UNITED STATES DISTRICT COURT EASTERN …...2016/07/19 · NO. 4:15-cv-05086-TOR (consolidated with...

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THOMAS J. YOUNG Senior Counsel JOHN A. LEVEL WILLIAM R. SHERMAN KELLY T. WOOD Assistant Attorneys General P.O. Box 40117 Olympia, WA 98504-0117 (360) 586-6770 Attorneys for Plaintiff State of Washington

UNITED STATES DISTRICT COURT EASTERN DISTRICT OF WASHINGTON

HANFORD CHALLENGE, UNITED ASSOCIATION OF PLUMBERS AND STEAMFITTERS LOCAL UNION, and the STATE OF WASHINGTON, Plaintiffs, v. ERNEST J. MONIZ, in his official capacity as Secretary, the UNITED STATES DEPARTMENT OF ENERGY, and WASHINGTON RIVER PROTECTION SOLUTIONS LLC, Defendants.

NO. 4:15-cv-05086-TOR (consolidated with NO. 4:15-cv-05087-TOR) DECLARATION OF JOYCE TSUJI IN SUPPORT OF PLAINTIFF STATE OF WASHINGTON’S MOTION FOR PRELIMINARY INJUNCTION

I, JOYCE TSUJI, declare under penalty of perjury under the laws of the

state of Washington that the following is true and correct.

DECLARATION OF JOYCE TSUJI IN SUPPORT OF PLAINTIFF STATE OF WASHINGTON’S MOTION FOR PRELIMINARY INJUNCTION

1 ATTORNEY GENERAL OF WASHINGTON PO Box 40117

Olympia, WA 98504-0117 (360) 586-6770

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I. INTRODUCTION

1. I am over the age of 18, competent to be a witness herein, and

make this declaration in that capacity. I state the following based upon my

personal knowledge. I have been requested to provide expert opinions on

behalf of the State of Washington regarding the imminent and substantial

endangerment to worker health and safety that is presented by volatile organic

compounds in the tank farms at the Hanford Nuclear Reservation.

A. Qualifications

2. I am a toxicologist and am employed as a Principal Scientist at

Exponent, a multidisciplinary sciences and engineering firm. I completed a

Ph.D. focused in physiology and ecology with postdoctoral research related to

quantitative genetics in the Department of Zoology (now Biology), University

of Washington. I am a Fellow of the Academy of Toxicological Sciences and

have been continuously certified in toxicology by the American Board of

Toxicology since 1992. I have served on various expert scientific committees

for the National Academy of Sciences (NAS)/National Research Council

(NRC), Institute of Medicine (IOM), U.S. Environmental Protection Agency

(EPA), and the State of Washington. My relevant appointments for this matter

include NAS/NRC’s Board on Environmental Studies and Toxicology,



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Committee on Toxicology, NAS Spacecraft Exposure Guidelines for chemicals

in air and water (sponsored by the U.S. National Aeronautics and Space

Administration), NAS Submarine Escape Action Levels for airborne

contaminants in disabled submarines (sponsored by the U.S. Navy), NAS

Submarine Emergency and Continuous Exposure Guidance Levels for Selected

Submarine Contaminants in operating submarines (sponsored by the U.S.

Navy), the IOM Committee on Airborne Hazards and Open Burn Pit Registry

(sponsored by the U.S. Department of Veterans Affairs), and the NAS Standing

Committee on Emerging Sciences in Health Decision Making (sponsored by the

U.S. National Institute of Environmental Health Sciences). I am also a member

of the Society of Toxicology and a member of Specialty Sections on Risk

Assessment, Medical Devices, and Nanotoxicology.

3. From 1987 until the present, I have worked as an environmental

consultant conducting, overseeing, and reviewing human health risk

assessments and exposure studies. I am familiar with exposures and health

effects of volatile organic chemicals from my service on expert committees and

numerous projects involving exposures and risk assessment of volatile organic

and inorganic chemicals, as noted in the section of my curriculum vitae on

airborne exposures. I have published in the peer-reviewed scientific literature



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on risk assessment, toxicology, biomonitoring (including mercury vapor), and

exposure pathways to substances in the environment. My current curriculum

vitae is attached as Exhibit 1.

B. Data and Other Sources of Information Considered

4. In addition to my education, experience, and training, I considered

the materials listed in the Appendix attached at the end of this declaration, the

Declarations of Bruce Miller, Russell Ogle, and Charles Halbert.

C. Limitations

5. This declaration summarizes work performed to date and presents

the findings resulting from that work. The findings presented herein are made

to a reasonable degree of scientific certainty. I reserve the right to supplement

this declaration and to expand or modify opinions based on review of additional

material as it becomes available through ongoing discovery and/or through any

additional work or review of additional work performed by others, including

additional sampling performed by any party to this litigation.

II. SUMMARY OF CASE BACKGROUND AND OPINIONS

A. Site History Related to Volatile Chemical Health Risks

6. There are 18 tank farms at the Hanford site in southeastern

Washington State; these farms contain 177 underground tanks that store 56



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million gallons of concentrated waste remaining from plutonium production

from 1943 to 1987. See Figure 1. In addition to radioactivity, the waste

contains thousands of other organic and inorganic chemicals that comprise

volatile air emissions. A multitude of chemicals within the waste are

continuously being produced and transformed through complex chemical and

radiolytic reactions. The radioactivity further enhances chemical reactions by

production of free radicals (strong oxidizers) and heat.

Figure 1. Hanford Site tank farms noted by letter code.

7. The first of the 149 single-shelled tanks (SSTs) were built to

contain waste in 1944, and over 60 of these tanks are known or suspected of

leaking waste into the surrounding soil. The 28 double-shelled tanks (DSTs)



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were built beginning in 1968. Since 1987, activities at the site primarily

concern management and remediation of waste in the aging tank farms.

Considerable efforts have focused on containment of waste from leaking or

potentially leaking tanks, and transferring waste from the SSTs to the DSTs.

Waste is also transferred among DSTs as needed to manage and contain the

material. Single-shelled tanks after waste retrieval still contain residual waste

that cannot be completely pumped from the tank. See Figure 2. These tanks

have a lower layer of residual interstitial liquid, covered by a layer of sludge

and salt cake over which lies a supernatant with a headspace of gases above.

Similar layers also occur in DSTs. See Figure 3. During waste retrieval, liquid

from other tanks may be introduced to break up or sluice the tank layers.



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Figure 2. Diagram of single-shelled tank.

Figure 3. Diagram of double-shelled tank.



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8. DSTs may also leak liquid waste between the shells, as has

occurred for tank 241 AY-102. As a result, pumping of waste has been ongoing

from this tank to other DSTs.

9. As vapors build up in the head space of the tanks from heat and

ongoing chemical reactions in the residual waste, the tanks release gases from

vents. The SSTs have passive ventilation and release periodically depending on

the pressure increase in the tank, whereas the DSTs have active forced

ventilation on a schedule.

10. Vapor releases from these tanks have regularly resulted in noxious

odors and health concerns to workers since at least 1977 to the present.

Numerous reports by the Department of Energy (DOE or Energy) and their

contractors for the past two decades have noted worker exposures to the

chemical vapors in the tanks as a health concern, assessed the toxicity of

chemicals of concern, and made recommendations for further assessment and

actions to prevent such health risks (e.g., Brown, et al. 1992; Maughan, et al.

1997; Stenner, et al. 2001; DOE 2004; NIOSH 2004; Burgeson, et al. 2004;

Mackerer 2006; Poet, et al. 2006; Anderson, et al. 2007; Jabara and Farler 2008;

Shultz and Knight 2008; Hanford Concerns Council 2008, 2010; TVAT 2014).

The recent independent expert review conducted in 2014 by the Tank Vapor



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Assessment Team (TVAT) of the Savannah River National Laboratory was the

latest comprehensive review of this issue, and made 10 overarching

recommendations, each with a number of detailed recommendations to address

worker health concerns. As noted by the TVAT Report: “The ongoing emission

of tank vapors, which contain a mixture of toxic chemicals, is inconsistent with

the provision of a safe and healthful workplace free from recognized hazards.”

See Declaration of Bruce Miller (Miller Decl.), Ex. 6 at 15. I agree that the

continued and frequently unpredictable emissions of tank vapors pose a serious

threat to worker safety.

11. In response to the TVAT Report, Washington River Protection

Solutions (WRPS), the DOE contractor at the site for administering the worker

health and safety program, released an implementation plan in 2015 to address

the TVAT’s recommendations. See Miller Decl., Ex. 8. However, worker

exposure incidents needing medical attention have continued to occur, with

approximately 60 worker exposure incidents reported to the onsite medical

clinic this year.

B. Summary of Opinions

12. I was asked to provide an assessment from a toxicological

perspective on whether worker exposures to volatile chemicals from the tank



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farms could result in a risk of serious health effects to Hanford tank farm

workers. A summary of my opinions is as follows:

a. Hanford tanks contain complex mixed radioactive and

chemical wastes involving thousands of organic and inorganic chemicals;

these chemicals are present in both the waste itself and in tank headspace

vapors.

1) Mixing of waste among tanks has resulted in

somewhat similar chemical composition overall among tanks and

over time; however, despite the number of samples analyzed,

characterization of the chemical content and concentrations of

tanks is limited by the large number of tanks, mixing of wastes,

and dynamic nature within tanks involving chemical and radiolytic

reactions and internal and external conditions (e.g., pressure and

temperature). Reported ranges in concentrations therefore do not

completely characterize tank headspace conposition and

concentrations, meaning that chemicals may be present at

concentrations that are higher than reported.

b. Workers in and around the tank farms have been, and

continue to be, exposed to elevated levels of chemicals from the tanks.



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1) Acute high-dose bolus exposures to largely undiluted

tank chemicals from venting of vapors, tank leakage, or releases

during waste disturbance have resulted in worker exposure events

for decades; recent reports of exposure events demonstrate that

these exposures continue to occur.

2) Longer-term exposure incidents over several hours

have also led to workers seeking medical attention.

3) Higher exposure concentrations are not well

quantified and the evidence indicates that vapor concentrations can

be even higher than measured.

c. Hanford tank farm headspace vapors contain some of the

most toxic chemicals known, as well as other toxicants that have been

reported to cause serious health impairment and even fatalities with acute

high-dose exposures. These chemicals, individually and collectively, can

be extremely harmful to human health.

1) Numerous site reports and the scientific literature

have acknowledged the toxicity and risk of serious health effects

posed by these chemicals.



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2) Many of the chemicals contribute to upper and lower

respiratory tract irritation and tissue injury, in addition to possible

neurological effects from acute exposures.

3) Numerous chemicals present in the tanks are also

carcinogenic or are of higher toxicity.

d. Tank exposures cause health effects and pose risks of

serious, irreversible impairment.

1) Workers have been, and continue to be, exposed to

chemical vapors at levels that require medical attention and have

led to adverse health impacts.

2) While it is possible to recover from some of these

health impacts with proper treatment, a subset of these health

effects are not immediately reversible, and some workers have

experienced permanent damage to their health.

3) Reported chemical concentrations in tank vapors for

certain chemicals individually are sufficiently high to cause or

contribute to serious health effects. The potential for higher

chemical concentrations, frequent worker exposures resulting in



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medical attention, and the combined effect of multiple chemicals

further increase the risk of serious health effects.

4) Without better characterization of bolus (i.e., short

duration, high concentration) exposures and the toxicity of tank

vapor mixtures, DOE and WRPS cannot effectively ensure that

workers are protected from serious health effects.

III. BASIS FOR OPINIONS

13. To form an opinion regarding the potential exposures and health

risks alleged in this case, I followed well-established toxicology and risk

assessment principles with consideration of relevant site-specific data and the

current scientific literature, including knowledge regarding the adverse effects

of acute exposures to volatile chemicals as well as potential chronic or long-

term consequences of such exposures. The following opinions express findings

in accordance with the general steps for assessing health risks from chemical

contamination of hazard identification, exposure evaluation, toxicity

assessment, and risk characterization (U.S. EPA 1989).

A. Hazard Identification: Hanford Tanks Contain Thousands of Chemicals in Both Waste and Headspace Vapors

14. Tank headspace vapors have been reported to contain thousands of

chemicals, whose concentrations and composition depend on dynamic



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conditions involving formation of chemical intermediates in the waste as

enhanced by the energy from the radioactivity, as well as temperature and

pressures relative to external conditions. Internal and external pressure

equalization is achieved via passive or active venting of vapors from tank

headspaces. A 2006 report by CH2MHill noted that 118 of the 149 SST

headspaces had been sampled, and although concentrations of chemicals could

vary over time depending on conditions, 95% of the chemical concentrations

within a tank varied by no more than 3 times (e.g., 100 to 300 ppm) for a given

chemical. See Ex. 2 at iii. Attached as Exhibit 2 to my declaration are true and

correct copies of excerpts from the CH2MHill, Industrial Hygiene Chemical

Vapor Technical Basis (May 2006). The 2006 CH2MHill report also noted that

the composition and concentrations of chemicals among tanks are generally

similar, which is consistent with the mixing of waste over time. Ex. 2 at 22.

Despite this overall similarity, concentrations of individual constituents are

variable within and among tanks at any given time, because of the complex and

dynamic processes that affect chemical composition and concentrations as

described by the 2006 CH2MHill report.

15. In spite of all of the sampling, the large number of tanks and the

dynamic nature of the waste/headspace vapors create considerable uncertainty



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regarding whether adequate characterization of chemical concentration

excursions has been completed, particularly those associated with a bolus event

that might cause harm to workers. A 2004 report noted that most tanks sampled

have only been sampled once, and some of the sampling methods were not able

to detect certain compounds, such as small molecular weight compounds (e.g.,

ammonia, nitrous oxide, formaldehyde) or unidentified organic compounds.

See Ex. 3 at 3. Attached as Exhibit 3 to my declaration is a true and correct

copy of a report Pacific Northwest National Laboratory (PNNL), A Survey of

Vapors in the Headspace of Single-Shell Waste Tanks (July 2004). In

summarizing maximum chemical concentrations, chemicals that could not be

separated in the analytical methods or that occurred as part of mixtures, were

further eliminated. Ex. 3 at 5. A review in 2008 likewise noted that not all

tanks have been sampled; only 30% have been sampled more than once, and a

comprehensive sampling strategy of tank headspace vapors during static and

waste disturbing activities was lacking (Hanford Concerns Council 2008).

16. Much of the sampling data also does not include periods or

situations in which tank chemical concentrations may be higher. Miller Decl.,

Ex. 6 at 27 (TVAT 2014). For example, sampling the tank headspace during

quiescent periods does not capture the concentrations that might occur just prior



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to a release event from increased tank pressure from chemical reactions, nor

does it represent conditions during waste disturbance activities, which can

greatly increase vapor concentrations (Stewart, et al. 2005). Even assuming the

variation in concentration reported by the 2006 CH2MHill report, 5% of the

time concentrations of chemicals varied by more than 3 times (e.g., 100 to 1000

ppm would be a difference of 10 times). Ex. 2 at 22. Thus, more extreme

concentrations, although infrequent, do occur and if they are associated with

conditions resulting in a release (increased tank pressure, accidental release,

leakage, or waste disturbance), could result in higher worker exposures.

17. The primary types of chemicals reported from analyses of tank

headspace vapors include inorganic constituents (e.g., hydrogen, nitrous oxide,

ammonia, carbon monoxide, carbon dioxide, elemental mercury, and sulfur-

containing compounds) and a variety of organic chemicals including alcohols;

ketones; ethers; esters, aldehydes; halogenated compounds; nitriles; aliphatic,

alicyclic, heterocyclic and some aromatic hydrocarbons, and dimethylmercury

(Stock and Huckaby 2004; Meachum 2006a,b).

18. Several DOE-sponsored studies have evaluated a short list of tank

chemicals of potential concern for worker health. The goal of identifying

potential chemicals of concern is to focus more detailed assessments of



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exposure and health risk as well as to provide information to guide industrial

hygiene sampling efforts. Burgeson, et al. (2004) recommended 52 chemicals

of potential concern based on: (1) a toxicological evaluation of chemicals

measured in tank headspace samples, and (2) on those chemicals predicted to be

present based on waste analyses. High priority chemicals recommended for the

industrial hygiene program included six known human carcinogens, 18

probable carcinogens,1 27 chemicals that were present in tank head space

samples at concentrations at least 10% of their lowest occupational exposure

guideline level,2 and dimethylmercury, a highly toxic form of mercury.

CH2MHill reviewed all tank characterization data as of January 2006 and

evaluated 1826 chemicals previously identified, 52 chemicals of potential

concern, 1538 chemicals needing further evaluation, and 236 chemicals with

low probability of exposure. Ex. 2 at 33. Based on this evaluation, CH2MHill

1 Chemicals found to be carcinogenic in animal studies that have no or

limited evidence of carcinogenicity in humans.

2 A screening level of 10% of a health-based limit is often used in an

attempt to account for potential additive effects when multiple chemicals are

present.



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developed a list of 48 chemicals of potential concern for worker health. Ex. 2 at

39. Finally WRPS currently lists 59 chemicals of potential concern. Attached

as Exhibit 4 to my declaration is a true and correct copy of WRPS’s list of

Chemicals of Potential Concern.

19. Although much of the sampling data is not recent and is largely

from headspace samples of SSTs, the contents of SSTs were and are being

pumped to DSTs, and WRPS noted in a May 2016 presentation that their recent

sampling data are similar to the previous sampling data. See Declaration of

Thomas Young (Young Decl.), Ex. 13, WRPS May 11, 2016 PowerPoint, Tank

Farm Vapors Protection Update (headspace samples taken since fiscal year

2015 “[v]alidated that previous characterization has not changed”). As part of

my review of tank waste documentation, I also have reviewed information from

Energy’s tank waste information systems (TWINS) database which contains

Energy’s data characterizing the Hanford tank wastes, including waste

measurements and sampling data. Most of the available data on the TWINS

database dates from 2005 and earlier.

20. For the purpose of this declaration, I developed a short-list of

chemicals of potential concern to evaluate the potential for serious health risks

(Table 1). I developed this list based on comparison of maximum reported



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levels of chemicals (e.g., Burgeson, et al. 2004; Anderson, et al. 2006;

Meachum, et al. 2006a,b; Hughey and Farler 2008) to short-term exposure

limits and occupational exposure levels with some consideration of the number

of tanks in which chemicals were detected. Following previous approaches

(e.g., Burgeson, et al. 2004), known human carcinogens were also included, and

some similar chemicals within a class (e.g., nitriles).

Table 1. Summary of initial list of chemicals for further evaluation

Chemical Name CAS RN 1,1'-Biphenyl 92-52-4 1-Butanol 71-36-3 3-Buten-2-one (methyl vinyl ketone) 78-94-4 Acetaldehyde 75-07-0 Acetonitrile 75-05-8 Ammonia 7664-41-7 Benzene 71-43-2 Butanenitrile 109-74-0 Dimethylmercury 593-74-8 Ethylamine 75-04-7 Formaldehyde 50-00-0 Mercury 7439-97-6 Methanol 67-56-1 Nitrous oxide (N2O) 10024-97-2

21. This assessment, of course, does not include the additive effects of

the many other chemicals that are present at lower levels compared to effect

levels. The additive effects of multiple chemicals in a mixture is discussed in

more detail below in paragraphs 77–81 regarding the assessment of chemical



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toxicity. In brief, the combined exposure to all chemicals present in tank vapor

releases contribute to the potential for health effects. Because of the multiple

chemicals involved (not all of which have been characterized), chemical

interactions are complex and difficult to assess. A number of chemicals have

similar effects (e.g., irritation or injury to the eyes or the respiratory tract lining

or nervous system effects). The action of such chemicals are expected to be

additive and potentially could be synergistic in which even greater than

expected harm may result.

B. Exposure Evaluation: Workers at the Tank Farms are Exposed to Elevated Levels of Chemicals Emitted by the Tanks

22. A large number of WRPS or DOE employees or contractors work

in the area of the tank farms. These workers are involved in a wide variety of

activities associated with monitoring, construction, and maintenance around

tanks, as well as in actively retrieving wastes and moving wastes among tanks.

Workers in the tank farm area who may be exposed to vapors include chemical

operators, tank farm specialists, training coordinators, pipe-fitters, general

maintenance workers, administrators, electricians, safety representatives,

project planners, health physics technicians, engineers, project facilitators,

carpenters, and quality control inspectors. See Young Decl., Ex. 2 (NIOSH

2004) at 8. Many workers perform their duties without personal protective



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equipment that would prevent exposure to chemical vapors (e.g., respiratory

and full-face protection equipment).

1. Exposure pathways to tank farm vapors

23. Workers have been and continue to be exposed to tank farm vapors

by various pathways or means of exposure, most notably:

a. Headspace venting through passive (SSTs) or active

mechanisms (DSTs) release chemical vapors. In the case of SSTs,

venting occurs sporadically from increased pressure within the tank due

to change in external barometric pressure or internal pressure from heat

and chemical byproduct formation in the waste that is released to the

headspace. In the case of DSTs, venting occurs on a set timeline via

controlled/engineered processes.

b. Vapors escaping underground from tanks that travel along

piping and electrical conduits and collect in weather-tight electrical

cabinets or other enclosed areas, thereby resulting in exposures when

such areas are opened or disturbed.

c. Release of vapors from fittings, valves, risers, or other tank

fixtures during maintenance or sampling activities.

d. Release of vapors from the 242-A Evaporator unit.



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e. Leakage or spills of waste, and/or release of headspace

vapors, during tank waste retrieval and transfer among tanks (i.e., waste

disturbing activities).

24. Exposure scenarios involving various types of workers and work

maintenance and operation activities at the tank farms have been described by

Stenner, et al. (2001) (Table 2). As presented by the various examples in this

table, workers have a number of opportunities to be exposed to elevated levels

of vapors released from the tanks.

Table 2. Worker Exposure Scenarios for Tank-Farm Operations Source: Stenner et al. (2001)

Type of Work Example Activities

Personnel in Main Area of Activity

Estimates for Task High-Risk

Exposure Time ( hours) Times/

Week Hours/ Task

Equipment installation (Waste-intrusive) Installation/removal of pump in waste

Health Physics and Industrial Hygiene technicians, Operations personnel, Electricians, Pipefitters, Riggers, Truck drivers

1 8 3

Saltwell pumping Line flushing

Health Physics and Industrial Hygiene technicians, Operations personnel, Pipefitters

5 12 3

Waste transfer Work around tanks, lift stations, valves

Health Physics and Industrial Hygiene technicians, Operations personnel, Pipefitters

1 8 4

Vapor pit reconfiguration Nozzle set up for waste transfer

Health Physics and Industrial Hygiene technicians, Operations personnel, Electricians, Pipefitters

1 8 3

Core sampling Setup/removal of equipment in waste

Health Physics and Industrial Hygiene technicians, Pipefitters, Riggers, Electricians, Instrument technicians

3 8 2



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Type of Work Example Activities

Personnel in Main Area of Activity

Estimates for Task High-Risk

Exposure Time ( hours) Times/

Week Hours/ Task

Maintenance activities (Waste-intrusive) Removal of equipment previous installed in waste

Health Physics and Industrial Hygiene technicians, Operations personnel, Electricians, Pipefitters, Riggers, Truck drivers

1 8 4

Pressure tests of transfer lines Bleed off gas in lines

Health Physics and Industrial Hygiene technicians, Pipefitters, Operations personnel

1 8 4

Ventilation testing and maintenance Near tank release points

Vent and balance personnel, Health Physics and Industrial Hygiene technicians, Operations personnel

2 8 4

Tank-intrusive activities Insert equipment in tank dome

Health Physics and Industrial Hygiene technicians, Operations personnel, Electricians, Pipefitters

3 8 3

Operation routines Tank monitoring and data collection

Health Physics and Industrial Hygiene technicians, Power operators, Operations personnel

5 12 4

Notes: Personnel listed have the highest probability of chemical exposure. Each activity would also include support personnel located farther away. Frequencies and duration of exposures are estimated and are highly variable, depending on the job and the requirements for the activity. The high-risk exposure time is the approximate time during an activity that personnel are at a higher risk for chemical exposure.

2. Reported exposure event

a. Frequency of events

25. Tank vapor problems have been ongoing for decades since at least

1977 Miller Depo., Ex. 6 (TVAT 2014). In more recent times, the number of

tank vapor exposure cases for 2001, 2002, 2003, and the first quarter of 2004,

were 9, 21, 30, and 10, respectively, Young Decl., Ex. 2 (NIOSH 2004).

Hocking (2005) reports even greater numbers of “vapor incidents” recorded in

the tank farm shift log for these years (32, 26, 49, and 25, respectively).



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Despite investigations of these events and recommendations to prevent such

exposures (e.g., DOE 2004; NIOSH 2004; DOE 2007; Hanford Concerns

Council 2008), the number of exposures in recent times has shown no sign of

decline. For example, 91 exposure incidents involved workers visiting the

onsite medical clinic between October 1, 2008 and March 31, 2010 (Hoffman

2010). A few workers during this period experienced such exposures more than

once (up to 3 times). Two separate incidents also resulted in workers being

referred to a hospital. An investigation of these incidents found no clear

relationship with industrial hygiene sampling results, although more symptoms

were associated with waste disturbance activities such as retrieval and

transferring of waste (Hoffman 2010). In “vapor incidents” recorded in shift

logs from 1995 through 2004, incidents involving SSTs (34%) and DSTs

(39.1%) were about equal (Hocking 2005). As noted by TVAT (2014),

industrial hygiene sampling is unable to characterize the peak concentrations

involved in these bolus exposures.

26. Between March 19 and April 3, 2014, 25 workers were exposed

and received medical evaluations. Young Decl., Exs. 13, 14. Since the 2014

TVAT review and recommendations and the implementation of the plan in

response to the TVAT Report by WRPS, vapor exposure events continue to be



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reported. These exposures have primarily occurred during the ongoing retrieval

and transfer of waste from the leaking DST 241 AY-102 to the AP tank farm.

Based upon review of WRPS’ publicly available data on AOP-15 (“Abnormal

Operating Procedure” or vapor exposure events), in 2015, 12 exposure events

occurred involving various numbers of workers at the effluent treatment facility,

242A Evaporator, and at or near tank farms SY, C, AZ, AY, and AN. In

addition, another vapor exposure event was reported in 2015 that was not

associated with a specific tank farm. In 2016, 14 exposure events occurred at

the 200-East area, including tank farms TX, AZ, AW, AP, AN, and A as well as

the 242-A Evaporator (WRPS 2016c). In one week in particular this year,

44 workers reported to the onsite medical clinic as a result of exposure events

on April 28, May 2, May 3, and May 4. See Young Decl., Ex. 14.

27. A summary of AOP-15 events in spring of 2016 by WRPS,

includes 48 workers who were exposed in the week of April 28 through May 3,

2016, as well as on April 6, 7, 11, and May 4, 2016, and were medically

evaluated. See id.; see also WRPS 2016b regarding definition of Abnormal

Operating Procedure 15. The majority of the workers had exposures associated

with the AP-Farm where waste from the leaking DST tank (AY-102) is being

pumped. At this location, most workers were exposed during waste disturbing



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activities, although some are noted as exposed during static conditions. Id.

Exposures at other locations in the tank farm areas are noted as well. Id. Most

workers were evaluated on the same day as the exposure event, but a few were

evaluated a day or more after the event. In addition, 10 other workers were

medically evaluated for vapor exposure between April 25 and May 17, 2016,

but were not associated with an official “Abnormal Operating Procedure 15”

exposure event. Id.

b. Nature of exposure events

28. In most cases, reported exposures are intense and relatively brief

causing workers to immediately exit the area and seek medical attention.

Exposures to vapors may also involve longer durations or repeated exposures to

varying concentrations. For example, during waste disturbing activities such as

retrieval of supernatant from Tank C-104 on January 25, 2010, workers were

smelling odors over a work shift (Klug 2010). Odors intensified and workers

began having more symptoms which continued into the next day. A spill event

on July 27, 2007, resulted in worker exposures and later health symptoms (DOE

2007). The accident investigation report noted that the event could have been

more severe if workers had been in the immediate vicinity of the spill at the

time the release happened. Workers had been present at that location just



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10 minutes prior to the release (DOE 2007). Modeling by the contractor

indicated a relatively brief peak exposure period; however, as noted by DOE

(2007), modeling assumptions may not be correct and elevated levels may not

have dissipated quickly.

29. Exposures to workers of varying durations that are not reported as

exposure events also appear to occur with some frequency (see Declarations of

Rose Calderon, Seth Ellingsworth, Abelardo Garza, David Fritch, Guy Johnson,

and Kevin Newcomb). Workers who are unable to smell the vapors may be

exposed to elevated concentrations without warning (see Declaration of

Abelardo Garza).

30. In some of the recent exposures reported during waste retrieval and

transfer among tanks, reduction in the respiratory protection exclusion zone has

resulted in exposure events outside this zone (Hanson 2016). Longer duration

of exposures or repeated acute exposures are also possible during waste

transfer. Such exposures are typically below industrial hygiene limits based on

monitoring results, although such monitoring has limitations for characterizing,

particularly brief exposures (TVAT 2014).



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3. Exposure concentrations

31. Sampling of chemical vapors at the tank farms has generally been

reported to be within occupational health and safety limits for time-weighted-

average exposures). See Miller Decl., Ex. 6 at 17, 47 (TVAT 2014). Sampling

at release events has occasionally resulted in levels exceeding short-term or

long-term time-weighted-average limits. As noted in the TVAT Report,

however, the sampling methods used are incapable of capturing the peak

exposures associated with bolus releases that have resulted in the need for

medical attention by workers, and sampling often was conducted some time

after the exposure event. See Miller Decl., Ex. 6 at 17 (TVAT 2014). Problems

with sample collection, handling, and industrial hygiene staff training have also

been reported (Declaration of Kevin Newcomb). Actual exposures can thus

greatly exceed the reported concentrations. As a result, I concur with the TVAT

Report’s conclusions that the reports of worker exposures being within

occupational exposure limits are not reliable for assessing potential health risks

to workers, and are insufficient to assure worker safety. See Miller Decl., Ex. 6

at 17.

32. As noted previously, chemical concentrations can be even higher

than measured even under relatively static conditions because, despite the



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number of samples collected, characterizing the full range of potential

concentrations in a complex dynamic system within tanks is not possible

without continuous sampling of tanks over time; such sampling is not done at

the Hanford tank farms. In addition, concentrations of chemicals would be

higher during waste disturbance in tanks than during quiescent periods (TVAT

2014), because of massive liberation of chemicals arising in the waste layers

compared to slow migration by diffusion into the headspace or by periodic,

smaller-scale releases (burps). Stack concentrations of DSTs may be diluted

relative to an individual tank because exhaust from more than one tank is

vented through a common stack. In such a situation, the individual

contributions from the different tanks is unknown.

33. Modeling assessments of vapor releases from tanks by Droppo

(2004) and the TVAT Report indicate that workers could be exposed to nearly

undiluted concentrations within a meter of a release, depending on local

environmental conditions. The TVAT Report estimated that 97% of the

headspace concentration would be present at one meter from the release point,

and 81% of the concentration would be present at three meters (about 10 feet).

Miller Decl., Ex. 6 at 87. Thus, maximum measured concentrations are

indicative of potential exposures to workers and, in fact, are likely not the



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highest possible exposures given the limitations of sampling (see also

Declarations of Bruce Miller, Russell Ogle, and Charles Halbert on the issue of

sampling and exposure concentrations).

C. Toxicity Assessment: Chemicals Within Headspace Vapors Individually and Collectively are Harmful to Human Health

34. The primary adverse effects induced by bolus exposures to the

chemicals measured in tank headspaces are eye and respiratory tract irritation

and potential damage, as well as neurological effects, such as dizziness,

headache, nausea, and other central nervous system effects.

35. For example, ammonia has been measured in a number of tanks at

levels that would individually cause offensive odors, irritation, and

potentially more severe effects. Other chemicals with maximum levels that

may also individually cause odor and irritation effects include

n-nitrosodimethylamine, n-butanol, and 2-buten-3-one (methyl vinyl ketone).

Those most likely chemicals contributing to neurological effects include

propanenitrile, nitrous oxide, n-butanol, and potentially elemental and

dimethylmercury. The collective effects of the entire mixture of chemicals

should also be evaluated for its combined toxicity. For example, hydrocarbon

and organic chemical mixtures can cause both eye and respiratory tract



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irritation/damage and central nervous system effects. The impacts of exposure

to these chemicals is discussed in greater detail below.

1. Toxicological principles and health effect limits related to accute exposures to volatile chemicals

a. Effects of concentration, time, and chemical properties on toxicity

36. The toxicity of airborne chemicals is typically related to the

concentration and duration of exposure, resulting in greater toxicity as

concentration and/or duration of exposure increase. At sufficient

concentrations, even brief exposures can cause serious harm to exposed

individuals. Effects produced by brief exposures to a chemical, if not

excessively high, may be reversible with proper treatment and recovery.

However, with longer exposure durations or repeated exposures, less recovery

is possible. Additionally, chemicals with high water solubility and chemical

reactivity, such as ammonia, alcohol, or aldehydes, dissolve readily into mucous

membranes and thus can cause immediate effects on these tissues (Jegal and

Kim 2016). The toxicity of these chemical are thus less time-dependent,

consistent with the harmful effects that occur from acute bolus exposures.

Highly soluble and chemically reactive vapors affect primarily the eyes and

upper respiratory tract (e.g., nose, throat), whereas less soluble chemicals such



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as nitrogen dioxide would affect the deeper lung (Jegal and Kim 2016). As the

airborne concentration increases, however, even more soluble chemicals are not

effectively scrubbed by the upper respiratory tract, resulting in effects along the

entire respiratory tract.

37. For substances causing central nervous system toxicity, rapid

uptake into the bloodstream and the brain facilitates greater toxicity with dose.

Mercury vapor and dimethylmercury both are highly fat soluble and rapidly

cross biological membranes (Berlin, et al. 2015). A number of organic

chemicals also cause central nervous system effects at higher concentrations

(e.g., hydrocarbons, McCoy 2008a).

b. Persistent or irreversible effects of acute exposure

38. Acute exposures to tank vapors, if sufficiently high or repeated,

can lead to more serious effects that are not immediately reversible. For

example, irritant gases (e.g., ammonia) or mixtures of gases have been

associated with damage to the air-exchange sacs in the lungs (aveoli; potentially

resulting in interstitial fibrosis or acute airway distress syndrome), pulmonary

edema (chemical pneumonia), and bronchitis and bronchiolitis (Akira and

Sugnuma 2014; Jegal and Kim 2016).



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39. Clear central nervous system effects are readily identified at high

chemical exposure levels. At lower exposure levels, however, such effects are

more subtle and difficult to distinguish as related to the exposure, and may

include effects such as inability to concentrate, memory loss, sleep disturbance,

headaches, anxiety, weakness, and apathy (Bolla 1991).

c. Individual differences in susceptibility

40. Individuals may vary in their susceptibility to the effects of

airborne chemical exposures. At lower concentrations, such susceptibility may

be related to differences in odor detection. At higher exposures causing direct

effects on tissues, individual responses are likely to be less variable because of

less dependence of toxicity on chemical metabolism by organs such as the liver

or on pharmacokinetic and pharmacodynamic efficiency, which can vary among

individuals. Toxicity of chemicals that are affected by metabolic enzymes in

respiratory tissue, however, can show differences in sensitivity among

individuals. For example, alcohols, such as n-butanol, are metabolized to

aldehydes which are more reactive and damaging to tissues than alcohols.

Alcohols thus contribute to aldehyde (e.g., formaldehyde) toxicity in tank

vapors, and individuals who are less able to reduce levels of aldehydes in their

respiratory tissues because of genetic susceptibility will suffer greater irritation



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and tissue damage (NRC 2009).

41. Older workers may be more susceptible than younger workers as

noted below for potential lung injury from ammonia exposures. Asthmatics and

those with prior respiratory disease or limitations would also be more sensitive

to lower respiratory tract exposures and effects of airborne chemicals.

Individuals may differ in susceptibility to the central nervous system effects of

chemicals, although such differences for acute effects have not been as well

studied. Although workers are considered to be healthier than the general

population, and Hanford workers receive health physicals prior to being cleared

for work, individuals may still differ in susceptibility and worker exposure

limits are therefore stated to protect nearly all workers, but not all (ACGIH

2016). Pregnant women may also represent a susceptible population because

effects on the developing fetus may result from relatively brief exposure during

gestation. Although pregnant women may be excluded from some duties, those

in the early stages of pregnancy may not know they are pregnant.

d. Extrapolation from animal data

42. In the absence of complete information in humans, the relationship

between dose and the magnitude and nature of response is quantified in

laboratory animals. For airborne chemical exposures, data in laboratory



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animals may also be useful for distinguishing between concentrations that

produce odors and subjective effects from those with more serious toxicity

(Arts, et al. 2006). In extrapolating between animals and humans, uncertainty

factors are typically used to be protective of possible greater sensitivity in

humans. For direct effects on the eyes or respiratory tract, however, less

difference between species is likely.

e. Acute toxicity limits

43. Short-term limits that provide useful benchmarks for assessing

bolus tank vapor exposures include short-term workplace limits such as ceiling

limits (peak exposure allowed in the workplace) or the National Institute for

Occupational Safety and Health’s (NIOSH’s) limit of Immediately Dangerous

to Life or Health. In addition, for chemicals lacking a ceiling limit, according

to TVAT (2014), a ceiling limit may be derived by multiplying the 8-hour

time-weighted-average exposure limit value for a chemical by five. TVAT

(2014) based this derivation on the statement of the American Conference of

Governmental and Industrial Hygienists (ACGIH) that under no circumstance

should exposures in the workplace exceed a level of 5 times the time-weighted-

average limit.



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44. In consideration of the relative severity of effects from acute

exposures, protective action criteria summarized by DOE (2016) were also

considered (protective action criteria are acute guideline levels intended to

assess exposure to the general public from chemical releases). The three tiers of

these levels include: (1) mild, transient health effects; (2) irreversible or serious

health effects that could impair the ability to take protective action; and (3) life-

threatening health effects. Some of these levels are based on acute exposure

guideline levels set by U.S. EPA (2016). In such cases, we focused on those

based on the shortest exposure time (10 minutes). Chemicals without acute

exposure guideline levels have temporary acute limits set by the DOE and are

based on 60-minute exposures. Although workers are considered less

susceptible than the general public, these limits are useful benchmarks for

assessing potential acute effects for more sensitive workers. Several of the

chemicals with immediate direct acting effects are also expected to be more

dependent on concentration than on exposure time.

2. Ammonia 45. Ammonia forms a colorless gas that is detectable at an odor

threshold as low as 5 ppm, with a penetrating odor at 53 ppm (EPA 2007). It is

very soluble in water and forms the highly alkaline (high pH) and corrosive



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compound, ammonium hydroxide (and heat), in the presence of moisture, such

as the surface of the eye or the respiratory tract lining. As a result, ammonia is

readily absorbed producing immediate effects when it contacts the eyes, mouth,

nose, and respiratory tract (NRC 2008). Sufficiently high doses cause

immediate damage, including severe irritation (resulting in airway inflammation

and tissue damage), and chemical burns, including to the skin. Much of inhaled

ammonia is absorbed by the upper respiratory tract, where effects are localized

to the nose and throat. At higher concentrations, above 500 ppm to around

1000 ppm, more ammonia will reach the lower respiratory tract. Case studies

of people exposed to ammonia indicate that very high concentrations result in

pulmonary edema and can be permanently damaging to the lungs (including

bronchiectasis, persistent air-flow obstruction, and bronchiolitis obliterans) or

lethal and that the severity of effects depends on concentration and time

(ATSDR 2004; Garcia 2008; NRC 2008; Akira and Suganuma 2014). Case

studies from accidental exposures do not typically provide adequate information

about exposure concentrations; however, ATSDR (2004) notes that brief

exposures to concentrations from 5000−10,000 ppm or 30-minute exposures to

concentrations of 2500−4500 ppm can be fatal to humans. By comparison,



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concentrations as high as 1000 to 2500 ppm have been reported in tank

headspace (Burgeson, et al. 2004; Meachum, et al. 2006a).

46. The primary effect experienced at low to moderate ammonia

concentrations is irritation of the upper respiratory tract and other moist

surfaces, including the eyes, nose, and mouth. Various controlled human

studies have reported mild eye and upper respiratory irritation following brief

exposures to ammonia concentrations at around 30 ppm (it affects some

individuals, during exercise, at levels as low as 5 to 25 ppm), with moderate

effects beginning around 50 ppm, and intense to unbearable irritation and tissue

inflammation and injury occurring at concentrations of approximately 100 ppm

and above (ATSDR 2004; Sundblad, et al. 2004; NRC 2008). Eye irritation

resulting in lacrimation (flow of tears) reportedly occurs at concentrations

above 100 ppm, with excessive irritation and lacrimation at concentrations at

about 500 ppm (EPA 2007), consistent with some symptoms reported by

exposed workers. Tolerance to non-disabling concentrations of ammonia may

develop with repeated or prolonged exposure (ATSDR 2004), which could

result in longer exposure durations and/or higher exposures as people develop

tolerance to immediate effects from low concentrations.



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47. A controlled human study involving 12 individuals randomly

exposed to 0, 5, and 25 ppm for three hours on different days reported

symptoms at various times over each exposure period (Sundblad, et al. 2004).

Half of the exposure time was spent seated and half the time was spent

exercising on a stationary bicycle, with switching between activities every 30

minutes. At 25 ppm, mild eye irritation was noted in a few individuals at the

first survey point at three minutes. Detailed responses for other symptoms with

time were not reported. Other irritant effects that increased with exposure

concentration were nasal or throat discomfort, breathing difficulties, and central

nervous system effects such as headache, dizziness, fatigue, nausea, and feeling

of intoxication. Average symptom scores were generally mild with little effect

on pulmonary function tests. The odor ratings were generally weakly and

nonsignificantly correlated with the other symptoms indicating that the effects

were generally not related to odor.

48. Reflex glottis (part of the larynx or windpipe) closure is a

protective mechanism that occurs in response to exposure to ammonia and other

noxious gases and effectively reduces lower respiratory system exposure

(EPA 2007). The effectiveness of this reflex appears to be age-dependent, with

healthy younger people responding to lower concentrations than older people.



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Erskine, et al. (1993) reported that older age groups required a higher ammonia

concentration to elicit the reflex response: about 570 ppm for 21–30 year olds,

1000 ppm for 60 year olds, and 1790 ppm for those 86 to 95 years old. Thus, it

is possible that as people age they could be exposed to higher, more damaging

concentrations of ammonia for longer periods of time before the protective

reflex glottis closure occurs, with a higher likelihood of more disabling and

irreversible effects.

49. While reflex glottis closure may result in less ammonia reaching

the lower respiratory tract, this reflex also causes a suffocating feeling and

shortness of breath. This reflex is unable to entirely prevent damage to the

respiratory tract at higher levels of exposure. Higher levels of exposure

(i.e., those in excess of 1000 ppm) readily reach the lower respiratory tract as

indicated by immediate coughing in controlled experimental studies, and lung

injury and disease after accidental exposures (NRC 2008).

50. Even more concerning, irreversible and/or disabling health effects

have been reported in people chronically or repeatedly exposed to relatively low

levels of ammonia (<50 ppm), including reduced respiratory function,

bronchiolitis/bronchitis, asthma, obstructive and restrictive lung disease, and

pulmonary fibrosis (summarized by Brautbar, et al. 2003; ATSDR 2004). In



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these instances, occasional higher peak exposures may have occurred. For

example, a photocopy and camera equipment worker developed debilitating

lung disease after 18 years of relatively low-level ammonia exposure

(e.g., 0-2 ppm, 15-20 ppm), with 30-400 ppm during leak episodes (Brautbar,

et al. 2003). Such exposures indicate some similarities to those described in

Hanford tank farm workers, in which variable low-level exposures may be

present generally within occupational exposure limits (e.g., time-weighted

average of 25 ppm based on the National Institute of Health Recommended

Exposure Limit), with occasional brief excursions, which for some workers at

the tank farms appear to be experienced repeatedly.

51. Low-level repeated acute exposures can also result in lasting

effects on the upper respiratory tract. A fish-processing worker exposed to

ammonia from a refrigeration leak experienced eye and nasal irritation and mild

facial skin burning (Prudhomme, et al. 1998). The worker had previously been

exposed at levels resulting in considerably milder effects. Ammonia air

concentrations in refrigeration reportedly are 9 to 38 ppm. After the event,

nasal congestion persisted and he had impairment to his sense of smell when

observed two years later.



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52. An occupational exposure limit based on an 8-hour time-weighted-

average is designed to be protective of chronic health effects to workers

potentially exposed five days per week for a working lifetime. However, as

noted in TVAT (2014), measurements that integrate chemical concentrations in

air over an 8 hour period will not necessarily detect short-term excursions, even

when those excursions are many times higher than the occupational exposure

level. These high excursions could result in ammonia causing serious health

effects even when the 8-hour time-weighted-average exposure limit is not

exceeded.

53. NRC (2008) derived acute exposure guideline levels (AEGLs) for

ammonia for varying time periods ranging from 10 minutes to 8 hours. The

AEGL-1 value, which is protective of non-disabling irritation of the respiratory

tract and eyes, is 30 ppm for all time periods. The AEGL-2 value, which is

protective of disabling eye and throat irritation, is 220 ppm for 10−30 minutes,

160 ppm for 1 hour, and 110 ppm for up to 8 hours. An AEGL-3 is reserved for

the most severe effects, including death. The AEGL-3 for ammonia is 2700 pm

for 10-minute exposures and decreases to 1600, 1100, 550, and 390 ppm for

30-minute, 1-hour, 4-hour, and 8-hour exposures, respectively. DOE adopted



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the 10-minute AEGL values as it’s protective action criteria for emergency

responders.

54. Higher ammonia levels of 1000 to 2500 ppm reported for tank

vapors are clearly at levels that would produce serious adverse effects to the

upper respiratory tract and lungs and are approaching lethal levels (Figure 4).

Ammonia concentrations reported in tank vapors also exceed the 300 ppm

upper limit defined by the National Institute of Occupational Health and Safety

as Immediately Dangerous to Life or Health.



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Figure 4. Guidance levels, maximum vapor concentration, and health effect levels for acute exposure to ammonia (ppm)



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3. Propanenitrile 55. Propanenitrile (proprionitrile) forms a colorless gas at ambient

temperatures that is described as having a pleasant, sweet odor and can cause

irritation and burning of the eyes and skin (NRC 2014). Case studies have

reported central nervous system effects in workers exposed to propanenitrile

(NRC 2014). For example, Scolnick, et al. (1993) reported a concentration of

34.4 ppm propanenitrile in the workspace air after two chemical plant workers

were overcome and taken to the hospital. One worker was disoriented after

two hours in the work area and a second worker was found unconscious after

seven hours. Additional symptoms included nausea, lethargy, headaches,

dizziness, confusion, seizures, and chronic occurrence of severe headaches.

Both men were treated for cyanide poisoning because propanenitrile breaks

down to cyanide once in the body. Symptoms, including headaches and

dizziness, lingered for several weeks in one of the men. Studies in rodents

support a mechanism of action consistent with cyanide toxicity, including signs

of difficulty breathing, disorientation, lethargy, tremors, convulsions, and death.

56. NRC (2014) derived an AEGL-3 value for severe, irreversible

effects, including death based on mortality in a rodent reproductive toxicity

study. Maternal mortality, non-surviving implants, and embryonic resorptions



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were significantly increased in rats exposed to 200 ppm for six hours per day

during gestational days 6−20. A no-effect level of 150 ppm was identified for

this study. The embryonic effects were considered relevant for an AEGL-3

because a single exposure during development, depending on timing could

result in developmental effects. An uncertainty factor of 30 to account for

species extrapolation and individual sensitivity and time-scaling were applied to

derive 8-hour, 4-hour, 1-hour, and 30-minute AEGL-3 values of 3.8, 5.7, 9.1

and 11 ppm, respectively. The 10-minute value was also set at the 30-minute

value of 11 ppm because of uncertainty about time-scaling to this extent. NRC

(2014) concluded that the severe central nervous system effects reported in the

workers exposed to 34 ppm for two hours were consistent with an AEGL-2, but

lack of information on a no-effect level for humans and precluded the use of the

available human data. Instead, the AEGL-2 values were derived by dividing the

AEGL-3 values by three. Thus, the AEGL-2 values for 8-hour, 4-hour, 1-hour,

30-minute, and 10-minute exposures are 1.3, 1.9, 3.0, 3.7, and 3.7 ppm,

respectively. There were inadequate data to derive AEGL-1 values. The

maximum reported concentration of propanenitrile in tank vapor was 5.3 ppm,

which exceeds the 10 minute AEGL for serious health effects that could include

direct irritation as well as possible central nervous system effects.



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4. Methyl vinyl ketone 57. Methyl vinyl ketone (3-buten-2-one) is a colorless to yellow liquid

at room temperature that has a pungent odor detectable at 0.2 ppm (U.S. EPA

2008). Although there are few studies available evaluating the effects of methyl

vinyl ketone in humans, studies in several animal species demonstrate that it is

highly irritating to the upper respiratory tract and eyes (U.S. EPA 2008).

Because it acts as a direct irritant on mucous membranes, the irritant and tissue

damaging properties in laboratory animals are considered relevant for humans.

58. U.S. EPA (2008) derived acute exposure guideline values based on

a rodent study in which rats and mice were exposed to 0, 0.25, 0.5, 1, 2, 4, or

8 ppm by inhalation six hours per day, five days per week, for 12 exposure days

(Morgan, et al. 2000). Rats were more sensitive to the acute effects of this

chemical than mice. In the 8 ppm group, airway necrosis resulted in death of all

rats after a single exposure and two of five mice by exposure day ten. Nasal

lesions occurred in both rats and mice at >1 ppm, and lung necrosis in rats at

>4 ppm. Differences in susceptibility may be related to differences in breathing

patterns (restriction of breathing in mice), respiratory tract anatomy and airflow,

or biochemical protective mechanisms (e.g., anti-oxidant levels). Observations

from this and other studies indicate that irritation associated with nasal lesions



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occurs after a single exposure (U.S. EPA 2008). EPA therefore based the

AEGL-1 values on irritation-induced nasal lesions with a no-observable-

adverse-effect level of 0.5 ppm and a threefold uncertainty factor was applied to

account for individual sensitivity. The same value (0.17 ppm) was applied to all

time periods because of the direct nature of the irritation. The AEGL-2 values

are based on the more severe irritation leading to lung necrosis, with a no-

observable-adverse-effect level of 2 ppm. EPA considered that the more severe

irritation from a single exposure above this level could impair some people’s

ability to escape. Time scaling was applied to derive 8-hour, 4-hour, 1-hour,

30-minute, and 10-minute AEGL-2 values of 0.5, 0.76, 1.2, 1.5, and 1.5 ppm,

respectively. The AEGL-3 values are based on lethality observed above 4 ppm

in this study as well as other animal studies. Time-scaling and a threefold

uncertainty factor for individual sensitivity were applied to derive 8-hour, 4-

hour, 1-hour, 30-minute, and 10-minute AEGL-3 values of 1, 1.5, 2.4, 3.1, and

3.1 ppm, respectively.

59. The maximum concentration associated with tank vapors of

1.2 ppm for methyl vinyl ketone reported by Burgeson, et al. (2004) exceeds the

occupational ceiling limit for worker safety (0.2 ppm), the first level of the

10 minute acute exposure guideline level, and is close to the second level of the



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acute exposure guildelines indicating serious effects. Therefore, tank vapor

concentrations of this chemical have the potential to cause serious irritation and

contribute to respiratory tract injury in workers.

5. N-Nitrosodimethylamine 60. N-Nitrosodimethylamine is a yellow, liquid at room temperature

with little to no odor, and is one of the most reactive and toxic of the

nitrosamine compounds (U.S. EPA 1976; ATSDR 1989, 2014).

61. In addition to affecting tissues at the point of contact,

n-nitrosodimethylamine targets the liver as the primary organ affected by

inhalation exposure to high concentrations (ATSDR 1989, 2014). Case studies

have identified severe liver toxicity in workers exposed to unknown

concentrations for as little as two weeks. Additional symptoms included

abdominal cramping and pain, nausea, dizziness, vomiting, jaundice, yellow

ascites (fluid accumulation in the abdominal cavity), liver cirrhosis, enlarged

liver and spleen, and death. Exposure also resulted in bronchial and tracheal

hemorrhaging in at least one person, indicating this chemical’s direct effect in

causing respiratory tissue damage. The more reactive nitrosamine compounds,

such as n-nitrosodimethylamine, are reported to cause irritation of eyes, lungs,



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and skin, and with higher exposures, hemorrhagic destructive lesions at the

point of contact (U.S. EPA 1976).

62. Liver toxicity and death have also been reported in laboratory

animals exposed to n-nitrosodimethylamine (ATSDR 1989). A single 4 hour of

exposure to 16 ppm n-nitrosodimethylamine resulted in hemorrhagic necrosis of

the liver and death in dogs. Liver necrosis and hemorrhage have also been

observed in rodents exposed to high concentrations of n-nitrosodimethylamine

for four hours. N-nitrosodimethylamine is also considered an inhalation

carcinogen based on increased incidence of liver, kidney, and lung tumors in

rodents exposed to n-nitrosodimethylamine for 17−24 months.

63. DOE developed protective action criteria values for protection

from health effects from acute exposure to n-nitrosodimethylamine. Such

airborne concentration limits for protection against slight, serious, or potential

life threatening health effects from 60-minute exposures are relatively low

compared to other chemicals at 0.027, 0.3, and 3.3 ppm respectively. The

maximum tank vapor concentration of 0.36 ppm reported by TVAT (2014)

exceeds the second tier criteria indicating that serious health effects might be

possible.



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64. As noted in the TVAT Report, the acute toxicity of

n-nitrosodimethylamine has been underappreciated and less studied because of

its genotoxicity (toxicity to genetic material) and potent liver carcinogenicity in

animals. Miller Decl., Ex. 6 at 135. However, given the available evidence in

animals and humans of its acute toxicity at relatively low concentrations, the

TVAT Report emphasizes the ability of this highly reactive nitrosamine

compound to “produce hemorrhagic destructive lesions at the site of contact”

and cautioned that even at 30% of the levels measured at the vent exit of some

tanks (>1100 ug/m3 or >0.36 ppm) this compound could be “highly irritating

even under very brief exposures.” Miller Decl., Ex. 6 at 133. High irritation is

concerning because of the reactive properties of this chemical resulting in tissue

lesions.

6. N-Butanol 65. N-Butanol is a colorless, flammable liquid at room temperature

with a strong, noxious odor detectable as low as 0.17 ppm (U.S. EPA 2011).

Both irritant and central nervous system effects have been reported in controlled

human exposure studies with n-butanol (U.S. EPA 2011). N-Butanol is 5–10

times more potent in inducing central nervous system effects than ethanol

(James 2008). A 3−5-minute exposure to as low as 25 ppm resulted in throat



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and nose irritation, and 50 ppm resulted in eye irritation (Nelson et al. 1943).

Unacclimatized volunteers experienced pronounced throat irritation and delayed

onset of headache at 50 ppm as well (Nelson, et al. 1943; NIOSH 1992).

Occupational epidemiology studies have also reported eye irritation and

dermatitis associated with exposure to n-butanol at concentrations of 20−65

ppm (Tabershaw et al 1944). Central nervous system effects typically do not

occur until exposure concentrations of approximately 100 ppm are reached

(James 2008). Workplace exposures have also been reported to result in hearing

loss (with concurrent noise), vertigo, dermatitis, and other systemic effects

(NIOSH 1992; U.S. EPA 2011). Although these exposures also included the

presence of other solvents, such a situation is similar to that resulting from tank

vapors.

66. A ceiling limit of 50 ppm has been set for n-butanol in the

workplace, which means at no time should this level be exceeded for protection

of workers (OSHA 2016). NASA set the 1 hour spacecraft maximum allowable

concentration to 50 ppm based on eye irritation, with a 24 hour level of 25 ppm

(James 2008). DOE developed protective action criteria values for protection

from health effects from acute exposure to n-butanol of 60, 800, and 8000 ppm



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for slight, serious, or life threatening health effects, respectively. The highest

value was set at 75% of the lower explosive limit.

67. The maximum reported tank vapor concentration of n-butanol

(58.3 ppm; Burgeson, et al. 2004) exceeds the occupational ceiling limit and is

approximately equal to the first tier of the protective action criteria. Thus,

n-butanol in tank vapors may contribute to some irritation effects.

7. Mercury 68. Mercury exists in tank waste and vapors in elemental and organic

forms and is continuously undergoing transformation between these major

forms. The forms noted in sampling data are usually mercury (assumed to be

elemental or vapor) and sometimes dimethylmercury, primarily in exhaust data

from vents of DSTs for compliance with air permitting (SSTs do not require air

permits). Because DST exhaust is derived from more than one tank,

concentrations emitted by a single tank can be higher. In addition, no

explanation is provided on whether the available sampling data that report

“mercury” concentrations represent total mercury forms (including

dimethylmercury) or only elemental mercury.

69. Mercury vapor has low solubility and reactivity in water and thus

passes through the upper respiratory tract without causing irritation. As a result,



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mercury exposure may go undetected until acute injury to the lower respiratory

system and/or systemic exposure has occurred (Jegal and Kim 2016; U.S. EPA

2010). Although chelation therapy can decrease body burden following

mercury absorption, chelation is not effective for reducing lung injury from

inhalation exposures, and has limited effectiveness in reducing central nervous

system effects once they become apparent. Exposures to airborne mercury have

occurred in both occupational and residential scenarios at high enough doses to

cause serious health effects ranging from chemical pneumonitis to death (Jegal

and Kim 2016). Mercury vapor is well absorbed into the brain by inhalation,

and the importance of this route of exposure is demonstrated by the 10 times

higher dose in the brain of mice and monkeys that results by inhalation as

compared to the same amount of elemental mercury injected in the blood

(Berlin, et al. 2015). Acute exposure to elemental mercury has been associated

with effects on the central nervous system, cough, difficulty breathing, and

chest tightness, corrosive bronchitis, and pneumonitis (U.S. EPA 2010).

70. Dimethylmercury is a colorless liquid with a weak, sweet odor and

is readily absorbed by inhalation or skin contact (OSHA 2016). It has a high

vapor pressure and so it evaporates quickly; consequently, it is an inhalation

hazard. Contact with dimethylmercury in spilled waste would also be well



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absorbed through the skin. Very little information is available specifically about

the relationship between dose and toxic response from dimethylmercury

exposure; although evidence indicates it is extremely toxic even after a single

exposure. A biomedical researcher spilled several drops of one or

dimethylmercury on the back of a latex gloved hand and removed the gloves

immediately. Five months later she reported progressive numbness and tingling

in her lower extremities, impairment of hearing and vision, slurred speech, and

difficulty walking. Although her exposure level was unknown, her blood and

urine mercury levels five months after exposure were 4000 and 234 µg/L,

respectively, compared to normal levels of 1−8 and 4−5 µg/L, respectively.

This blood mercury level was 80 times the toxic threshold of 50 µg/L. Her

symptoms worsened over the following three weeks and she subsequently fell

into a coma and died ten months after the single exposure, despite aggressive

chelation therapy (Blayney, et al. 1991; OSHA 2016). Organic mercury

exposures during pregnancy are also a concern for neurodevelopmental effects

(Berlin, et al. 2015).

71. Although the reported concentrations of dimethylmercury in DST

tank exhaust vapors would likely result in a much lower dose than absorption of

a drop of the pure compound, the high toxicity, rapid absorption, delay in



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effects, and uncertainty regarding exposure concentrations indicate great

caution should be exercised in preventing exposures to this compound.

72. U.S. EPA (2010) derived acute exposure guideline levels for

mercury vapor for varying time periods ranging from 10 minutes to 8 hours.

EPA recommended against AEGL-1 values because mercury vapor has low

warning properties; it is odorless and not an upper respiratory irritant. In

addition, no studies were available that document mild, reversible effects

consistent with an AEGL-1 effect level. The AEGL-2 value is based on

developmental effects observed in rats after 2 hours per day exposure to

elemetal mercury for ten days during pregnancy. Uncertainty factors and time-

scaling were applied to the no adverse effects level from this study (4 mg/m3) to

derive AEGL-2 values of 3.1, 2.1, 1.7, 0.67, and 0.33 mg/m3 for 10-minutes,

30-minutes, 1-hour, 4-hours, and 8-hours, respectively. The AEGL-3 values are

based on a dose level (26.7 mg/m3) that caused non-lethal effects, including

lung edema and necrosis, in rats after a single 1 hour exposure. A 2-hour

exposure to approximately the same dose level resulted in mortality for most

animals tested. After application of an uncertainty factor and time-scaling, EPA

developed AEGL-3 values of 16, 11, 8.9, and 2.2 mg/m3 for 10-minutes, 30-

minutes, 1-hour, and 4-hours, respectively. The 2.2 mg/m3 value was also



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applied for 8 hour exposures because of uncertainty in time-scaling. DOE

adopted the 1 hour AEGL-2 and -3 values for elemental mercury as its

protective action criteria for emergency responders. DOE also set a protective

action criteria of 0.15 mg/m3 for mild effects. In addition, DOE set protective

action criteria for dimethylmercury of 0.034, 0.046, and 2.3 mg/m3 for slight,

serious, or life threatening health effects, respectively based on existing

occupational exposure limits.

73. The maximum elemental mercury level of 0.456 mg/m3 reported

for tank vapors is below the short term AEGL-2 value for serious effects but

higher than the DOE protective action criteria for mild effects. The available

tank vapor dimethylmercury concentrations reviewed (sampling of DST tank

exhaust) have not exceeded the dimethylmercury protective action criteria.

However, considering that individual tank levels may be higher, the low

warning properties of mercury vapor or dimethylmercury and the potential for

bioaccumulation and serious health effects, additional caution should be taken.

8. Nitrous oxide 74. Nitrous oxide is an anesthetic commonly used in hospital and

dental operating rooms (NIOSH 1994). It affects the central nervous system,

causing drowsiness, euphoria, and unconsciousness; and impairing mental



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performance, vision, hearing, and motor skills (NIOSH 1994, 2014). At very

high concentrations there is risk of hypoxia, resulting in hypotension, cardiac

arrhythmias, headache, dizziness, brain damage, cerebral edema, permanent

mental deficit, and death (NLM 2011). Chronic exposure may also affect

neurological and reproductive function and harm the liver, kidney, and blood

system (OSHA 2000; NLM 2011). Nitrous oxide is a colorless gas with a mild,

slightly sweet odor and taste. It has low solubility in water and is not irritating

to the upper respiratory system (NLM 2011).

75. NIOSH set an 8-hour time-weighted-average occupational

exposure limit for nitrous oxide of 25 ppm (NIOSH 2016). NIOSH has not set

a short-term exposure limit. ACGIH recommends an 8-hour time-weighted-

average threshold limit value (TLV) of 50 ppm for nitrous oxide. ACGIH

further recommends that nitrous oxide concentrations should not exceed 3 times

the TLV (150 ppm) for more than 30 minutes and should never exceed 5 times

the TLV (250 ppm) (NLM 2011). DOE set protective action criteria for mild,

serious, or life threatening health effects of 910, 10,000, and 20,000 ppm,

respectively.

76. Nitrous oxide has been detected in tank vapors at concentrations as

high as 1099 to 4700 ppm. This exceeds the DOE protective action criteria for



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slight effects and is much higher than the never to exceed limit of 250 ppm

recommended by ACGIH. Release of this chemical at this level could therefore

contribute to central nervous system effects in workers.

9. Toxicity of mixtures 77. The chemicals described above, as well as the many other

chemicals present in tank vapor (e.g., aldehydes, Langford 2008, McCoy

2008b; hydrocarbons, McCoy 2008a), may also act in combination to produce

even greater effects, particularly if they produce the same types of effects

individually and/or produce those effects by the same mechanism of action

biologically. A number of the chemicals of concern are respiratory irritants that

act on the mucous membranes of the eyes or respiratory epithelial tissue to

produce progressively disabling effects with increasing concentration and

duration of exposure (e.g., ammonia, methyl vinyl ketone). Chemicals are also

more likely to have additive or greater than additive (i.e., synergistic) effects if

some of the chemicals are present at sufficiently high levels to cause toxic

effects. In such cases, the body is already compromised, and damage to the

respiratory tract can be exacerbated by exposure to other chemicals acting on

this endpoint even though the chemicals do not have similar mechanisms of

action. In other words, even if the some of the individual chemicals are present



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in levels that, by themselves, would not cause harm or not cause serious harm,

their additive effects would contribute to adverse impacts and/or serious harm.

As noted in the TVAT Report, “Of course NDMA [n-nitrosodimethylamine] is

but one compound among what is almost certainly scores of potentially acutely

irritating compounds extant in the tank head space, vents and subsequent

sporadic ground level plume exposures.” Miller Decl., Ex. 6 at 134. The

cumulative effect of such irritants can lead to greater tissue damage and more

serious health consequences.

78. Similarly, other chemicals of concern are central nervous system

toxicants (e.g., propanenitrile, nitrous oxide) with effects that progress from

headache and dizziness to confusion, disorientation, and more serious effects at

higher concentrations and/or exposure duration. The effects of such chemicals

are also likely to be additive or potentially more than additive once some

chemicals are at levels causing effects.

79. It is standard regulatory practice to consider risks from chemicals

producing similar effects (e.g., irritation) or to the same organ system (e.g.,

respiratory system) as additive (EPA 1989; SCHER, et al. 2011). DOE applies

this approach in its Chemical Mixture Methodology (CMM) to protect

emergency and other workers from exposure to releases with multiple



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chemicals at DOE facilities (Yu, et al., 2010). The CMM assumes that chemical

exposures that act on the same organ system or through the same mode of

action are additive unless there is evidence to the contrary. Thus, exposure to

two chemicals that are present at concentrations just below their threshold for

nervous system effects could additively exceed a threshold and impair the

nervous system. This is particularly so for chemicals that utilize the same

mechanism of action for inducing toxicity.

80. For example, several of the chemical classes released from the

tanks have similar metabolic pathways in the body involving the same enzyme,

including alcohols (e.g., n-butanol, methanol), ketones (e.g., methyl vinyl

ketone, acetone), aromatic compounds (e.g., benzene), and alkanes (e.g.,

hexane) among other industrial chemicals, pharmaceuticals, or recreational

chemicals (e.g., ethanol) (Pohl and Scinicariello 2011). Such metabolic

enzymes are involved in the conversion of a chemical into other compounds to

eventually metabolically utilize or excrete the chemical. Intermediates involved

in chemical metabolism can be more or less toxic than the original compound.

This impacts not only the potential additivity of effects from multiple chemical

exposures, but because of several known polymorphisms in the gene for this

enzyme, also impacts the potential for differential sensitivity of individuals



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within the general working population. As noted previously, other genetic

polymorphisms that affect how people handle alcohols and aldehdyes results in

differences in susceptibility to the effects of these types of chemicals.

81. Given the thousands of chemicals present in the waste and

headspace vapor that potentially could be released, the lack of toxicity data for

many of these chemicals, and unknown effects of interactions, mixture toxicity

must be given serious consideration before chemical exposure levels can be

assumed to be protective of worker health. Simple additive effects may not be

sufficient to characterize toxicity. The TVAT Report recommended conducting

in vitro and in vivo state-of-the-art toxicity studies and biologically-based

dosimetry modeling studies of tank vapors. Miller Decl., Ex. 6 at 45. Timchalk

of PNNL appears to have outlined some proposed research to address this

recommendation. Whether such studies have been funded and have started is

less clear. Among the research activities ongoing at the PNNL, research on

chemical mixture toxicology is not mentioned on their website

(http://www.pnnl.gov/biology/programs/).



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D. Risk Characterization: Tank Exposures Cause Health Effects and Pose Risks of Serious Irreversible Impairment

1. Health effects from acute exposure to key chemicals 82. Reported maximum concentrations of ammonia, n-butanol, methyl

vinyl ketone, nitrous oxide, n-nitrosodimethylamine, and propanenitrile exceed

various limits indicative of potential acute health effects and risk of permanent

impairment (Table 3). With the exception of ammonia, most of these chemicals

contribute to both irritation and central nervous system effects, depending on

the concentration. The chemical with the most acute toxicology data, ammonia,

has a maximum concentration that would clearly cause serious health effects

even with brief exposures. At such an exposure level, effects would occur

immediately, involve the whole respiratory tract, and would likely produce

respiratory tract injury leading to irreversible effects that have been noted for

this chemical. Maximum concentrations of n-nitrosodimethylamine and

propanenitrile also exceed the second tier level of the EPA acute exposure

guideline levels or DOE protective action criteria, indicating that serious eye

and respiratory effects are possible from tank vapor exposures. Methyl vinyl

ketone exceeds its occupational ceiling limit and would contribute to these

direct acute effects. Nitrous oxide would have less contribution to irritation and

direct tissue injury but could contribute to central nervous system depression,



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along with the many other chemicals with these toxic effects (e.g.,

hydrocarbons).

Table 3. Comparison of maximum vapor concentrations to short-term limits

Short-Term Limits4

Chemical

Maximum tank vapor

concentration (ppmv)1

Short-term occupational

limit2 (ppmv)

Acute Effect3

Reversible PAC-1 (ppm)

Serious PAC-2 (ppm)

Life-threatening

PAC-3 (ppm)

Ammonia 1042, 2498 5 125 (T) I 30A 220A 2,700A

300 (I)

N-Butanol 58.3

100 (T) I, N 60 800 8000

50 (C)

3-buten-2-one 1.2

0.2 (C) I, N 0.17A 1.5A 3.1A (methyl vinyl ketone)

Dimethylmercury 0.0007 6 0.05 (T) I, N 0.034 0.046 2.3 (mg/m3)

0.04 (C)

10 (I)

Elemental Mercury 0.456 7 0.125 (T) I, N 0.15 3.1A 16A (mg/m3)

10 (I)

Nitrous Oxide (N2O) 1099, 4700 5 250 (T) N 910 10,000 20,000

N-Nitrosodimethylamine 0.082, 0.36 8 0.0015 (T) I, N 0.027 0.3 3.3

Propanenitrile 5.3

30 (T) I, N NR9 3.7A 11A (Propionitrile)

Bolded text indicates that the concentration exceeds the limit or action criteria. A - Acute exposure guideline level (U.S. EPA 2016) IDLH - Immediately Dangerous to Life or Health (NIOSH) NR - Not recommended PAC - Protective Action Criterion (DOE 2016). TWA - Time-weighted average; occupational exposure level

1 Burgeson et al. (2004) 2 Occupational exposure limits: Ceiling limit (C), IDLH (I), or 5 times the TWA (T) 3 Health effects: irritation (I) and/or nervous system effects (N) 4 Levels 1-3 for 60 min. exposure action criteria or 10 min. AEGL (A) 5 Meachum et al. (2006a) 6 702 AN Exhauster collected 3/4/16 7 AN Exhauster Stack sample port collected over 8 hours on 8/11/12 WA00003232 8 TVAT (2014) Appendix I 9 Lack of AEGL-1 value does not imply that exposure below the AEGL-2 value is without adverse effects



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83. Mercury vapor exceeds 5 times the time-weighted-average limit

(equivalent to a ceiling limit not to be exceeded at any time in the workplace),

and the first level of the DOE protective action criteria for protection against

reversible effects. Repeated exposures to elemental and its more toxic organic

form, dimethylmercury, however, are concerning because of their rapid

absorption by inhalation, ability to cross the blood brain barrier, slow

elimination, and neurotoxic effects from accumulation in the body.

2. Consistency with reported health effects 84. Health effects reported by workers are consistent with those

reported in the literature for the chemicals in the tank waste and vapors. Noted

effects are related to odor, upper respiratory and eye irritation, as well as acute

injury to respiratory tissue and lower respiratory tract effects. Other effects

appear to involve the central nervous system (e.g., dizziness, fatigue). Reports

of worker exposures (e.g., Hoffman 2010), also indicate the occurrence of

repeated peak exposures resulting in medical evaluations. Repeated exposures

increase the potential for permanent respiratory tract or neurological injury.

85. As summarized in the TVAT Report, vapor exposure incidents have

resulted in health effects consistent with the effects of bolus exposures to tank

vapor chemicals: shortness of breath, upper respiratory tract irritation,



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coughing, nasal bleeding, headaches, and a case of chemical pneumonitis

(diagnosed). Miller Decl., Ex. 6 at 51.

86. A voluntary survey involving 54 workers by NIOSH (2004)

reported immediate symptoms that included (N of workers):

• Headache (13)

• Bloody nose (7)

• Throat irritation (6)

• Coughing (5)

• Skin rash (5)

• Metallic taste (5)

• Eye irritation (3)

• Dizziness (3)

• Shortness of breath (3)

• Nausea (2)

• Nose irritation (2)

• Chest tightness (1)

• Skin itching (1)



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Symptoms and effects that persisted or occurred after exposure included:

• Frequent headaches (10)

• Decrease in pulmonary function test values (8)

• New-onset asthma (6)

• Chronic cough (5)

• Frequent nose bleeds (5)

• Sinus infections (4)

• Hoarseness (3)

• Memory loss (3)

• Shortness of breath (3)

• Bronchitis (2)

• Pneumonia (2)

• Ringing in ears (1)

• Blood in stools (1)

• Scarring of lungs (1)

87. Generally similar proportions of symptoms in workers were

reported in records from the onsite medical clinic from October 1, 2008 to

March 31, 2010 (Hoffman 2010) and in the 58 workers who received medical

evaluations in April and May 2016. Young Decl., Ex. 14. Overall, about 30%



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of symptoms reported were headaches, and 17 to 24% involved irritation and

injury to the upper airway (nose, mouth, throat) whereas 10 to 12% of

symptoms involved the lower airways (lungs and related passages as indicated

by cough, shortness of breath). A metallic taste was also a relatively prevalent

symptom that has been associated with mercury (Dart, et al. 2000), other metals

(Jegal and Kim 20165) or with ammonia (Prudhomme, et al. 1998) exposure

although other substances and drugs may also produce this symptom (Smith, et

al. 2009; Barlow 2015). Possible central nervous system depressive effects also

occurred among symptoms in both time periods (dizziness, disorientation,

fatigue, weakness), although 2016 appeared to have more cognitive effects than

in 2008–2010. As for headache, stomach upset and nausea may also be related

to effects on the nervous system as a result of chemical toxicity or reaction to

strong odors. Effects on the eyes also were reported in some workers, although

at a lower frequency than for effects on the respiratory tract or nervous system.



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Table 4. Prevalence of types of symptoms in workers medically evaluated in 2016 and 2008-2010

% of Symptoms

April 2016– May 2016

N=89

October 2008– March 2010

N=94

Headache 29% 33%

Upper airway effects 18% 24%

Dizzy/light headed/disoriented 14% 1%

Lower respiratory effects 11% 10%

Metallic/bad taste 9% 11%

Nausea/stomach upset 9% 6%

Burning/watery eyes 3% 6%

Fever/flu-like symptoms 2% 0%

Tingling lips/mouth numbness 1% 3%

Fatigue/weakness 1% 2%

Numbness/tingling in hands and feet 1% 0%

Kidney pain 1% 0%

Hypertension 1% 0%

Ear irritation 0% 2%

Tinnitus 0% 1%

Sources: Hoffman (2010); Young Decl., Ex. 14.

88. The effects in the 58 workers who received medical evaluations in

April and May 2016 thus show overall consistency with previously reported

symptoms from tank vapor exposures and are consistent with the direct harmful

effects of tank vapor chemicals on mucous membranes (upper and lower

respiratory tract, eyes) or on the central nervous system.



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89. Reports of workers being seen for health effects that occur after the

day of the exposure event (See, e.g., Young Decl., Ex. 14) is possibly indicative

of persistent effects or more serious injury than transient acute irritation that is

immediately reversible.

a. Past reports of reduced lung function and disability from

chemical pneumonitis also are concerning, and are consistent with

serious respiratory effects of tank vapor chemicals. Declarations by

workers report continuous sinus problems and lung impairments

consistent with vapor exposures, including from recent exposure events

(Rose Calderon, Seth Ellingsworth, Abelardo Garza, Guy Johnson, and

Kevin Newcomb).

b. One worker lost his sense of smell and was unable to

recognize odors that were noted by others (Declaration of Abelardo

Garza), similar to the published case report of relatively low-level

exposure to ammonia (Prudhomme, et al. 1998). As a result, WRPS

cannot assume that workers would not be exposed to harmful levels of

vapors because the tank vapor odors give ample warning. The loss of the

sense of smell places a worker at increased risk of serious exposure

because of the lack of warning from odors.



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90. Repeated exposures by workers, as noted above, also increase the

likelihood of serious respiratory tract or central nervous system effects, as well

as the potential for other effects associated with exposures to the mixture of

chemicals. As recommended in the TVAT Report, “appropriately designed

epidemiological studies focused on tank farm workers are recommended to

evaluate the potential long-term health consequences.” Miller Decl., Ex. 6 at

52. I concur that a comprehensive program is needed to investigate the

potential long-term consequences of exposures as well as to help ensure that

workers receive appropriate health monitoring and treatment for their specific

health issues.

3. Cancer risk

91. A number of chemicals identified in tank waste and headspace

vapors are known human carcinogens or are considered potentially carcinogenic

based on studies in animals (Burgeson, et al. 2004). A risk assessment

conducted by the PNNL in 1997 examined 204 chemicals in vapors from Tank

C-103 for carcinogenic risk (Maughan, et al. 1997). The focus of the cancer

assessment was on worker exposures over a duration of 25 years; however, the

full report was not available for review of its assumptions and calculations.

Total cancer risks reported ranged from 1.4 in 10,000 to 1.6 in 1000, depending



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on stack configuration. These risks were compared to U.S. EPA target cancer

risks of 1 in 1,000,000 to 1 in 10,000. Maughan, et al. (1997) also considered

possible synergistic effects of chemicals in magnifying risks by a factor of

1000, resulting in risks well in excess of the EPA target range.

92. Although cancer risk using EPA methods developed for Superfund

and RCRA risk assessments are not typically applied to workplace exposures to

protect workers, such a screening may be appropriate in a situation involving

many chemicals with unknown potential for health risk. These results indicate

that investigation of the mutagenic and carcinogenic potential of tank vapors

using advanced toxicological testing as recommended by TVAT would be

prudent to inform risk management decisions on worker protection.

IV. CONCLUSIONS

93. The Hanford tank farms contain thousands of known and unknown

chemicals for which the available sampling data incompletely characterize their

potential ranges in concentrations. Bolus concentrations affecting workers have

also been inadequately characterized because of sampling limitations. Since

WRPS’s implementation of actions to address the recommendations of the 2014

TVAT Report, worker exposures to tank vapors continue to occur. Given such

ongoing exposure events, the toxicity of the key chemicals at their upper levels



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83. Washington River Protection Solutions, LLC. Waste retrieval. http://wrpstoc.com/tank-operations/waste-retrieval/. (Accessed: June 30, 2016)

84. Washington State Department of Ecology. Frequently asked questions: Leaking underground tanks at Hanford. http://www.ecy.wa.gov/ programs/nwp/sections/tankwaste/closure/pages /tank_leak_FAQ.html. (Accessed: March 2016)

85. Yu, X-Y., A.J. Petrocchi, D.K. Craig, C.S. Glantz, D.M. Trott, J. Ciolek, P-Y. Lu, J-A. Bond, T.E. Tuccinardi, and P. Bouslaugh. The Development and Application of the Chemical Mixture Methodology in Analysis of Potential Health Impacts from Airborne Release in Emergencies. J. Appl. Toxicol. 30:513–524. (2010)



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PROOF OF SERVICE

I certify that I electronically filed the foregoing document and

accompanying exhibits with the Clerk of the U. S. District Court using the

CM/ECF system which will send notification of such filing to all parties of

record as follows:

• Thomas J. Young [email protected], [email protected]

• John A. Level [email protected], [email protected], [email protected]

• Kelly T. Wood [email protected], [email protected], [email protected]

• William R. Sherman [email protected]

• Meredith A. Crafton [email protected]

• Richard A. Smith [email protected]

• Richard Webster [email protected]

• Beth E. Terrell [email protected]

• Blythe H. Chandler [email protected]

• Sheila Baynes [email protected], [email protected]



Olympia, WA 98504-0117 (360) 586-6770

mailto:[email protected]














mailto:[email protected],%[email protected]

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• Elizabeth B. Dawson [email protected], [email protected]

• Austin David Saylor [email protected], [email protected]

• Vanessa Ruth Waldref [email protected], [email protected], [email protected]

• J. Chad Mitchell [email protected], [email protected], [email protected]

• David M. Heineck [email protected], [email protected]

• Sara A. Kelly [email protected]

In addition, the following individuals have received the foregoing

document via e-mail, pursuant to the parties’ e-service agreement:

• Steve Cherry [email protected]

• Nada Barnes [email protected]

• Mark Nitczynski [email protected]

• Mark Silberstein [email protected]

• Ann Duer [email protected]



Olympia, WA 98504-0117 (360) 586-6770





mailto:[email protected],%[email protected],%[email protected]












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• Jennifer [email protected]

• Molly [email protected]

DATED this 20th day of July 2016.

s/ Thomas J. Young THOMAS J. YOUNG



Olympia, WA 98504-0117 (360) 586-6770



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UNITED STATES DISTRICT COURT EASTERN …...2016/07/19 · NO. 4:15-cv-05086-TOR (consolidated with...

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