U.S. ENVIRONMENTAL PROTECTION AGENCY

REGION III

In re: BWX Technologies, Inc. )

Mt. Athos Site )

Lynchburg, Virginia )

F006 Delisting Petition under 42 U.S.C. 6921(f) )

)

)

Declaration of David W. Griffiths, Ph.D. )

Use and Disposition of Fluorine )

Containing Compounds at Mt. Athos Site )

)

DECLARATION

QUALIFICATIONS

1. I currently serve as President of and Senior Scientist for Olver 

Laboratories, Inc., a Blacksburg, Virginia-based environmental services firm. I 

earned my Ph.D. in the field of physical organic chemistry from Washington 

University, St. Louis, Missouri, in 1971.

2. Following close to three years of postdoctoral study at Northwestern 

University, I began my industrial career with Petrolite Corp., St. Louis, Missouri, 

where I engaged in research and development activities concerned with 

enhanced production of crude oil, and with the management of oilfield production 

wastes in an environmentally sound manner. 

3. Subsequently, I served for five years as Director of Research and 

Technology for the Olin Water Services division of Olin Corp. In this capacity, I 

focused my attention on the development of improved technologies for the 

management and disposal of industrial wastewater streams. 
4. For the last 13 years, with Olver Laboratories, I have been applying the 

principles of chemistry and physics to resolve a wide variety of environmental 

issues. My areas of special expertise include:

· Analysis of environmental samples for chemicals of interest;

· Data validation and interpretation;

· Assessment of risks and/or fate and transport mechanisms for 

chemicals in the environment; and

· Development of effective strategies for the remediation of 

contaminated soils, wastewaters, and groundwater reservoirs.

5. A curriculum vitae is attached as Exhibit 1.

BACKGROUND

6. BWX Technologies, Inc. (“BWXT”) owns and operates a manufacturing 

facility at its Mt. Athos site in Lynchburg, Virginia. Operations at this site are 

subdivided into those of BWXT’s Nuclear Products Division (“NPD”), and its 

Lynchburg Technology Center (“LTC”).

7. NPD is primarily engaged in the fabrication of components for the U.S. 

Government and other customers. Unit operations at NPD consist of machining, 

welding, grinding, pickling, and cleaning of metallic substrates, followed by 

assembly of the finished products. 

8. Activities at the LTC are widely diversified, consisting mainly of research 

and development, process control activities, and laboratory testing operations. 

9. Support functions at the Mt. Athos site include a steam generation plant, a 

water purification plant that produces deionized water for plant-wide use, and 

three wastewater treatment plants (“WWTP”). One of the WWTPs is dedicated 
to the treatment of plant-wide sanitary wastes, while the other two, one of which 

is designated as the pickle acid (“PA”) waste treatment plant and the other as the 

low-level radioactive (“LLR”) waste treatment plant, are dedicated to the 

treatment of process wastewaters. 

10. Treated effluent from these two plants, together with non-contact cooling 

water which does not require treatment, are directed to and retained in two Final 

Effluent Ponds (FEP No. 1 and FEP No. 2) prior to discharge through Outfall 001 

to the James River pursuant to BWXT’s VPDES permit. 

11. The nature of the materials that are or have been introduced into FEP 1 

and FEP 2, especially with respect to the possible presence of fluorine-containing 

hazardous constituents, are the focus of this Declaration. As to the nature of 

BWXT's processes, operations, and raw materials, I have relied on information 

supplied by BWXT personnel, the Delisting Petition itself, and VPDES program 

and other data supplied by BWXT.

OVERVIEW OF MANUFACTURING AND WASTEWATER TREATMENT 

OPERATIONS

12. The only fluorine-based compound in past, present, or anticipated future 

use at BWXT’s Mt. Athos facility is hydrofluoric acid ("HF"). This compound, 

together with other strong acids, is used in a variety of metal finishing 

applications. It is always used as an aqueous solution. For example, an 

aqueous solution containing HF and nitric acid is used to pickle certain zirconium 

alloy components after machining, heat treatment, and grit blasting operations, 

all of which tend to roughen the metallic surface. The pickling operation, by 

smoothing the surface, serves to restore the surface to its original condition.
13. Similar solutions of HF and nitric acid in water are used for the pickling of 

hafnium components, and for the cleaning of Inconel and aluminum components. 

A specialized acid cleaning solution consisting of an aqueous mixture of HF, 

nitric, hydrochloric, and phosphoric acids, plus ferric chloride, has been used 

since 1994 to clean Inconel components. Lesser quantities of HF are used in 

uranium recovery operations, and in complete dissolution and recovery of 

uranium.

14. The acid cleaning solution that is used to clean Inconel components, when 

spent, is accumulated in secure containers, then shipped offsite as a hazardous 

waste for treatment and disposal. Otherwise, HF-containing spent pickling 

solutions and rinse waters are treated onsite in the PA and LLR wastewater 

treatment plants. The chemical and physical reactions and disposition of the HF 

component of these various metals processing and fabrication wastestreams are 

all largely identical. 

15. Both the PA and LLR wastewater treatment plants are equipped with 

elementary neutralization chambers wherein HF is converted to inert salts. First, 

a lime slurry is added in a stoichiometric amount calculated to convert the 

amount of HF entering the system, then liquid sodium hydroxide is added for 

purposes of further pH adjustment. The lime slurry serves to remove fluoride ion 

from solution as an insoluble salt (calcium fluoride), while the sodium hydroxide 

serves to encourage complete precipitation of calcium fluoride salts, and to 

convert any residual HF to a mixture of sodium fluoride and water. 
16. Following neutralization, the calcium fluoride-containing solids are

collected, dewatered, then shipped for final disposal at landfills that are approved 

to receive industrial and/or low-level radioactive solid wastes. This is the (former 

F006) sludge that EPA delisted in year 2000. 

17. After solids removal, the purified wastewaters are initially discharged to 

FEP 2. Because no wastewater treatment solids removal process is completely 

effective for removing all of the solid materials from the wastewaters, very small 

amounts of the calcium fluoride-containing solids are in the treated wastewater, 

and settle out in FEP 2. 

18. After flowing through FEP 2, the wastewaters are mixed with treated 

effluent from FEP 1 and the sanitary wastewater treatment plant, then discharged 

to the James River in compliance with the requirements of the facility’s VPDES 

Discharge Permit Number VA0003697. 

19. Historically, comparably-generated and treated fluoride-containing 

wastewaters were also treated and discharged through FEP 1. Also historically, 

wastewater treatment solids removal processes were not as efficient as the 

current processes, and larger quantities of calcium fluoride-containing solids 

settled in the FEPs. These materials make up the current sludge blankets in the 

FEPs.

PROPERTIES OF HF

20. By virtue of its identification at 40 CFR Part 261, Appendix VIII, the U.S. 

EPA has defined HF as a “Hazardous Constituent,” a defined regulatory term. In 

chemical terms it is a specific and unique composition of matter to which has 
been assigned Chemical Abstracts Services Registry Number (CASRN) 7664-

39-3.

21. The types of hazards associated with HF tend to be limited to occupational 

exposure, and are derived mainly from the fact that it exhibits the properties of a 

strong acid. HF does not exhibit significant toxicity properties, separate from its 

acidity. For example, in its Public Health Statement for HF,1the federal Agency 

for Toxic Substances and Disease Registry (ATSDR) concludes that 

“[h]ydrofluoric acid is dangerous to humans because it can burn the eyes and 

skin.” ATSDR further concludes in the same document that “[t]he major public 

health concern regarding hydrofluoric acid is related to short-term exposure to 

[concentrated forms of HF] at work.” It is because of its strength as an acid that 

HF proves useful to BWXT for purposes of pickling metallic surfaces, including 

those of such metals and metallic alloys as hafnium and Inconel which would 

otherwise resist the pickling action of acids of lesser strength.

22. An acid such as HF, not unlike nitric, sulfuric, and/or phosphoric acids, is 

by definition an acid because it is a proton donor. This means that when it is 

dissolved in water, it readily undergoes ionization to create hydrogen and fluoride 

ions. The chemical equation that represents this process is as follows:

HF  H

+

+ F23. Like any and all acids, the acidity of HF, and its associated hazardous 

properties, can be negated by neutralization. The process of neutralization 

entails providing HF with a proton acceptor. One such acceptor is sodium 

 

1

http://www.atsdr.cdc.gov/toxprofiles/phs11.html.
hydroxide (NaOH). The chemical equation that represents neutralization of HF 

by NaOH is as follows:

HF + NaOH NaF + H20

The products of neutralization are sodium fluoride (NaF) and water (H2O).

24. HF can also be neutralized by calcium hydroxide (Ca (OH)2), in which 

case the chemical reaction takes the following form:

2HF + Ca(OH)2 CaF2 + 2H20

Since calcium fluoride (CaF2) is, for all practical purposes, a water insoluble salt, 

this reaction serves not only to neutralize HF, but also to remove fluoride ion from 

solution.

25. The above-described reactions are those that take place in the elementary 

neutralization chambers within BWXT’s PA and LLR wastewater treatment 

plants. The by-products of the reactions are water, CaF2 , and NaF . CASRNs 

for the latter two compounds are 7789-75-5 and 7681-49-4. They are classified 

as salts. They are not identified at 40 CFR Part 261 Appendix VIII as Hazardous 

Constituents. Accordingly, because of the neutralization by calcium hydroxide 

and sodium hydroxide, the only Hazardous Constituent in these reactions (HF) is 

for all practical purposes removed.

26. The dissociation of HF to form hydrogen and fluoride ions is governed by 

an equilibrium constant, also referred to as an acid dissociation constant, 

symbolized as “Ka”. For solutions of HF in pure water at 25oC, the value of Ka = 

3.53 x 10-4. 

2

 Mathematically, Ka represents the product of the hydrogen ion and 

 

2

 Handbook of Chemistry and Physics, 73rd Edition, CRC Press, Inc., 1993, Section 8, p. 41.
fluoride ion concentrations, divided by the HF concentration, where all 

concentrations are expressed in units of moles/liter (M):

K x moles liter HF

H x F

a 3.53 10 /

4

Since hydrogen ion concentration appears in the numerator of this 

equation, the distribution of total fluoride between its ionized and unionized 

forms (Fand HF, respectively) is pH-dependent. By substituting into the 

equation the hydrogen ion concentrations that correspond to various pH values, 

the equation can be solved to obtain a measure of the percent ionization (i.e., 

percent of total F converted to F-) as a function of pH. Starting with the 

hydrogen ion concentration that corresponds to the numerical value of Ka, the 

derived values for percent ionization are as follows:

pH [H+], mol/l % Ionization [F-]/[HF]

3.45

4.00

5.00

6.00

7.00

8.00

9.00

3.53 x 10-4

1.00 x 10-4

1.00 x 10-5

1.00 x 10-6

1.00 x 10-7

1.00 x 10-8

1.00 x 10-9

50.000

77.925

97.245

99.718

99.972

99.997

99.999+

1.00

3.53

35.3

353

3,530

35,300

353,000

27. These calculations are relevant in the sense that the BWXT facility is 

obligated by virtue of its VPDES permit to control the pH of its effluent at values 
ranging from 6.0 to 9.0. These limits apply not only to final effluent discharged 

through Outfall 001, but also to the effluents that are discharged from both FEP 1 

and FEP 2 (designated as internal Outfalls 601 and 701, respectively). Based on 

my review of one year’s worth of pH compliance-monitoring data for the BWXT 

facility, I have verified that the facility operates in compliance with these limits. In 

fact, the minimum pH is normally at or above a value of 7.0.

28. From above, at a pH of 7.0, 99.972% of the total fluoride will exist as 

fluoride ion. As an example, if total fluoride is present at a concentration of 

exactly 5.0000 x 10-4 M (corresponding, approximately, to a combined total of 10 

mg/L), then the fluoride ion concentration at a pH of 7.0 will equal 4.9986 x 10-4

M, whereas the HF concentration will equal 1.40 x 10-7 M. Converted to units of 

mg/L, these values coincide to concentrations of 9.9964 mg/L for fluoride ion, 

and 0.00294 mg/L for HF. Strictly speaking, these figures represent the F-/HF 

distribution under the conditions that were used to determine the HF acid 

dissociation constant (i.e., in pure water, at 25oC). Deviations from these 

conditions will lead to slight modifications in the distribution but not to any extent

that would invalidate the conclusion that at the pH values encountered in FEP 1 

and FEP 2 wastewaters at the BWXT facility, the overwhelming majority of the 

total fluoride exists as fluoride ion. Conversely, the HF concentration is so low as 

to be analytically unmeasurable, and inconsequential with respect to any adverse 

effects on human health or the environment. Therefore, in addition to the 

removal of HF through the neutralization reactions referred to above, any minute 
remaining concentrations would be nearly entirely in the form of fluoride ion in the 

BWXT wastewaters. 

29. Finally, the chemistry that is responsible for the removal of HF as calcium 

fluoride, and for the conversion of any residual HF to sodium fluoride, takes place 

prior to the Final Effluent Ponds. Therefore, wastewaters that enter the FEPs 

can be considered to be virtually HF-free. Since no further HF is added to or 

created in wastewaters contained in the FEPs, it follows that wastewaters that 

leave the ponds are also virtually free of HF. This applies not only to 

wastewaters that leave by way of the designated Outfalls 601 and 701, but also 

to any wastewaters that may migrate to underlying groundwater reservoirs by 

infiltration through underlying soils. Similarly, the solids that accumulate in the 

FEPs, which may contain small amount of entrained wastewater, will also for all 

practical purposes be HF-free.

Comments on the Likelihood, if Any, That Fluorine-Containing Hazardous 

Constituents Other Than HF Might be Present in BWXT’s Wastewater 

Streams, or Created During Manufacturing or Wastewater Treatment 

Operations

30. In addition to HF, the following fluorine-containing compounds are 

members of the Appendix VIII list of Hazardous Constituents:

Compound Name Empirical Formula CASRN

Fluorine F2 7782-41-4

Fluoroacetamide C2H4FNO 640-19-7

Fluoroacetic acid, sodium salt C2H2FO2Na 62-74-8

Diisopropylfluorophosphate C6H14FO3P 55-91-4
Carbon oxyfluoride CF2O 353-50-4

Dichlorodifluoromethane CCl2F2 75-71-8

Trichloromonofluoromethane CCl3F 75-69-4

31. For a variety of reasons, none of these constituents would be expected to 

be present in BWXT’s wastewater streams or in FEP sludge. One reason in 

particular is that there are no clear reasons for their use at the facility and, so far 

as can be determined, they have never been purchased, synthesized, or 

otherwise acquired by the facility. Other reasons for their absence include their 

reactivity and/or instability in water, as well as the absence of raw materials 

and/or favorable reaction conditions for their creation.

32. Specific properties and/or characteristics that preclude the presence of 

these constituents in BWXT wastewaters or in FEP sludge, on a case-by-case 

basis, are as follows:

Fluorine3: Fluorine is a greenish diatomic gas with a boiling point of –

188.13oC. It is the most chemically reactive of all elements. Because of 

its reactivity, it rarely, if ever, exists as F2 in the natural environment. If it 

were to be somehow introduced into one of the BWXT wastewater 

streams, it would be almost immediately converted to HF, which would be 

indistinguishable from the HF that is otherwise used in pickling processes.

Fluoroactamide and Fluoroacetic acid, Sodium Salt4: These two 

compounds are closely related. In its acid form, the sodium salt of 

fluoroacetic acid is a natural product that occurs in “Gifblaar”, a poisonous 

plant that grows in South Africa. Both compounds are highly poisonous 

and both, in years past, have been used as rodenticides and/or 

insecticides. In the late 1980s, EPA banned all uses of fluoroacetamide in 

 

3 Cotton, F. Albert and Wilkinson, G., Advanced Inorganic Chemistry, A Comprehensive Text, 

Interscience Publishers, 1962, pp. 286-290.

4 The Merck Index, 10th Edition, 1983, entries 4071 and 4072.
the U.S.5

 The sodium salt of fluoroacetic acid remains registered for 

limited use as a component of livestock protection collars but, like 

fluoroacetamide, has been banned from all other uses. The synthesis of 

these compounds would require specialized raw materials and reaction 

conditions that do not exist at the BWXT facility.

Diisopropylfluorophosphate6: This compound was at one time 

developed for use as a cholinesterase inhibitor, and as a nerve gas. For

lack of the necessary raw materials and reaction conditions, it could not be 

created at the BWXT facility. Were it to be somehow introduced into one 

or more of the facility’s wastewater streams, it would undergo rapid 

hydrolysis to form non-hazardous by-products (the diisopropyl ester of 

phosphoric acid, and fluoride ion).

Carbon Oxyfluoride: This compound is the fluorine analog of phosgene. 

According to the Merck Index 7, it is “instantly” hydrolyzed in water. The 

hydrolysis products are carbonic acid (or its salts), and fluoride ion, both of 

which are non-hazardous compounds.

Dichlorodifluoromethane and Trichloromonofluoromethane8: These 

two compounds are members of the class of compounds known as 

chlorofluorocarbons, or CFCs for short. Both are defined as Class I 

Ozone-Depleting Substances which, as a class, are subject to the 

accelerated phaseout rule issued by EPA in July of 1992. This rule 

required cessation of production by January 1, 2000 (57FR33754). Had 

these compounds been used at the BWXT facility, they would have been 

used as refrigerants in closed systems that would have afforded no direct 

or indirect mechanism for release of the CFCs to the BWXT wastewater 

streams. Moreover, CFC compounds would not have been created during 

manufacturing or wastewater treatment operations for lack of the 

necessary raw materials or reaction conditions.

33. As a note added in proof, a sampling and analysis event was undertaken 

to provide affirmative evidence concerning the presence or absence of those 

members of the above-listed hazardous constituents that are classified as 

organic compounds. These consist of fluoroacetamide, the sodium salt of 

 

5 Restricted Use Products (RUP) “Report, June 2002: 

http://www.epa.gov/opppmsd1/RestProd/rupjun02.htm

6 TOXNET: http://toxnet.nlm.nih.gov/

7 The Merck Index, 10th Edition, 1983, entry 1803.
fluoroacetic acid, diisopropylfluorophosphate, dichlorodifluoromethane, and 

trichloromonofluoromethane. The sampling and analysis event was initiated on 

October 10, 2002 with the collection of three (3) sets of samples from the site. 

One sample set was collected to be representative of effluent being discharged 

from FEP 1 (Outfall 601); a second set was collected to be representative of 

effluent being discharged from FEP 2 (Outfall 701); and the third was collected 

to be representative of groundwater in the uppermost aquifer at a location 

known to be hydraulically downgradient from the two final effluent ponds (MWA17). The samples were collected, containerized, and preserved by BWXT

personnel in accordance with requirements specified in SW-846, then shipped 

by overnight delivery for analysis at Olver Laboratories, Inc., Blacksburg, 

Virginia.

34. The samples were analyzed for volatile organic compounds (VOCs) and 

for semivolatile organic compounds (SVOCs) using SW-846 Method Nos. 8260B 

and 8270C, respectively. Instruments used for the analyses consisted in both 

cases of Hewlett-Packard Model 5890 gas chromatographs coupled to HewlettPackard Model 5972 mass selective detectors. Chromatography was performed 

using a Restek RTX-502.2 column for VOCs and a Restek RTX-5MS column for 

SVOCs. Mass spectral pattern matching against the NIST 129K database of 

authentic mass spectra (which includes spectra for each of the above-listed 

target analytes) was used to search for the compounds of interest. 

Subsequently, a more detailed search was carried out by selective ion 

monitoring. The latter technique involves searching the experimental results for 

 

8 U.S. EPA Ozone Depletion: http://www.epa.gov/ozone/ods.html
the presence of mass spectral signals uniquely associated with the target 

analytes. 

35. None were found, leading to the conclusion that fluorine-containing 

Hazardous Constituents are absent from wastewaters and from groundwater at 

the BWXT site. This conclusion is unqualified, except to note that the estimated 

minimum detection limit for these analyses is stated to be 1 μg/L. The results of 

these analyses are documented in Olver Laboratories, Inc. Report No. 15599, a 

copy of which is included as Exhibit 2.

36. In conclusion, fluorine-containing Hazardous Constituents other than HF 

could not be present in BWXT wastewaters or in FEP sludge for one or more of 

the following reasons:

1) No practical end uses;

2) Compounds banned by EPA from use and/or production;

3) Raw materials and/or reaction conditions needed for their formation 

are absent;

4) Would not survive in water or wastewater due to high reactivity;

5) Analytically, the compounds have been proved to be absent

Consideration of Potential Risks Associated with the Theoretical Presence 

of HF in Wastewater and Groundwater at the BWXT Site

37. For the simple reason that all but minute, unmeasurable quantities of HF 

are eliminated from wastewater streams generated at the BWXT facility, any and 

all risks to human health and the environment that might otherwise be attributed 

to HF are absent. The same conclusion can be drawn about groundwater, 
because the elimination of HF takes place prior to any opportunity for treated 

wastewaters to migrate by infiltration into the underlying aquifer. For similar 

reasons, the same conclusions apply to FEP sludges. 

38. My conclusions concerning any possible threats to human health or the 

environment that might be attributed to the presence of HF in FEP 1 and FEP 2 

at the BWXT facility are as follows:

HF, a defined Hazardous Constituent, does not represent a threat 

because

a. The overwhelming majority of HF used at the facility is removed from 

process wastewaters by precipitation to form an inert solid (CaF2).

b. Residual quantities of HF are neutralized to a pH of at least 6.0 prior to 

discharge such that the remaining HF is reduced to an amount that can 

only be theoretically calculated, not measured.

c. At the BWXT facility HF poses no substantial present or potential 

hazard to human health or the environment.

I declare under penalty of perjury that the foregoing is true and correct.

Executed this 17th day of February, 2003.

_______________________________

David W. Griffiths