from three days at one refinery cracker stack32
300 times Average reformer process water at three refineries20
20,000 times Emission/kg burned at two Bay Area refinery boiler/heaters_234,36,59
3,000 times Emissionlbbl from refinery reformers at Avon and Bakersfield4,22.5S
100-2,700 times
Full scale tests of similar (non-refinery) processes during different
operating conditions. grouped by process type27.29,44
100-2,000 times
Lab & pilot tests of a single boiler or incinerator that measured changes
in chlorine, catalyst, heat distribution, & upsets (sooting)24-26,28
Further, the average that is directly measured may not represent the true long-term release, espe-
cially for stack tests. This is because existing tests taken during only a small fraction of the time
that releases occur may not measure a representative sample of overall releases. Lab- and pilot-
scale experiments show that variability in dioxins release (a hundred-fold or greater change, like
those shown in Table 7) can be caused by changes in process or chlorine input, catalyst activity,
19






heat distribution in the process, and com-
bustion efficiency.23-29 Even a relatively
minor 'upset' in combustion efficiency
increased dioxins generation greatly for
hundreds of hours afterward, because car-
bon buildup (sooting) continued to cat-
alyze dioxins formation.26
These conditions exist in refineries, as
shown by the routine regeneration of
reformer and cracking catalyst needed to
clean carbon deposits from process materi-
als. In fact, frequent upsets in refineries
suggest that periods when these conditions
do not exist may be the exception rather
than the rule.
Table 8 lists 41 incidents that were classi-
fied as "major" by Contra Costa County
officials at five refineries operating in the
County from March 1989 to April 1997 -
nearly one major spill, fire or explosion
per refinery each year. In one case where
independent analysis was performed (the
fatal January 21, 1997 cracking unit fire at
the Tosco Avon plant), the process was
operating inefficiently for much of the
year before the major incident.60.61
Closer inspection of Table 8 reveals that
for each plant, major upsets tend to be
grouped around the same time. There were
other upsets that were not classified as
8. "Major incidents" in Contra Costa refineries 1989-97.
Plant County-classified "major" incident
3/25/89 Tosco Fatal lube oil sumo exolosion
4/10/89 Chevr lsomax Uni t explosion and fire
9/5/89 Shell Hvdrotreater explosions and fire
9/9/89 Paciti Pioe nioole break. soilJ and fire
2/28/90 Shell Tank liner fire
1/4/91 Shell LDU Lube Crude heater spill and fare
4129/91 Tosco Relief valve hvdroeen sulfide soill to air
10n9/91 Chevr Catalytic Cracking Unit fire
12/5/91 Chevr Cracking Unit catalyst spill to air
3/31/92 Pacifi Heat exchanger tube rupture and fire
5/29/92 Pacifi Flare overload spill to air and homes
6/23/92 Chevr Cracker pump failure. smoke release
8112/92 Tosco Refinery fire trig,eers explosion
9/20/92 Tosco Power failure and flarine soark fire
12/11/92 Tosco Major flare odor release to air
3n/93 Tosco Major butane/hydrocarbons spill to air
4/1/93 Shell Sludge storaee tank explosion
6/18/93 Tosco Hydrocarbon/hydroeen sulfide soillto air
10/5/93 Shell Acid tank exQiosion and fireball
10n/93 Tosco Oil spill to Hastings Slough
214/94 Pacifi Fire in crude oil tank seals
2/10/94 Chevr Sulfur Recovery Unit spill to air
3/30/94 Chevr Instrument & flare failure spill to air
8/22194 Unoc 16-dav. I 00-ton catacarb so ill to air
9115/94 Unoc Compressor failure H2S spill to air
619195 Tosco Heat exchaneer fire
6116/95 Unoc Tank fire
9/25/95 Tosco Boiler malfunction/ bvpass spill to air
9/27/95 Pacifi Naotha and sulfur chemicals soill to air
2/1196 Shell Hydrogen Unit explosion
411/96 Shell Hydrot:reater explosion and fi re
5117/96 Unoc Coker fire
8/1/96 Pacifi Heavy vacuum eas spill to air
8/10/96 Chevr Power outaee causes flare smoke
8/16/96 Unoc Compressor malfunction. H2S to air
9/21196 Unoc Malfunction spills H2S to a1r
9122196 Unoc Tank leak releases sulfuric acid
1/21/97 Tosco Fatal hydrocracker explosion and fire
2/17/97 Unoc Odor release traced to refinery
4/13/97 Chevr Hydrocarbon and sour eas leak
4/16/97 Tosco Hydrogen sulfide and S02 spill to air
"major incidents." Flaring- a sort of NOTES: Data from reference 45.
"safety valve" for the buildup of explosive
gases in refineries6
2
- is an indirect mea-
surement of such process problems.
Data from special study of Bay Area refin- 9. Flaring by four Bay Area refineries
ery flares are summarized in Table 9.
Flaring was reported in all 18 months
studied, and the largest refineries flared
virtually all the time. Major refinery
processes could be involved in flaring for
hours every month (as a per-process grand
average), based on these data.62
Upsets that could increase dioxins may be
occurring on a monthly basis in refineries.
Flare-hours Percent Hours/pro-
per month a of time cesslmonthb
Chevron
338 46% 8
Shell (Martinez)c
989 100% 25
Tosco (A von)d
730 100% 18
Unocal (Rodeo)e
89 13% 2
Totals 2146 100% 13
Notes: a Reported for March 1988 through December 198961
hAssumes 40 major process units/refinery. CNow Sheli/Equilon. dsale to
Ultramar announced in June, 2000. eNow Tosco. Data from reference 62.
20
The effect of such minor upsets was reported this year from a controlled experiment that mea-
sured changes in total CDD/F formation and emission from an industrial boiler.2
6
Relatively
poor combustion efficiency was created by increasing the feed rate and slightly misaligning a
burner nozzle for about 50 hours. This formed carbon deposits contaminated with chlorine and
dioxins precursors and catalysts, that in tum created more dioxins with continued source opera-
tion long after the upset.
2
6 As shown in Figure 7 stack release increased from 4 to 1,953 pglm
3
100 hours after the beginning of this upset, increased further (based on deposit testing) until
about 250 hours after the beginning of the upset, and remained elevated for approximately 300
hours after the upset ended. (Due to sampling and analysis considerations noted in the figure,
the stack tests provide the best measurement of the extent of dioxins increase while the tests of
carbon deposits in the unit provide the best measurement of its duration.)
7. Timing and extent of dioxins source generation after upset in combustion efficiency.
2000
r::: 1800
1600
~ 1400
~ 1200
~ 1000
0
~ 800
!:::
:13 600
0
400
u
200
0
Hours of operation from beginning to end of tests
0 100 200 300 400 500 600
1,953 pgfm3
., 1,840 ng/100 mg
-
,,
-
Stack releases (pglm3)a
-
, ~
, ~
~
~ . ,, ~
--
Carbon deposits
-
I
' ,, ~ (ng/100 mg)a
-
I
,,, ~
I
~
- ~
I ~
- I ......
-
I
......
-0 ng/100 mg
I
......
......
-
in deposits\ I
...
4pgfm3 . ~
...... t
-
...... ,
in stack 'A.
A
Combustion Chlorine and metal zeroed out of inputs Chlorine and metal
upset begins Combustion upset ends
reintroduced
NOTES: as tack measurements analyzed by high resolution GC/MS more accurately reflect extent of emission; deposit measurements
(measured by low resolution GC/MS in boiler pass 2) more accurately reflect emission duration while chlorine and metals source is
interrupted ( 150-560 hours) because stack measurements were not made during this period. Data from reference 26.
There is a clear bias in existing release measurements made only when releases tend to be small-
er. The dioxins release tests that were taken were not taken during the major upsets at Bay Area
refineries. Also, the data in Figure 7 show that relatively clean operation for 300-400 hours (2-3
weeks) results in a drastic drop in stack emission, and refiners always had this much advance
notice of stack tests. One refiner set up its own test with its contractor.3
6
The Bay Area Air
District began public discussions of the cracking and reforming unit tests that were negotiated
with the other companies for months before these tests.32,22,34,63,64 Refinery management have a
strong and explicit interest in being seen as "insignificant" sources of dioxins, as evidenced by
the energy Bay Area refiners have expended to to assert this point of view.6
5
-72 Thus, there is
no scientific basis for concluding that the few measurements taken represent an accurate average
of actual releases over time, because these measurements may instead represent the portion of
the distribution of highly variable releases that was measured when releases were smaller.
In sum, existing tests measure only during a small fraction of the time, and stack releases could
be much smaller during these tests, because the tests are announced in advance and are taken at
times when the recent history of operating conditions could result in much less dioxins release.
21






Therefore, this analysis measures dioxins release rates from Bay Area refinery stacks as follows .
To account for the greater magnitude of these releases at times when they were not measured
without ignoring source-specific data, it applies a variability factor to the existing source-specif-
ic measurements. This variability factor integrates (averages) the source-specific measurements
of (partial) variability, and the general measurements of the full variability due to minor upsets
shown in Figure 7. To account for the duration of greater releases than source-specific tests
measured, given frequent process changes that are not distributed evenly over time (as reflected
by the lognormal distribution of industrial releases), this variability factor is calculated as the
median of the log-transformed source-specific and general data. For example:
Example of variability factor derivation for upper bound dioxins stack releases.
a. Partial range of release at a Bay Area reformer (Table 7): Log of 6.8 times =
b. Full range of release in controlled tests (from Figure 7): Log of 488 times =
c. Median of log-transformed source-specific and general data:
d. Median of log-transformed data, back-transformed from c above:
(58 is the variability factor applied to source-specific release rate data for reforming.)
0.83
2.69
lli
58
To account for the evidence suggesting that a sampling bias may skew the data from direct mea-
surements of stacks toward a false "average" that underestimates releases, this analysis includes
these variability factors in upper bound stack release measurements for Bay Area refineries.
Error and bias when there is no testing of a known or suspected source. As
shown in part 1, there is strong evidence that several major refinery processes which have not
been tested for dioxins, refinery products such as petroleum coke and furnace ash (used by other
industries), and uncontrolled fires may cause additional dioxins releases from refineries. Indeed,
dioxins releases are likely due to one or more of these suspected sources and products.
The failure of refinery monitoring programs to measure for releases from these sources and
products results in measurement uncertainty. Though estimating possible dioxins releases from
these sources is difficult, nevertheless, any assumption that such unmeasured releases do not
exist would introduce a bias into release estimates which fails to account for this uncertainty.
Since no measurements confirming these releases exist in the Bay Area or elsewhere, and it is at
least possible that these suspected sources are all free of dioxins, this analysis uses zero release
from these sources and products as the lower bound measurement of dioxins release from these
suspected sources.
To address the problem of uncertainty (and that of bias when it is assumed that sources which
are ignored do not exist), this analysis estimates possible upper bound dioxins release from sus-
pected process sources and uncontrolled fires at refineries from data on refinery processes that
have been measured, using environmental data as a check on these estimates. The data and
methods are described in the analysis of other (suspected) refinery sources below.
For upper bound releases from refined products suspected to contain dioxins (and motor oil as
well) this analysis applies the diesel release factor discussed below to distillate fuel production .
22
Error and bias related to sampling of release pathways. No data on dioxins releases
caused by refinery contamination of diesel or motor oil exist from tests in the Bay Area, despite
the fact that both of these products are known to be contaminated with dioxins as they leave
refineries based on direct measurements in southern California. Nor are other products tested.
This analysis measures the lower bound of dioxins release in products shipped from Bay Area
refineries using the measurements of diesel reported from southern California refineries and the
estimates of Bay Area production of CARE reformulated diesel discussed in part 1. This lower
bound production estimate includes only diesel produced for on-road use in California, and does
not include motor oil (known to be dioxins contaminated), other distillates, petroleum coke, or
ash shipped to cement kilns (suspected to contain dioxins). The upper bound of dioxins release
accounts for these possible releases in products using the diesel contamination data and the total
distillate production rate estimated for Bay Area refineries.
ANALYSIS OF SOURCE-SPECIFIC MEASUREMENTS:
Reforming catalyst regeneration.
There are six reforming units in Bay Area refineries that process an estimated 170,000 barrels
per day. Releases of dioxins from reformer stacks are estimated here. Since these releases
deposit to land and water, and a portion of these releases enter rainstorm runoff from refineries,
stack estimates include the amounts of refinery dioxin in refinery runoff (to avoid double-count-
ing releases). Other reformer dioxins releases mix with other dioxins released into the combined
effluent discharge and products from refineries, and are addressed below.
Data from tests that measured stack releases from the Tosco Avon Refinery No.3 Reformer in
1998 are shown in Table l, part 1 above. All 17 CDD/Fs as well as total PCB homologue
groups were detected in all three tests of this stack release. The CDD/F TEQ measured ranged
by 6.8 times, averaged 2.69 ng/barrel and reached 5.51 ng/bbl in these tests. Dioxin-like releas-
es are also reported from a reformer stack test at a Bakersfield refinery,5
5
but this test was con-
ducted in 1991, did not detect all dioxins analyzed, and did not measure a Bay Area refinery.
The partial range of release found in limited source-specific tests and the full range of release
from controlled experiments performed elsewhere yield a variability factor of 58 for this source,
as shown in the example on the previous page. Thus, the range of release including dioxin-like
PCBs (10-60% ofTEQ) is 2.96-770 ng/bbl. However, while the No.3 Reformer at Avon uses
continuous regeneration to process 31,500 bbl/d, the other five units process nearly 140,000
bbls/day but may operate only about one week per year.
4
7,17,20 A separate factor to account for
releases only 1/50th of the year must be applied to this portion of the source category.
Therefore, the lower bound long-term dioxins release rate from this Bay Area source is 100 mil-
lion picograms per day, and the upper bound of this release rate is 26.3 billion pg/day.
Cracking catalyst regeneration.
There are at least seven cracking units in Bay Area refineries that process an estimated 511,740
barrels per day.
17
19 Releases of dioxins from cracker stacks are estimated here. These stack
estimates include the amounts of dioxin in refinery runoff, to avoid double-counting releases.
23






The amounts of cracker dioxins releases contributed to effluent discharge and products from
refineries are addressed below.
Data from tests that measured stack releases from the Chevron Richmond Refinery Fluid
Catalytic Cracking Unit in 1997 are shown in Table 3, part 1 above. Three CDD/Fs were detect-
ed in these tests. One test detected only one of the least toxic CDFs: using this result would
underestimate CDD/F TEQ present in that test and overestimate the range during testing.
CDDIF TEQ ranged from 0.177 nglbbl when CDD/Fs are assumed present at half the detection
limits in this test, to 0.535 nglbbl if dioxins are at their detection limits in the test measuring the
most release in this refinery's 55,600 bbl/day cracking throughput. (The dioxin detected in all
tests exhibits similar variability.) This is the only dioxins test reported for a refinery cracker.
The partial range of release found in these limited source-specific tests (0.177 -0.535 nglbbl), and
the full range of release from controlled experiments performed elsewhere, yield a variability
factor of 38 for this source. Thus, the range of release including dioxin-like PCBs is 0.19 to
50.8 nglbbl. Applying these factors to the Bay Area production rate for this process source, the
lower bound long-term dioxins release rate from this Bay Area source is 97.2 million picograms
per day, and the upper bound of this release rate is 26 billion pg/day.
Oil- and waste-fired process heaters and boilers.
These processes bum an estimated 40,000 to 160,000 barrels of oil, intermediates, petroleum
wastes and/or petroleum fuels ranging from No. 2 fuel oil and heavier in Bay Area refineries
each day, as discussed in part 1. Releases of dioxins from their stacks are estimated here. These
stack estimates include the amounts of dioxin in refinery runoff to avoid double-counting these
releases. Releases into effluent discharge and products are addressed below.
Data from 1997 tests of stack releases from a process heater firing about 22.4 barrels of oil per
day at the Evergreen Oil refinery in 1997 are shown in Table 4. Fourteen CDD/Fs were detected
in these tests. Analysis of these data suggests that CDD/Fs present below detection limits may
have been present at half the detection limits, or at greater concentrations in these samples.
CDDIF TEQ ranged from 27 to 29.8 pg/test when dioxins present below detection limits are set
to half the detection limits in this test. Based on production and release rates, average CDD/F
TEQ in these tests was 0.23 ng per liter of oil bumed.2,59 The Air Quality Management District
estimated CDD/F releases of 0.007 pglkg of waste feed from tests of a boiler at the Shell
Martinez plant, but these tests used older methods that did not detect dioxin-like CDD/Fs from a
known source type -waste incineration with electrostatic precipitation treatment
2

34
- so this
result is suspect. EPA reported dioxins releases ranging from 0.06 to 0.6 ng per liter of oil
burned in boilers tested elsewhere.2
This analysis uses the Bay Area source data from Evergreen Oil for the CDD/F emission tested
(0.23 ng/L burned) and for source-specific variability data (27-29.8 pg/test). Combining this
partial range of release with the full range of release from controlled experiments performed
elsewhere yields a variability factor of 23 for this source. However, the resulting release rate is
near the high end of the range reported by EPA, and this test may have been associated with rel-
atively high chlorine in the feed.
2

35
The variability caused by changes in the chlorine content
and rate of feed input at most refinery oil and waste-fired heaters and boilers may be significant-
ly less than that found at the Evergreen process.2 For these reasons, many or most of these
24
process sources may release dioxins at the rate measured by these source specific tests rather
than the greater (upperbound) rate measured by the variability factor.
Thus, the range of release rate including PCBs is 0.53-13.23 ng/L burned, but the smaller value
(0.53 ng/L) defines the lower bound possible release (sources burning 40,000 bbVday) and 80%
of the upper bound of possible release (sources burning 160,000 bbVday) for these processes.
Therefore, oil- and waste-fired refinery processes release more than a lower bound of 1.61 bil-
lion pg/day, and less than an upper bound of 72.4 billion pg/day in the Bay Area.
Contamination of refined products in refineries.
Bay Area refineries produce 80,000 bbVday of CARB reformulated diesel and 136,000 bbl/day
of total distillates (which includes diesel and other products).17-19 Some of the dioxins formed
by refinery sources leave these refineries in diesel. Dioxins contamination of motor oil in
refineries is confirmed as well, and evidence suggests contamination of petroleum coke, furnace
ash, and/or other refined products. Evidence for these conclusions is discussed in part 1 above.
Data from tests that measured diesel from southern California refineries in 1998 are shown in
Table I 0. OCDD was found in both samples at high concentrations. Other CDD/Fs were below
the high detection limits of these analyses. The analysis in Table 10 shows that the true concen-
tration of CDDIF TEQ in the diesel was between 0.72 and 302 picograms per liter, however, it is
probably well within this range.
Diesel, motor oil and other distillates probably con-
tain all the dioxin compounds produced in refiner-
ies, because dioxins have high affinity for fats and
oils, and move into the oil content of these prod-
ucts upon contact in refinery sources. This likely
presence of many dioxins means that the relatively
high detection limits in the diesel analyses present
an artificially expanded range of possible TEQ in
these samples. The best estimate of the average
dioxins present in this product based on data in
Table I 0 is represented by the narrower measure-
ment range of 0.14 to 65.6 pg/L CDD/F TEQ.
Dioxins are confirmed in known amounts of refor-
mulated diesel production, and are confirmed or
suspected in other distillates (including diesel and
other products). The lower and upper bounds of
release use reformulated diesel, and total distillate,
production rates, respectively. Including PCBs,
these lower and upper bounds of release in refined
products are 1.96 million and 3.5 billion pg/day.
25
I 0. CDD/Fs in diesel leaving California refineries.
CARB Pre-
In picograms
reformula 1993
per liter TEP ted diesel diesel
2.3.7.8-TCDD I sob (26> BD ( 100)
1.2.3,7,8-PeCDO I BO (21) 80(89)
1,2,3,4,7,8-HxCDD 0. 1 BO (21) BD ( 110)
1,2,3,6,7,8-HxCDO 0.1 BO (23) BO (120)
I ,2,3,7 ,8,9-HxCDD 0.1 BD (20) BO (110)
1.2,3,4,6.7.8- 0.01 BO (47) BO (230)
OCDO 0.0001 720 1400
2,3,7.8-TCOF 0.1 BO (II) 80(21)
1,2,3,7.8-PeCDF 0.05 80 (8. 1) BD (110)
2,3,4,7 ,8-PeCDF 0.5 BD (II) BO (100)
I ,2.3,4,7 ,8-HxCDF 0. 1 BD (6.4) BD (36)
l ,2,3,6,7 ,8-HxCOF 0.1 BD(6.l) BO (34)
2,3,4,6,7,8-HxCDF 0. 1 BO (17) BD (66)
l ,2,3,7 ,8,9-HxCDF 0.1 BD (7.5) BD (36)
1,2,3,4,6,7,8- 0.01 BD (48) BO (92)
1.2,3,4,7,8,9- 0.01 BO (50) BO (98)
OCDF 0.0001 BD (4 1) BD (260>
TEQ(BD=O) 0.072 0. 14
TEQ(BD=OL) 65.6 302
NOTES: aToxicity equivalence factor.
bsetow detection (detection limit). Data from reference 38.

I





Contamination of effluent in refineries .
At least five Bay Area refineries discharge an average of 77 million liters per day of partially
treated waste water into San Francisco Bay. Some of the dioxins released by reforming and
other refinery dioxins sources are discharged in these effluents.
On average, less than 20% of CDD/Fs analyzed were detected in dozens of one-liter grab sam-
ples of refinery effluent. The more toxic CDD/Fs were seldom or never detected in final refin-
ery effluents due to the small volumes of samples analyzed, but these dioxins are known to be
discharged below detection limits because they are confirmed by tests of internal waste water in
refineries,20.21 and in discharge canal sediment of one of the plants.7
3
Analysis of these data
suggests that dioxins below detection limits in these effluents may be present at levels near or
below one-half the reported detection limits.
On the Hook for Zero Dioxin reported average CDD/F TEQ in refinery effluent at 0.88 pg/L
with below detection results set to zero, and 7.86 pg/L with these results set to half the detection
limits of the analyses.
2
Including PCBs this yields a discharge rate of 74.5 million to 1.5 billion
picograms per day. The low end of this range is six times greater the Regional Water Board
staff estimate of this discharge rate (0.4 grams per year of CDD/F TEQ, or 12.1 million pg/day
including PCBs as 10% of TEQ). Expanding the range of this estimate at its lower bound to
encompass this analysis, the lower and upper bounds of Bay Area refinery dioxins releases in
effluent are 12.1 million and 1.5 billion pg/day, respectively.
Other (suspected) refinery sources .
The strong evidence suggesting dioxins generation and release due to flaring, coking, distilla-
tion, desalting and/or uncontrolled fires in refineries establishes a need to address the uncertainty
caused by failure to measure these suspected sources by estimating some upper bound of their
possible releases.
However, too little data exist for any detailed analysis of any of these individual source types.
For example, structure and vehicle fire data are too uncertain for confident release estimates to
be extrapolated to refinery fires,
4
and doing so produces a result that is orders of magnitude
above existing estimates of total dioxins releases in the Bay Area.3
4
Even though these existing
estimates by the regional Air District have been criticized (correctly) for underestimation, the
refinery fires estimate extrapolated from these data also approaches an amount that may not be
supported by observed dioxins levels in the Bay Area environment. While this suggests a possi-
bility of catastrophic dioxins contamination fromfuture refinery fires, it does not suggest these
extremely high levels of dioxins release are already occurring from refinery sources.
Given evidence that one or more of these many suspected sources may form and release dioxins,
and evidence suggesting that these releases are unlikely to exceed upper bound releases from
confirmed sources by orders of magnitude, the best estimate based on existing data would com-
pare possible releases from suspected sources to those from confirmed refinery sources. This
analysis estimates suspected source release as an upper bound amount equal to the average of
confirmed stack releases (from reforming, cracking and oil-fired processes), due to one or anoth-
er of the many suspected sources. This maximum dioxins release from suspected refinery
sources is less than 41.6 billion pg/day. The possible lower bound of these releases is zero.
26
MINIMUM AND MAXIMUM BOUNDS OF
REFINERY DIOXINS RELEASE:
Each of the individual source assessments above
addresses information gaps explicitly by quanti-
fying uncertainty within lower and upper bounds
of possible release. This allows overall regional
refining industry releases to be measured with
confidence by adding the bounds from these
assessments: the chances that releases from
many sources might fall above or below the
cumulative bounds of this measurement become
increasingly remote; and the likelihood that true
release rates will fall closer to the midpoint of
the range is strengthened.
Based on the detailed analysis here, the long-
term rate of dioxins release from S.F. Bay Area
oil refineries: a) exceeds a lower bound of 1.82
billion picograms-per-day; b) is less than an
upper bound of 171 billion pg/day; c) is very
likely to be significantly less than 171 billion
pg/day; and d) is very likely to be significantly
greater than 1.82 billion pg/day. These mea-
surements are shown in Figure 8.
Review of Figure 8 reveals total refinery dioxins
releases 13 to 15,000 times past estimates that
included only some of the dioxins from some of
the refinery sources.34.53
Review of Figure 8 also shows that refinery
dioxins releases are not significantly smaller
than those estimated from residential wood
burning, and are probably significantly larger
than these releases. This observation is impor-
tant because Bay Area Air District estimates
suggest that more dioxins are released via resi-
dential wood burning than via any other activity,
whether residential or industrial, in the Bay
Area.34.74
This rate of dioxins release suggests that refiner-
ies pollute the Bay Area environment. If envi-
ronmental measurement is adequate this contam-
ination should be observed. Part 3 of this analy-
sis investigates whether existing data support
this observation.
27
8. Lower and upper bounds of dioxins release
by Bay Area oil refineries, in picograms/day
(TEQoFP-WHOgg), and estimates by others.
(Scale compressed)
it
1.82
billion
pglday
or more
r ...... ........................................................................ ..
Key
II
D
0

t
2.2
billion
pg/day
. ;.;. ';;. ; ...
.. ,
...
Lower bound of amount
Upper bound of amount
Estimates by others
Arrows point to
increasing likelihood
of true release rate
Bay Area Wood Refineries Refineries
refineriesa burning (Bay Area (Water
(AQMD)b AQMD)C Board)d
NOTES: arhis analysis. boata from reference 74.
CBAAQMD refinery (reforming) estimate from reference 34.
dRWQCB refinery (effluent) estimate from reference 53.






Part 3. Measurements linking dioxins in the Bay Area environment to
refinery sources.
Environmental measurements have been used to investigate sources of dioxins in several ways.
Aquatic contamination has been linked to effluent discharges from known sources through
analysis of pollution "gradients" that revealed more dioxins in aquatic sediment and aquatic life
near sources.I,2,6,47,76-78 Dioxins sources have been linked to increased dioxins in soil, local
food chains, and people who live near sources and/or eat locally produced food.2,47,77-82
In addition, source emission has been linked to greater dioxins concentrations in urban-industrial
regions' air than in air elsewhere, linked to dioxins fallout on land and water over long distances
with greater fallout near sources, and linked to the contamination of runoff, which carries a por-
tion of the dioxins deposited on land into water bodies when it rains.l-4,47,49,50,56,57,75,80-95,99
Further, the relative mix, or "profile" of dioxins has been used to trace contamination to sources
in some cases,77-8I although this requires relatively high-quality measurements of this "profile"
of dioxins and how it changes when dioxins move through the environment. 8
4
.86-95 Finally,
environmental measurements have been used to suggest that source emission rates may be
underestimated in comparison with the amount of dioxins fallout from the air.84-86,I09,111
ANALYSIS OF DIOXINS POLLUTION GRADIENTS IN SEDIMENT, WATER AND FISH:
CBE's 1998 report On the Hookfor Zero
Dioxin and our further work during 1999
found that there is more dioxin pollution
near 27 industrial sources than there is fur-
ther away from these sources in the Bay
Area.2.4
7
To focus on the part of this pollu-
tion that is from refineries, it is useful to
know the locations of al1 these sources. This
allows better analysis of pollution from
refineries because it identifies which envi-
ronmental measurements are near other
.sources, and that helps to distinguish the pol-
lution caused by refineries from the pollution
caused by other sources.
Aquatic sediment has been analyzed for
dioxins in 19 samples from seven Bay Area
sites, that are shown along with locations of
industrial dioxins sources in Figure 9_73,96
Except for the refinery site (the Avon plant's
discharge canal), the Antioch site near an old
paper plant (not shown), and the San Joaquin
River site (downstream from a dioxin conta-
mination cleanup site that is not shown),
these sites are not very near known sources.
9. Oil refineries, other industrial dioxin sources identified,
and sites tested for dioxins in aquatic sediment in the
S.F. Bay Area.
Source key:
oil refineries

incinerators
0
scrap
furnaces

chemical
drum
furnaces
0
foundries
0
other
industries

Sediment
test sites
0
NOTES: Data from references 2, 47, 73 and 96.
28
0
Figure 10 shows the dioxins concentrations in
sediment from these sites. The refinery site is
nearly twenty times more contaminated than any
other sediment site tested in S.F. Bay or its trib-
utary rivers. When the San Joaquin River site is
excluded (due to the "hot spot" upstream), the
refinery site is 140 times more contaminated
than the other Bay Area sites.
Average and maximum concentrations of total
CDDIF in this refinery site sediment are slightly
higher than those reported in grossly contami-
nated sediment near a polyvinyl chloride (PVC)
plant,76 and the average is 87 times larger than
the highest level reported by EPA in a survey of
U.S. lake sediment.83 Average refinery TEQ
also exceeds the highest soil level in a survey of
backyards contaminated by PCP burning. 80
Storm water runoff concentrations of diox-
ins in 74 grab samples, from 31 Bay Area sites
at known distances from industrial dioxin
sources, are shown in Figure 11.97.98 (Black
dots show results from 13 tests at 5 refineries.)
The many sites measured provide a picture of
regional differences in dioxins pollution. The
grab samples measure the changing amounts of
CDDIF swept into dramatically changing runoff
flows from highly dynamic storm events. These
data show the range of minimum to maximum
dioxins runoff concentrations, not the averages.
This runoff is carrying some of the dioxins fall-
out that accumulated from source emissions
before the storms. Since dioxins tend to deposit
at greater rates near sources, runoff near impor-
tant sources should be more contaminated than
runoff far away from these sources. In fact,
review of Figure 11 reveals a clear and consis-
tent gradient in the maximum concentrations
measured, which decrease from high levels near
sources to levels about 100 times smaller 15-25
km. away from the nearest source. The greater
differences between maximum and minimum
concentrations near refineries are also consistent
with emission rates that change drastically over
time (as shown in part 2 of this analysis).
Statistical analysis of the data in Figure 11 sug-
gests that dioxins are significantly higher in
29
10. Dioxins in S.F. Bay Area aquatic sediment, in pglg.
700
600
500
400
300
200
100
0
630
34.9
3.14 1.99 J.O 0.79
Refinery San
canala Pablo
Bayb
Delta Peta- Napa San Sacra-
at Ant- luma Rivera Joaquin menta
iochb Rivera Riverb Riverb
NOTES: aTEQoF -WH09g. bn;QDFP -WH09g. Dioxins below de
tection set to half the detection limit. Refinery (9 samples; 78<;< detected)
and Petaluma and Napa river (6 samples: 23% detected) data from refer
ence 73: Other four samples (39% detected) from reference 96.
II. Dioxins in Bay Area runoff v. source distance
70
o rl.-.tc (213 r g{LJ
Runoff sample at refineries
o Runoff sample at other sites
60
u:-5o
0
Cl

.J40
Oh
-5-
"0
B
u
B30
.,
"0
"'
" ;c
0
Ci 20
10



D
!l

.
0
D
D
D
D D D
Do
cEil
5 10 15 20
Distance to nearest source (km)
25
NOTES: Results below detection set to zero. References 2. 97, 98.






refinery runoff than in runoff 4-10 kilometers,
and 15-25 km. from the nearest source.
However, dioxins levels in runoff can also
increase because dioxins have a high affinity for
particles, and the amount of particulate pollu-
tion in runoff changes with changes in pollution
sources and changes in storm runoff events.
Thus, a more sophisticated analysis of runoff
pollution can provide more information.
Figure 12 compares dioxins in runoff to particu-
lates ("suspended solids") in the runoff, for 47
Bay Area samples where both types of data are
reported. A disproportionate percentage of the
refinery samples have dioxins levels far differ-
ent from the levels that could be explained by
changes in suspended solids levels in the major-
ity of these 47 samples. Suspended solids lev-
els might explain 38% (R-squared = 0.378) of
the changes in runoff dioxins at all sites, but
other factors are affecting refinery runoff con-
centrations of dioxins.
One of these other factors is particulate pollu-
tion from refineries. Figure 13 graphs runoff
contamination by dioxins and suspended solids
with distance from sources, for the 47 samples
with both measurements. The dioxins TEQ
detected in each sample is the height of the col-
umn for each sample. The amount of suspend-
ed solids is shown by how far "out" (down and
to the left) each column is placed on the graph.
Distance to the nearest industrial source is
shown by how far each column is placed down
and to the right. In this graph, refinery site tests
are shown in gray, while other sites are shown
in black.
Review of Figure 13 reveals pollution gradients
for both dioxins and particulate pollution: maxi-
mum levels of both types of pollution in runoff
are highest near sources; decrease at sites 4-10
km. from sources; and are lowest at sites 15-25
km. away from sources. Refineries (and other
sources) are known to cause particulate as well
as dioxin pollution. Some of the greater dioxin
pollution in runoff samples with high suspended
solids near refineries is because portions of both
pollutants are from the same sources.
30
12. Dioxins v. suspended solids in Bay Area runoff.
70
60
ti:' 50
0
Cl
~
...140
Oil
.,e.
-g
0
.!:! 30
u
"C
"' c
;c
c
i5 20
10

0
0
0

Runoff sample at refineries
0 Runoff sample at other sites
0 500 1000 1500 2000 2500 3000 3500
Suspended solids (ppm)
NOlES: 47 samples of i o x i n s n ~ suspended solids from references 97
and 9H. (Dues not include data from a barrel reclamation site where solids
dala were not available for the full range of cJioxins levels measured.)
13. Dioxins and suspended solids gradient in Bay Area runoff.
-: Runoff sample at refineries
I Runoff sample at
other sites
NOTES: 47 samplc.s with CDDIF and solids data. Data from references 2. 47,97 and 98.
Regression analyses (shown in Table 11) indicate that variability in suspended solids may
explain 38% of the change in runoff dioxins concentrations, while closeness to dioxins sources
may explain 39% of this change, but these factors overlap, and neither of these factors can
explain as much of the dioxin pollution gradient in these runoff samples as the combined effect
of both factors. Together with the observation that refineries cause particulate pollution, this
indicates that sources at refineries influence runoff concentrations of dioxins.
11. Regression analyses of factors affecting the dioxins gradient
from refineries to the Bay Area environment in runoff.
Regression assumption: TEQ is a function of: R-squared
Suspended solids affect dioxins Solids concentration 0.378
Closeness to source affects dioxins 1/lan. to nearest source 0.388
Solids and closeness affect dioxins Solids x 1/km to source 0.412
Solids, closeness, and source SS x 1/km; outliers excluded 0.696
NOTES: For 47 samples including solids (p=.OOI). References 2. 47, 97, and 98.
Changing dioxin release rates at nearby sources further influence the dioxins runoff pollution
gradient. This effect is highlighted by the observation that nearly one-fourth of the refinery
runoff samples have more dioxins than can be explained by suspended solids. The 60, 68 and
8.8 pg/L refinery site samples in figures 12 and 13 have high dioxins, even in relation to their
suspended solids content, indicating a source effect independent from the effect of solids content
in these samples. The way this effect can occur is obvious from the analysis in part 2, which
shows drastic changes in dioxins release rates from refinery sources: changes in stack emission
lead to changes in fallout, and in dioxins content carried in runoff.
When variability in refinery dioxins release is included as a factor affecting refinery site runoff
concentrations (when the extreme high dioxins/solids samples are not "forced" into the correla-
tion), the correlation shown in Table 11 can explain 70% rather than 41% of the dioxins pollu-
tion gradient in the 47 runoff samples from Bay Area sites.
The remaining 30% of changes in dioxins concentrations observed in these samples is probably
explained by changes in storm runoff events that are not measured by thes.e data, other measure-
ment errors, and/or other sources of dioxins. However, dioxins concentrations and variability in
runoff samples far from industrial sources and near areas of residential wood burning are the
smallest observed in these Bay Area data. This indicates that dioxins release from residential
wood burning (see Air District estimate in Figure 8) does not have a major influence on this
runoff gradient, and cannot explain the remaining 30% of runoff dioxins variability.
This evidence links an important amount of the dioxins flow entering San Francisco Bay in
runoff to oil refinery dioxins sources. It also indicates that refinery releases have a more signifi-
cant effect on the Bay Area dioxins pollution gradient in runoff than releases through residential
wood burning, further supporting the findings about refinery release rates in part 2 of this analy-
sts.
31 .






Fish tissue analyses measure dioxins in the
food chain at many Bay Area sites. The largest
number of comparable S.F. Bay fish tissue sam-
ples analyzed includes fillets with skin from
105 white croaker.2.47.IOO,IOI Comparable tis-
sues from other fish feeding at similar positions
on the food chain were analyzed for dioxins at
a Bay Area drinking water reservoir a few km.
away from refineries, and a rural lake 160 km.
north of the Bay (largemouth bass fillets with
skin and catfish fillets).
2

47

1
02,103 Catfish are
stocked in the reservoir, however, comparisons
with other reservoir fish suggest the hatchery is
not the source of the dioxins in these catfish.! 03
Figure 14 shows these data.
Dioxins levels in Bay Area fish clearly exceed
those in fish from the rural lake. The ranges of
dioxins TEQ measured do not overlap between
these sites. This is true for CDD/Fs, PCBs and
total TEQ. The only one of these 18 compar-
isons to overlap is CDD/Fs in bass, and even in
this case the reservoir average is higher.
Higher pollution in the Bay Area than the rural
lake is not explained by fallout from sources
outside the Bay Area. Both the Bay Area and
the rural lake receive ocean air flows2.47 (See
Figure 15). There is less dioxins fallout from
ocean air masses than from air masses that have
passed over land-based sources,49,50,84-95,99 and
a U.S. lakes sediment closer to the Pacific has
lower dioxins levels than inland U.S. lakes.83
Consistent with low fallout from distant
sources, average TEQ in fish from the rural
lake (0.04-0.3 pg/g) is less than 50% of the lev-
els in fish from U.S. marine waters that are not
near known sources (0.61 pg/g), and 13% of
levels in fish from U.S. fresh waters (2.4
pg/g).
4
(Levels are TEQDFP-WH0
98
.)
However, the average dioxins concentration in
Bay croaker (9.5-10 pg/g as TEQDFP-WH0
98
)
is four times the freshwater fish average, 16
times the marine fish average, and 30-250 times
the dioxins content of fish from the rural lake
160 km. north of the Bay. This indicates signif-
icant dioxins releases in the Bay Area.
32
14. Ranges of dioxins in fish from S.F. Bay, a nearby
drinking water reservoir, and a lake 160 km. north.
S.F. Bay (105 croaker)
Reservoir (4 catfish)
Reservoir (3 bass)
Rural lake (8 catfish)
Rural lake (6 bass)
S.F. Bay ( 105 croaker)
Reservoir ( 4 catfish)
Reservoir (3 bass)
Rural lake (8 catfish)
Rural lake (6 bass)
I
I
0 5 10 15
Total TEQ (Range pglg wet wt.)a
-
I


0 0.5 I 1.5 2 2.5
CDD/F TEQ (Range-- pglg wet wt.)a
S.F. Bay ( 105 croaker)
Reservoir (4 catfish)
Reservoir (3 bass)
Rural lake (8 catfish)
Rural lake (6 bass)
0
I
I
5 10 15
PCBs TEQ (Range - pglg wet wt.)a
NOTES:
0
Each range includes the least contaminated sample
(analytes below detection or with blank contamination or
with interferences set to zero) and the most contaminated
sample (all analytes set to reported values). Data from refer-
ences 100-102. Calculated as WH09g TEQ for mammals.
15. Dioxins in fish from two sites along the U.S.
Pacific coast: San Francisco Bay, and a rural
lake approximately 160 krn. north of the Bay.
PCicijic
Oct an
NOTES: The 0.04 and 9.5 pglg values are calculated
with results below detection. with contamination of
blanks. or with interference set to zero; the 0.3 and I 0
pglg values set these results to reported values. Data
from references I 00-1 02. Figure from reference 2.
ANALYSIS OF DIOXINS PROFILES:
In theory, the relative amounts of the different dioxins
in the environment match this "profile" of dioxins
from the sources. In practice, however, three types of
information are needed: 1) the amount of each dioxin
in the environmental sample; 2) the amount expected
to end up in the environmental sample; and 3) the rel-
ative amount of each dioxin released by the sources.
Amounts of individual dioxins in environ-
mental samples are poorly detected and measured
in most cases due to the same analytical detection
problems found in source data.
2
.4
7
Only samples of
fish,I00-102 and of sediment (at the Avon refinery)
have more than 50% of dioxins (even CDD/Fs) reli-
ably quantified in the Bay Area environment.73
Amounts of dioxins expected to end up in a par-
ticular environmental sample are hard to predict,
because different dioxins go to different parts of the
environment. Different animals concentrate different
dioxins in different amounts, 16,86 as shown by rela-
tively higher CDDs, CDFs, and PCBs in S.F. Bay
bivalves, sharks, and seals, respectively than in
fish.96,tot,I02,104 This changes the profile of dioxins
so that it is difficult to compare it with a source.
The profile of dioxins also changes after they are
emitted to air.
4
9,50,
8
4-95 The amounts that attach to
particles and become fallout near sources are affected
by the size and amount of particles in the air, and
each chemicals' specific affinity for the particles.
4
.86
Vapor pressure is one factor in this affinity, and some
dioxins have 1,000 to 10,000 times greater vapor
pressure than other dioxins.
4
,86 Further, as some
dioxins attach to soot, soil or vegetation better than
others, they deposit faster, and resist breakdown
(which occurs when they are not attached to particles
and light hits them) longer than other dioxins. 86,92,95
The top box in Figure 16 compares the CDD/F homo-
logue profile in air near sources elsewhere to the pro-
file deposited in soil. The profiles do not match.
After emissions travel, however, the profile in urban
air begins to resemble that in the soil (see middle
box). Finally, the bottom box in Figure 16 suggests
that the difference in each chemical's vapor pressure
is a factor that might cause the profile to shift.
33
16. Dioxins profiles in U.S. air and urban soil
(homologue group/sum of homologue groups)
TCDD
PeCDD
HxCDD
HpCDD
OCDD
TCDF
PeCDF
HxCDF
HpCDF
OCDF
TCDD
PeCDD
HxCDD
HpCDD
OCDD
TCDF
PeCDF
HxCDF
HpCDF
OCDF
TCDD
PeCDD
HxCDD
HpCDD
OCDD
TCDF
PeCDF
HxCDF
HpCDF
OCDF
Air near source
D Urban soil
0 0.5
Urban air
D Urban soil
'
0 0.5

Air near source
(adjusted)"
D
Urban soil


If
0 0.5
NOTES: a Adjusted by dividing by the
median homologue vapor pressure value.
Data from references 4.






The amount of many dioxins released is not
detected and measured, even for CDD/Fs, at most
refinery sources (as shown in this analysis). The
same is true for many other Bay Area sources.
Dioxins profiles were not be measured for many of
these sources that release dioxins to the Bay Area.
The unconfirmed possibility of OCDD and HpCDD
sources from PCP breakdown in the ambient air is
another uncertainty.
1
09-J
11
This does not decrease the
importance of other sources (OCDD is 10,000 times
less toxic than TCDD), but it could mask their pro-
files in ambient samples. Due to these uncertainties,
even a refinery source with a known profile is diffi-
cult to compare with distant environmental samples
that may also be impacted by these other sources.
Thus, Bay Area information is limited (for many
sources) on dioxins profiles of releases, on the move-
ment of different dioxins into different parts of the
environment, and on the dioxins profiles in most
environmental samples. Further, these problems have
a cumulative effect on the ability to use profile analy-
sis to trace sources. Therefore, profile analysis, if it
is useful at all in these circumstances, will be most
useful in comparing the best measured refinery
source profile (reforming)2
2
to the best measured
nearby environmental samples (from sediment sam-
ples of stations 4 through 7C in the two-mile dis-
charge canal at the same refinery).73
Figure 17 shows that the vapor pressure effect noted
above is also a factor in this comparison. When the
_source profile is adjusted for vapor pressure, it
appears similar to the sediment profile, and can
explain most of the elevated HpCDD and OCDD.
Figure 18 shows that, within each homologue group
(HxCDDs, PeCDFs, etc.), the same dioxin that is
most abundant in the source profile is also highest in
the sediment. Further, within each group the same
dioxin is least abundant in both profiles. Given the
other sources nearby in the refinery, this indicates a
reasonably good match between these profiles.
Only in one intermediate comparison do the refinery
source and sediment profiles not match. In this case
1,2,3,6,7,8-HxCDF is greater than 2,3,4,6,7,8-HxCDF
from the reformer while the opposite is true in the
34
17. Refonner stack and canal sediment profiles
(homologue group/sum of homologue groups)
TCDD
Rcfonner (unadjuslcd)D
PeCDD 0 Discharge canal scdimentb
HxCDD
HpCDD
OCDD
TCDF
PeCDF
HxCDF
HpCDF
OCDF
0 0.5
TCDD
Refonner (adjusted)a
PeCDD 0 Discharge canal sedimentb
HxCDD
HpCDD
OCDD
TCDF
PeCDF
HxCDF
HpCDF
OCDF
0 0.5
NOTES: "Adjusted by dividing by the median
vapor pressure for each homologue. bStations 4-7C.
I 00% of reformer and 99% of canal analytes
detected. Data from references 4, 22 and 73.
18. Refonner stack and canal sediment profiles
(COD or CDF/2,3,7,8 congeners in homologue group)
1.2.3,4,7,8-HxCDD
1,2,3 ,6, 7 ,8-HxCDD
1,2,3,7,8.9-HxCDD
1,2.3.7.8-PeCDF
2.3,4.7.8-PeCDF
1,2,3.4.7,8-HxCDF
1,2.3,6,7,8-HxCDF
2.3.4.6.7.8-HxCDF
1,2,3,7,8.9-HxCDF
1,2.3,4.6,7.8-HpCDF
1,2.3,4,7,8.9-HpCDF

I Refonner slack emission I
0 Discharge canal sediment
!==I
!==I



0 0.5
NOTES: 100% of rcfonner and 94% of
canal analytes (stations 4 through 7C)
detected. Data from references 22, 43.
sediment. Other refinery sources may cause this difference (and other more minor differences)
in the sediment profile, but these other refinery sources are not measured adequately to know the
exact amounts of many of the dioxins released by them.
Thus, profile analysis based on existing data is consistent with the known link between sources
in a refinery and pollution of its canal sediment, but existing data may be too limited for profile
analysis alone to prove the link - that is shown by other evidence - between refinery sources
and dioxins contamination of the Bay Area environment.
COMPARISON OF RELEASES WITH REFINERY FALLOUT FROM OTHER SOURCES:
The Regional Water Quality Control Board has estimated that fallout of CDD/F TEQ to San
Francisco Bay equals approximately 2.6 picograms per square meter per day.53 Though EPA
staff report informally that money is budgeted for gathering more information related to this
issue, however, dioxins fallout to refineries and other sites is not yet measured in the Bay Area.
Further, measurements of this fallout outside the Bay Area range over three orders of magnitude
(a thousand times), and it is not yet known how much of these vast differences are caused by
real differences between sites versus errors related to measurement techniques, which are not yet
well developed.4
Fallout includes 'old' dioxins releases that recirculate in the environment as well as
newly-formed dioxins. For example, Table 12 shows that the Water Board's estimate of fallout
to S.F. Bay from the airlOO is three times EPA's estimate of how much sources now release into
the environment.
4
The real overestimate of new source fallout is even greater, since some diox-
ins are emitted as vapor and destroyed by sunlight,
4
and many U.S. dioxins source emissions are
carried on the winds outside the U.S., while few blow west to the Bay Area.
12. U.S. dioxins releases estimated by EPA versus fallout to the S.F. Bay surface
estimated by the RWQCB (compared as pollution per square meter of area).
Estimated CDD/F TEQ (pg/yr) Area (m2)a,b Estimated pgtm2-day
U.S. emissionsc 2.800 trilli on 9,520 bil lion 0.8
S.F. Bay falloutd 1.2trillion 1.24 billion 2.6
NOTES: au.s. surface area including Great Lakes from reference 105. bs.F. Bay surface area from
references 106 and 107. CEstimate from reference 4. ds.F. Estimate from reference 100.
Consistent with the greater fallout than ongoing releases illustrated in Table 12, various compar-
isons worldwide suggest that dioxins fallout estimates exceed emission estimates by up to ten
times.
4
This could be because measurements underestimate emission, because measurements
overestimate fallout, because much of the dioxins in the air now are resuspended from old emis-
sions that built up in the environment, or because of a combination of these factors.
1

2
.4.4?.84-
94
.99
Some evidence suggests that pentachlorophenol (PCP) circulating in the air from past pollution
might be converted to OCDD by chemical reactions in water droplets hit by sunlight, and this
might be another source causing OCDD fallout to appear greater than emission from known
sources.
109
-
111
Refinery source underestimation is a factor (as shown by this report), but recircu-
lation of past dioxins emission in the atmosphere also occurs, and many researchers believe this
is a major reason why fallout is greater than emission today.4,85,87,91,93,94,108
35






Thus, two types of comparison appear possible in theory: comparison of all past and ongoing
source emission with all past and ongoing fallout; and comparison of emission today with the
portion of fallout that is from emission today. Data are limited for both comparisons, however,
because few fallout measurements separate past from present emission, and measurements of
past emission and fallout rates are even more sparse than recent measurements. Since the refm-
ers and Water Board compare fallout with ongoing emission, and present emission can be
addressed now, this analysis addresses fallout related to recent (ongoing) emission.
Bay Area fallout from distant sources should be small as compared with other areas
that have many sources to windward. As discussed above, the prevailing winds move air masses
from the Pacific Ocean over the Bay Area for most of the year. Many data provide evidence to
demonstrate that there is less dioxins contamination and fallout associated with air masses pass-
ing over large expanses of ocean than those passing over urban-industrial land areas.49,50,84-
95.99.109-111 Evidence of this effect on the U.S. Pacific coast is summarized in Table 13.
13. Comparisons indicating Jess dioxins fallout from distant sources on the continental U.S.
Pacific Coast than inland (data from ambient samples with no dominating sources nearby).
Ocean air influence Land air influence Comparison
Air: greater LA Areaa pgtm3 as TEOoF pgtm3 as TEOoF
Air mass from ocean v. land 0.057 to 0.225 0.598 tO 0.669 3 to 12 times
Sediment: continental U.s .b pg/g dry wt. as TEOoF pg/g dry wt. as TEQoF
Beaver L., WA v. inland lakes 0.86 to 0.98 5.59 to 6.36 6 to 8 times
Freshwater fish: U.s .c.d pg/g wet wt. as TEQoFP pg/g wet wt. as TEQoFP
Rural CA lake v. U.S. average 0.04 to 0.3 2.4 8 to 60 times
NOTES: Average dioxins concentrations. Ranges express uncertainty due to analytical detection problems for
some analytes: minima set results below detection to zero; maxima set these results to reported detection limit
values. aoata from reference 50. boata from references 4 and 83. CRural California lake data from reference
102. dAverage in U.S. freshwater fish from reference 4.
Air measurements summarized in Table 13 indicate that concentrations of CDD/Fs were three to
twelve times greater when the air mass measured was recently over land-based sources in the
greater Los Angeles Area (when the wind was blowing from land to sea), than during the pre-
vailing climate conditions (wind blowing from sea to land).so There is less dioxins fallout from
these ocean air masses. Average concentrations of CDD/Fs were six to eight times greater in
sediment of lakes elsewhere in the U.S. than in a lake tested near the Pacific Coast.4.83
Similarly, in freshwater fish, average concentrations of dioxins (TEQ
0
FP-WH0
98
) throughout
the U.S. are eight to sixty times greater than those in a rural California lake.4,102
This ocean air effect does not mean that total fallout of dioxins to Bay Area refineries is low. A
portion of the dioxins emitted by refineries deposits on refinery land, and the analysis of runoff,
sediment and fish above shows that refineries cause significant dioxins pollution at refineries as
well as at other Bay Area sites. Instead, this site-specific effect of climate and geography sug-
gests that fallout from distant sources is a smaller (possibly 3-60 times smaller) in the Bay Area
than on the same acreage in most parts of the U.S .
36
Refineries may collect less fallout from the same air than other sites because
\
other sites have more vegetation while refinery sites generate more heat. A given amount of
dioxins in air will deposit differently on different surfaces. Importantly, the lipids (wax) of the
leaves of plants attract dioxins strongly and collect more dioxins fallout than most other features
on land.4,S0,92,IOS Dioxins concentrations were greater in soil under trees, cow pasture, and espe-
cially vegetation-covered soil than in exposed soil in a survey of contamination associated with
pentachlorophenol burning at Oroville, CA.SO
In another study, a spruce forest collected up to 16 times more of the same dioxins that have the
highest vapor concentrations in air, but not more of the dioxins with lower vapor concentrations
(those with seven or eight chlorine atoms).
4
These hepta and octa congeners attach to particles,
deposit more strongly with particles, and are found in greater amounts near refinery sources, fur-
ther supporting this vegetation effect. This effect could be important at Bay Area refinery sites.
Visual inspections by CBE staff reveal that refinery process areas and the contiguous plant site
properties have less trees and other vegetation than typical residential and rural areas. Refinery
properties may collect relatively smaller amounts of dioxin air emission from other sources
because these dioxins are selectively attracted by vegetation at other sites.
Also, dioxins will move between air and site property differently at different temperatures.
More dioxins vaporize (evaporate) at higher temperatures. Further, localized heat sources cause
air to rise, as shown by the characteristic plumes of steam and smoke observed at refineries. In
this way, increased temperatures in and around refinery processes can reduce dioxins fallout on
refinery land, and increase dioxins movement into the air from refinery land.
Taken together, these factors suggest that dioxins fallout on Bay Area refinery land due to
ongoing sources other than refineries should be very low for distant emission (relative to urban-
industrial areas that are inland), and low for other Bay Area sources (relative to other Bay Area
sites that have more vegetation and/or generate less heat).
Accordingly, the true amount of CDD/F fallout from other ongoing sources on Bay Area refiner-
ies is more likely to approach the rate calculated from EPA's national release estimate than that
calculated from the Water Board fallout estimate in Table I 2. For purposes of comparison with
refinery releases, the same dioxin-like PCBs factor is used as in part 2 (10-60% ofTEQ), yield-
ing an estimated fallout rate of 0.89 to 2.0 picograms TEQ per square meter, per day. From
acreage given in Environmental Impact reports and Air District files, property areas at Bay Area
refineries total approximately 30.3 million square meters, and this fallout is an estimated 27 mil-
lion to 6 I million picograms per day on average.
Bay Area refinery dioxins releases given in part 2 above exceed this estimated fallout from other
sources on refinery land by 30 to 6,000 times. This finding is consistent with the findings above
that refineries contribute significant Bay Area dioxins contamination, and it thus provides fur-
ther support for the refinery release rate measured in this analysis.
This estimate is more appropriate for comparison with Bay Area refinery releases than applying
the Water Board estimate to the refineries, but Bay Area refinery releases shown in part 2 of this
analysis also exceed the fallout to refinery land that would be calculated using the Water Board
estimate. Future Bay Area air measurements that are now planned by EPA should provide better
infonnation for a more accurate region-wide fallout estimate, which is not attempted here.
37






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