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 environ mental 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 w ith 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 ch emicals 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 o perations.
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 dedicatedto the tre atment 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 wastew aters. 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 Decl aration. 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 WASTEWAT ER 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
ap plications. 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 clea ning 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 quantitie s 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 hazard ous 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 va rious 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 purifie d 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 requi rements 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 identificatio n 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 hasbeen assigned Chemical Abstracts Services Registry N umber (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, s eparate from its acidity. For example, in its Public Health Statement for HF, 1 the 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 f urther 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 phos phoric 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 + + F 23. 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.g ov/toxprofiles/phs11.html.hydroxide (NaOH). The chemical equation that represents neutralization of HF

by NaOH is as follows: HF + NaOH  NaF + H 2 0 The products of neutralization are sodium fluoride (NaF) and water (H 2 O).
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  CaF 2 + 2H 2 0 Since calcium fluoride (CaF 2 ) 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, CaF 2 , 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 Const ituent 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 “K a ”. For solution s of HF in pure water at 25oC, the value of K a = 3.53 x 10 - 4

. 2 Mathematically, K a represents the product of the hydrogen ion and

2 Handbook of Chemistry and Physics, 73 rd 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):

Since hydrogen ion concentration appears in the numerator of this equation, the distribution of total fluoride between its ionized and unionized forms (F and HF, respectively) is pH

- dependent. By substituting into the equati on 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 K a , 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 a t valuesranging 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 r epresent 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 analyt ically 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 minuteremaining 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 fre e 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 W astewater 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 F 2 7782

- 41

- 4
Fluoroacetamide C 2 H 4 FNO 640

- 19

- 7 Fluoroacetic acid, sodium salt C 2 H 2 FO 2 Na 62

- 74

- 8 Diisopropylfluorophosphate C 6 H 14 FO 3 P 55

- 91

- 4Carbon oxyfluoride CF 2 O 353

- 50

- 4

Dichlorodifluoromethane CCl 2 F 2 75

- 71

- 8 Trichloromonofluoromethane CCl 3 F 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

a s 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 reactio n 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: Fluorine 3 : Fluorine is a greenish diatomic gas w ith a boiling point of

– 188.13 o C. It is the most chemically reactive of all elements. Because of its reactivity, it rarely, if ever, exists as F 2 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 Salt 4 : These two compounds are closely related. In its acid form, the s odium 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 198 0s, 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 , 10 th 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 o f these compounds would require specialized raw materials and reaction conditions that do not exist at the BWXT facility. Diisopropylfluorophosphate 6 : 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 aci d (or its salts), and fluoride ion, both of which are non

- hazardous compounds. Dichlorodifluoromethane and Trichloromonofluoromethane 8 : These two compounds are members of the class of compounds known as chlorofluorocarbons, or CFCs for short. Both are d efined 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 BW XT 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 manufactur ing 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

m embers 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 , 10 th Edition, 1983, entry 1803.fluoroacetic acid, diisopropylfluorophosphate, dichlorodifluoromethane, and

trichloromonofluoromethane. The s ampling 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 collecte d 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 (M WA

17). 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 chromatograp hs coupled to Hewlett

Packard 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 mas s 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 th e experimental results for

8 U.S. EPA Ozone Depletion: http://www.epa.gov/ozone/ods.htmlthe 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 w hich 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 f rom 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 an d 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 an d 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 (CaF 2 ).
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 potenti al 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