CABRERA_2011a._Memorandum_USACE_Determination_of_Eligible_Contaminants_for_FUSRAP,_Investigation,_DuPont_Chambers_Works_FUSRAP_Site,_Deepwater,_NJ._June_2011..pdf

FINAL - June 2011

Memorandum USACE Determination of Eligible

Contaminants for FUSRAP Investigation

DuPont Chambers Works FUSRAP Site Deepwater, New Jersey

June 2011

Prepared by:

U.S. Army Corps of Engineers – Philadelphia District

With Technical Support from:

CABRERA Services, Inc.

1106 North Charles Street, Suite 300 Baltimore, MD 21201

Page i

TABLE OF CONTENTS

SECTION PAGE

1.0 INTRODUCTION

1.1 Authority and Scope of FUSRAP Cleanup Efforts

1.2 Definition of Eligible Contaminants

2.0 BACKGROUND

2.1 DuPont Chambers Works Manufacturing History

2.2 History of MED Production Activities at Chambers Works

2.3 MED Decontamination and FUSRAP Cleanup Activities

2.4 Identification of MED Radioactive and Chemical Compounds for Evaluation as Potentially Eligible Contaminants under FUSRAP

3.0 EVALUATION PROCESS FOR DETERMINING ELIGIBLE

CONTAMINANTS

3.1 CERCLA Hazardous Substance?

3.2 Persistence in the Environment?

3.3 Used by MED for Uranium Refinement Onsite?

4.0 FUSRAP ELIGIBLE CONTAMINANTS

4.1.1 Potentially Commingled Radioactive and Chemical Materials

4.2 Comingled Radioactive Contaminants

4.3 DuPont Chemical Contaminants

5.0 CONCLUSIONS

6.0 REFERENCES

LIST OF FIGURES

Figure 1: Locations of Chambers Works Site

Figure 2: Process Flow Diagram for MED Uranium Refinement Processes

Figure 3: FUSRAP MED-Related Operable Units (OUs) and Areas of Concern (AOCs)

Page ii

LIST OF TABLES

Table 1: Materials Produced under MED Contracts

Table 2: Constituents Screened for CERCLA Hazardous Substances, Environmental Persistence, Association with Uranium Processing Onsite

Table 3: FUSRAP Eligible Contaminants

Table A-1: Uranium Compounds and Chemical Compounds Identified for Potential FUSRAP Eligibility

Table A-2: Potentially FUSRAP Eligible Radionuclides

Page iii

LIST OF PRIMARY ACRONYMS AND ABBREVIATIONS

AEA Atomic Energy Act

AEC Atomic Energy Commission

AOC Area of Concern

CERCLA Comprehensive Environmental Response, Compensation, and Liability Act

CFR Code of Federal Regulations

DOE U.S. Department of Energy

DuPont E.I. DuPont de Nemours & Company

EPA U.S. Environmental Protection Agency

F2 fluorine gas

FUSRAP Formerly Utilized Sites Remedial Action Program

FY Fiscal Year

HSWA Hazardous and Solid Waste Amendments of 1984

MED Manhattan Engineer District

NaU2O7·6H20 sodium diuranate

NJDEP New Jersey Department of Environmental Protection

NRC Nuclear Regulatory Commission

OSRD Office of Scientific Research and Development

Pa-234m protactinium-234m

Ra-226 radium-226

RCRA Resource Conservation and Recovery Act

Th-230 thorium-230

Th-234 thorium-234

Th-231 thorium-231

U-234 uranium-234

U-235 uranium-235

U-238 uranium-238

UF4 uranium tetrafluoride, green salt

UF6 uranium hexafluoride

UO2 uranium dioxide, brown oxide

UO2(NO3)2 uranium nitrate, uranyl nitrate

UO3 uranium trioxide, orange oxide

UO4·2H2O uranium peroxide dihydrate

U3O8 triuranium octoxide, black oxide

USACE U.S. Army Corps of Engineers

USC United States Code

1.0 INTRODUCTION

This memorandum summarizes the determination of which contaminants are eligible for cleanup under the Formerly Utilized Sites Remedial Action Program (FUSRAP) at the E.I. DuPont de Nemours & Company (DuPont) Chambers Works in Deepwater, New Jersey. Certain areas on the property were used to process uranium in support of the nation’s early atomic energy program. These areas are subject to FUSRAP investigation and response actions in order to address low levels of residual contamination resulting from these activities. The areas are collectively identified as the DuPont Chambers Works FUSRAP Site (“the Site”) in order to distinguish these FUSRAP locations from the company’s commercial chemical manufacturing operations. FUSRAP is a program established in 1974 by the Atomic Energy Commission (AEC) to assess and clean up radioactive contamination at sites formerly used by the Manhattan Engineer District (MED) or AEC in support of the nation’s early atomic energy program.

Throughout this memorandum “MED” will be used to describe the processes, contaminants, and work related to the nation’s early atomic energy program whether or not the activities were performed under contract to MED or later to AEC.

In the 1940s, DuPont performed chemical and radioactive material production under seven MED contracts. DuPont processed sodium diuranate, uranium oxides, and uranium scrap to produce uranium tetrafluoride, uranium hexafluoride, and small quantities of uranium metal at Chambers Works. AEC conducted radiological surveys and decontamination activities in 1949 and released buildings based on the regulations and cleanup standards in effect at the time (Bechtel National, Inc., 1985).

Chambers Works is a 1,455-acre complex, owned and operated by DuPont, consisting of the Chambers Works manufacturing area and the former Carneys Point Works. Chambers Works is located along the eastern shore of the Delaware River on State Highway 130 (Shell Road) in Deepwater, New Jersey. Since the late 1890s, Chambers Works has had a long history of gunpowder, chemical and dye manufacturing which has resulted in widespread contamination of the property. The U.S. Environmental Protection Agency (EPA) Hazardous and Solid Waste Amendments (HSWA) permit and an agreement between the New Jersey Department of Environmental Protection (NJDEP) and DuPont require environmental investigation and cleanup actions including sitewide groundwater monitoring and containment.

In 1977, the U.S. Department of Energy (DOE), the responsible agency after AEC, designated a portion of Chambers Works as a FUSRAP site based on results of a DOE-conducted radiological survey (Oak Ridge National Laboratory, 1978). Residual radioactive contamination was identified in various media, primarily soil and groundwater, and determined to be a result of MED operations in support of the nation’s early atomic energy program. The DOE confirmed the presence of residual contamination during a subsequent survey in 1983 in accordance with the existing radioactive material guidelines and standards (Bechtel, 1985).

The purpose of this Memorandum is to review the radioactive and chemical materials used onsite in support of the MED uranium processing activities conducted by DuPont for the federal government and to determine whether or not the materials are eligible for FUSRAP investigation and cleanup.

1.1 Authority and Scope of FUSRAP Cleanup Efforts

The DOE, as the successor agency to MED and AEC, had independent authority under the Atomic Energy Act (AEA) to clean up sites within its jurisdiction. Congress transferred responsibility for FUSRAP to the USACE in the Energy and Water Development Appropriations Act for Fiscal Year (FY) 1998. Provisions in the Appropriations Acts for FY1999 and FY2000 (Pubic Laws 105-245 and 106-60) clarified Congressional intent that USACE should conduct cleanup work at FUSRAP sites subject to the Comprehensive Environmental Response, Compensation, and Liability Act of 1980, as amended (CERCLA) (42 United States Code [U.S.C.] Section 9601 et seq.), as amended, and the National Oil and Hazardous Substances Pollution Contingency Plan (40 Code of Federal Regulations [CFR] Part 300). Congress provided CERCLA lead agency authority to USACE for the selection of remedial actions at FUSRAP sites where there is federal responsibility for the contamination (USACE, 2003).

1.2 Definition of Eligible Contaminants

The scope of FUSRAP cleanup is defined by USACE document ER 200-1-4: Environmental Quality - Formerly Utilized Sites Remedial Action Program FUSRAP - Site Designation, Remediation Scope, and Recovering Costs (USACE, 2003). The types of hazardous substances considered within the scope of FUSRAP investigation and cleanup activities include the following:

• Radioactive contamination (primarily uranium and thorium and associated radionuclides) resulting from the Nation’s early atomic energy program activities, i.e., related to MED or AEC activities, to include hazardous substances associated with these activities (e.g., chemical separation, purification) (USACE 2003, paragraph 6(b)(2)(a)); and

• Other radioactive contamination or hazardous substances that are mixed or commingled with contamination from the early atomic energy program activities (USACE 2003, paragraph 6(b)(2)(b)).

Hazardous substances included in the eligible contaminants definition above are those listed in 40 CFR, Part 302, Table 302.4, List of Hazardous Substances and Reportable Quantities, and 40 CFR Part 355, Appendices A or B, The List of Extremely Hazardous Substances and Their Threshold Planning Quantities. As presented in the footnotes to Table 302.4, Appendix B, the final reportable quantities for all radionuclides apply to chemical compounds containing the radionuclides and elemental forms regardless of the diameter of pieces of solid material.

Materials not included in the two referenced lists are excluded from the scope of the FUSRAP cleanup.

Radioactive contamination and hazardous substances unrelated to activities conducted at Chambers Works in support of the nation’s early atomic energy program will be addressed under FUSRAP response actions only to the extent they are commingled with FUSRAP eligible contaminants. Residual radioactive contamination or hazardous substances unrelated to the nation’s early atomic energy program remaining after the completion of FUSRAP response actions and all radioactive contamination or hazardous substances not identified as FUSRAP-eligible contaminants are outside the scope of FUSRAP response actions at Chambers Works.

2.0 BACKGROUND

This section summarizes DuPont’s industrial and manufacturing history at the Chambers Works complex (formerly called the Dye Works). Activities associated with DuPont’s extensive chemical production operations are described as well as the manufacturing processes and materials employed at the site in the 1940s in support of MED uranium refinement operations (Bechtel National, Inc., 1985)(Weston, 2001).

2.1 DuPont Chambers Works Manufacturing History

The DuPont Chambers Works traces its industrial history back to 1892, when DuPont constructed the Carneys Point smokeless gunpowder plant at the northern end of Carneys Point.

This plant manufactured most of the black gunpowder used during World War I. DuPont then expanded its commercial chemical manufacturing operations into the low-lying area located to the south of Carneys Point, now known as the Chambers Works manufacturing area. By 1917, DuPont manufactured dye and specialty chemicals, producing Freon and tetraethyl lead in the 1920s, followed by aromatic chemical manufacturing in the 1940s. In the 1960s, DuPont began production of elastomers (elastic polymers) at Chambers Works (Bechtel, 1985)(Weston, 2001) (DuPont RFI).

DuPont, the EPA, and NJDEP include both the former Carneys Point Works (smokeless gunpowder plant) and Chambers Works in their description of the 1,455-acre complex.

Activities in support of the early atomic energy program were located only within a portion of the 700-acre manufacturing area referred to as Chambers Works. Figure 1 shows the overall DuPont property boundary including both areas: Chambers Works and the Carneys Point Works. DuPont Chambers Works FUSRAP Site collectively refers to the six specific areas identified and investigated as locations where activities occurred in support of the nation’s early atomic energy program. As mentioned these areas are located entirely within Chambers Works as shown in Figure 1. (Bechtel, 1985)(Weston, 2001).

As a result of DuPont’s long manufacturing history, constituent releases have impacted the environment at Chambers Works. In accordance with regulatory requirements of the Resource Conservation and Recovery Act (RCRA), DuPont is investigating several solid waste management units (SWMUs) to address these releases. Widespread contamination exists in soil and groundwater as a result of DuPont’s commercial chemical manufacturing operations. The RCRA investigations are separate from and outside the scope of the FUSRAP cleanup activities.

2.2 History of MED Production Activities at Chambers Works

During the time period 1942 to 1947, DuPont performed both chemical and radioactive material production in support of MED operations. Early in 1942, DuPont conducted research with uranium compounds to produce uranium tetrafluoride (UF4) and uranium hexafluoride (UF6) under contract to the Office of Scientific Research and Development (OSRD). When MED was chartered, it took over existing OSRD contracts. Chambers Works was contracted to perform uranium refinement activities due in large part to its existing fluorinated compound production capabilities. Fluorine and hydrofluoric acid (HF) were already being produced onsite. Initial MED contracts were for fluorocarbon production in late 1942, followed in early 1943 by contracts associated with uranium processing and refinement. Fluorocarbons were produced because of their properties as coolants, lubricants and plastics which would not react with uranium compounds (i.e., uranium hexafluoride) (Kesaris, 1997) and (DOE, 1997). There is no record that fluorocarbons were used for uranium refinement onsite.

The uranium refinement processes required large quantities of fluorine in order to: 1) treat metal surfaces to make them less reactive with uranium hexafluoride; and 2) produce fluorinated coolants, lubricants, and plastics that would not react with uranium hexafluoride (Kesaris, 1977).

Fluorinated coolants (Freon™), fluorinated lubricants (Fluorolube™), and fluorinated plastic (Teflon™) were invented and used at Chambers Works prior to MED operations. Fluorine was used onsite for uranium refinement.

At Chambers Works, DuPont operations in support of the nation’s early atomic energy program included the following:

• Production of fluorocarbons;

• Recovery of uranium from scrap materials and industrial residues to produce uranium compounds for further processing. Scrap materials were brought to Chambers Works from other MED facilities for processing;

• Conversion of black oxide (U3O8) and sodium diuranate to orange oxide (UO3) and then to brown oxide (UO2);

• Production of uranium tetrafluoride (UF4) from uranium oxides (UO2 and UO3);

• Production of uranium hexafluoride (UF6) from uranium tetrafluoride (and fluorine); and

• Production of uranium metal using magnesium and uranium tetrafluoride (green salt) (DOE, 1996 letter) (Weston, 2001).

Figure 2 presents a simplified process flow diagram of the uranium processing that took place at Chambers Works in support of the nation’s early atomic energy program. The MED processes involving uranium were conducted in various buildings within the Chambers Works manufacturing area. No MED activities took place at the Carneys Point Works, located in the northern portion of the property. Table 1 provides a summary of the DuPont projects or contracts related to MED activities from 1942 to 1947 and the materials used or produced in support of the early atomic energy program (DOE, 1996, Weston, 2001).

The MED uranium production and refinement processes that were conducted at Chambers Works are illustrated in Figure 2 and described below. The feedstock materials, other chemicals used or produced during the processes, and end products as well as their use are provided for each process. Neither enriched nor depleted uranium was produced or used.

• Recovery Process — designed to recover uranium from scrap materials and byproducts created during uranium processing. The recovery process converted uranium metal sludge, uranium metal dross and slag (waste residues) from the metal production process to uranium peroxide dihydrate. Uranium peroxide dihydrate was then converted to black oxide (U3O8).

o feedstock - uranium scrap materials or waste residues (dross and slag) o other chemical compounds used/produced - sulfuric acid, lime, hydrogen peroxide o end product - uranium peroxide dihydrate, black oxide [products used as feedstock in brown oxide process]

• Brown Oxide Process — designed to convert sodium diuranate, commercial black oxide, and uranium peroxide dihydrate to brown oxide (UO2).

o feedstock - black oxide, sodium diuranate, or uranium peroxide dihydrate o other chemical compounds used/produced - uranium nitrate, uranium trioxide (orange oxide), ethyl ether, nitric acid, hydrogen gas o end product – brown oxide (uranium dioxide) [product used as feedstock in the green salt process]

• Green Salt Process — designed to convert brown oxide using hydrofluoric acid into green salt (uranium tetrafluoride) (UF4).

o feedstock - uranium dioxide (brown oxide from the brown oxide process) o other chemical compounds used/produced - hydrofluoric acid, magnesium tray, carbon o end product – green salt (uranium tetrafluoride) [green salt was then used as feedstock for both the metal and hexafluoride processes]

• Hexafluoride Process — designed to convert green salt (uranium tetrafluoride) to uranium hexafluoride which was then shipped offsite for further processing.

o feedstock – green salt (uranium tetrafluoride) and fluorine gas, o other chemical compounds used/produced - fluorine o end product - uranium hexafluoride [sent to the Oak Ridge Reservation (Kesaris, 1997)]

• Metal Process— designed to convert green salt (uranium tetrafluoride) to uranium metal in the form of billets.

o feedstock – magnesium and green salt (uranium tetrafluoride) o other chemical compounds used/produced – magnesium o end product – uranium metal and uranium slag [uranium slag was used as feedstock for recovery process]

2.3 MED Decontamination and FUSRAP Cleanup Activities

In 1948 and 1949, AEC conducted radiological surveys and decontamination of building surfaces. Some buildings were dismantled. Remaining buildings were released back to DuPont in 1949, after radiological surveys based on the existing radiological criteria. Subsequent surveys were conducted in 1977 by Oak Ridge National Laboratory (ORNL) on behalf of DOE to evaluate potential contamination. Based on survey results, DOE designated Chambers Works for further investigation under FUSRAP in 1980. In 1983, DOE conducted further evaluation of the MED areas to further define the boundaries and depth of contamination (Bechtel National, Inc, 1985). This survey identified uranium-238 as the primary onsite contaminant in environmental samples (soil, water) and building materials. Based on historical records, MED activities primarily took place in six locations within Chambers Works as shown in Figure 3. These locations, later called Areas of Concern (AOCs), were designated for further evaluation under FUSRAP for residual radioactive contamination. USACE then grouped these AOCs into three separate operable units (OUs) to facilitate a phased site characterization and remedial investigation (Weston, 2004).

2.4 Identification of MED Radioactive and Chemical Compounds for Evaluation as Potentially Eligible Contaminants under FUSRAP

A historical records review was conducted as part of this report to identify which radionuclides and chemical compounds were associated with MED operations at Chambers Works between 1942 and 1947. The review included available MED contract documents, declassified documents relating to the Manhattan Engineer District history, and DOE correspondence and technical reports. The review identified the processes and use of specific compounds at the site as well as examination of general industry references. From this review, the USACE compiled an initial list of potential radioactive and chemical compounds for further consideration. These compounds are listed below and presented in Tables A-1 and A-2 located in Appendix A.

Radioactive Compounds: DuPont received various uranium oxides as feedstock for refinement, including sodium diuranate and triuranium octoxide (black oxide). Uranium ore was not used as a feedstock at the Site; instead the ore was processed at other MED locations and shipped to Chambers Works. The nine uranium compounds listed below include the feedstocks, intermediates and products associated with MED activity onsite. These compounds are regulated due to their radioactivity rather than their chemical characteristics.

1. uranium peroxide dihydrate UO4∙2(H2O)

2. uranium dioxide (brown oxide) UO2

3. triuranium octoxide (black oxide) U3O8

4. sodium diuranate Na2U2O7∙ 6H2O

5. uranium nitrate solution UO2(NO3)2∙6H2O

6. uranium trioxide (orange oxide) UO3

7. uranium tetrafluoride (green salt) UF4

8. uranium hexafluoride UF6

9. uranium metal (metal biscuit) U

Radionuclides: Uranium ore typically contains all of the progeny of Uranium-238 (U-238) which have been in-grown through the natural radioactive decay process. The beneficiation of uranium ore was performed by offsite suppliers to make the sodium diuranate and black oxide feedstocks used at Chambers Works. Beneficiation is the process of crushing and separating ore into useable materials. This was performed at Vitro Chemicals of Canonsburg, Pennsylvania.

and resulted in the removal of impurities, including any uranium daughters. Since the uranium was refined approximately 65 years ago, there would not yet be enough time for significant re-ingrowth of daughters. However, USACE evaluated the relative concentrations of Th-230 and Ra-226 found in site samples and compared them with concentrations expected from progeny in-growth. It was found that the progeny activities were greater than would be expected from daughter in-growth alone. USACE concluded that the excess concentrations of Th-230 and Ra- 226 could be due to the presence of impurities within the original feedstock.

The uranium parents and their short-lived progeny are:

o Uranium-238 (U-238) – 4.5 billion year half-life

- short-lived decay progeny:

Thorium-234 (Th-234) – 24-day half-life

Protactinium-234m (Pa-234m) – 1.17-minute half-life o Uranium-235 (U-235) - 700 million year half-life

- short-lived decay progeny:

Thorium-231 (Th-231) - 25-hour half-life o Uranium-234 (U-234) – 240,000 year half-life (no short-lived decay progeny)

The long-lived decay progeny of U-238 are:

o Thorium-230 (Th-230) – 77,000 year half life o Radium-226 (Ra-226) – 1600 year half life

Thorium-234, Pa-234m, and Th-231 were not considered as distinct constituents due to their short half-lives. Decay progeny of Ra-226 are not considered to have sufficiently grown in since beneficiation and therefore are not considered as distinct constituents. The three uranium parents and the long-lived decay progeny of U-238 are retained for further consideration as potential FUSRAP eligible contaminants in Section 3.

Other Chemical Compounds: Based on the review of available historical documents, USACE identified the following chemical compounds as either being used in the uranium refinement processes or as chemical materials produced under MED contract. Evaluation of eligibility of these compounds for FUSRAP response actions is further discussed in Section 3.

1. Ethyl Ether

2. Fluorine Gas

3. Fluorolube

4. Freon 113

5. Gyp cake

6. Hexadecafluorodimethylcyclo-hexane

7. Hydrofluoric Acid

8. Hydrogen Gas

9. Hydrogen Peroxide

10. Lime

11. Magnesium

12. Magnesium Fluoride

13. Monochlorohexadeca-fluorodimethylcyclohexane

14. Monochlorohexafluoroxylene

15. Nitric Acid

16. N-perfluoroheptane

17. Sulfuric acid

3.0 EVALUATION PROCESS FOR DETERMINING ELIGIBLE

CONTAMINANTS

After compilation of the initial lists of chemical and radioactive compounds/radionuclides, USACE further evaluated the lists in order to identify the eligible contaminants for the FUSRAP response in accordance with CERCLA. Physical and chemical properties of each compound were also reviewed to evaluate the likelihood that the substance would still exist in the environment more than 65 years after MED operations. Finally, remaining contaminants were evaluated to determine if their presence is a direct result of MED uranium processing. In summary, the following criteria or questions were considered in order to make the eligibility determination and identify constituents of potential concern for the FUSRAP investigations:

• Is the compound a CERCLA hazardous substance?

• Do circumstances support a reasonable conclusion that the contaminant resulting from DuPont activities in support of MED contracts would still be present at the Site?

• Do circumstances support a reasonable conclusion that the contaminant present is due to MED uranium processing operations at the Site and not a result of DuPont chemical production or other industrial contamination?

3.1 CERCLA Hazardous Substances

As presented in Section 1.0, CERCLA hazardous substances are those listed in 40 CFR, Part 302, Table 302.4, List of Hazardous Substances and Reportable Quantities, and 40 CFR Part 355, Appendices A or B, The List of Extremely Hazardous Substances and Their Threshold Planning Quantities. The 17 chemical compounds identified in Table A-1 were compared to the lists of CERCLA hazardous substances. A total of five (5) MED-related chemicals were identified as meeting this criteria and were retained for further evaluation: ethyl ether; fluorine;

hydrofluoric acid; nitric acid; and sulfuric acid. These compounds, with the exclusion of ethyl ether, were determined to be used in the extraction and recovery processes to convert radioactive materials to a usable product. Ethyl ether was used in the initial extraction process.

While only one of the nine uranium compounds was specifically identified as being a CERCLA hazardous substance (uranyl nitrate), each of the five MED-related radionuclides (U-234, U-235, U-238, Th-230 and Ra-226) presented in Section 2.0 were determined to meet this criteria and thus were retained for further evaluation.

3.2 Persistence in the Environment

The five MED-related chemicals identified as CERCLA hazardous substances in Table 2 exist as acids or gases which are readily oxidized or neutralized in the environment. Therefore, none of the five chemicals are considered to be persistent in the environment and therefore are not expected to be found at the site. The five chemicals (ethyl ether, fluorine, hydrofluoric acid, nitric acid, and sulfuric acid) have been removed from further consideration as possible eligible contaminants.

Based upon radioactive half-lives, all five radionuclides (U-234, U-235, U-238, Th-230 and Ra-

226) are considered to still be present at the site. The radioactive half-life of these constituents range from 1,600 years (Ra-226) to 4.5 x109 years (U-238).

3.3 Used by MED for Uranium Refinement Onsite

DuPont manufactured fluorinated solvents, fluorinated lubricants and fluorinated polymers onsite under MED contract, including intermediates. However, this production was not associated with uranium refinement onsite, nor was their production exclusive to MED, therefore these compounds are not eligible for FUSRAP cleanup.

4.0 FUSRAP ELIGIBLE CONTAMINANTS

Upon consideration of the eligibility criteria (Section 1.1) and the results of the screening process (Section 3.0), the review found five radiological contaminants eligible for FUSRAP investigation and response action. Table 3 lists each radionuclide and provides the basis for its inclusion as an eligible contaminant. Each radioactive constituent listed was determined to be unique to MED by its association with the nine MED-unique uranium compounds used in the uranium refinement processes.

4.1 Potentially Commingled Radioactive and Chemical Materials Certain radioactive and chemical materials may be encountered during the FUSRAP investigations that are related to DuPont’s commercial chemical manufacturing operations.

These materials, although unrelated to MED activities at Chambers Works, may be commingled with the FUSRAP eligible contaminants that need to be addressed through a CERCLA response action. In this case the remediation of non-MED commingled contaminants will be performed according to the location and remediation goals established for the MED eligible contaminants.

In other words, the non-MED contaminants will be removed along with the MED-related contaminants to the extent necessary to clean up FUSRAP eligible contaminants.

Historical documents show that DuPont radioactive waste may have been co-located with FUSRAP-eligible contaminants in AOC 6 (East Area). Also, due to historical use of “naturally occurring” radioactive materials by Chambers Works, non-MED radioactive material could potentially be commingled with FUSRAP eligible contaminants.

4.2 Commingled Radioactive Contaminants

Tritium, thoriated nickel, and carbon-14 were identified as being used at Chambers Works for non-MED activities and were reportedly disposed of in a FUSRAP area. Since there are no records indicating their use in the uranium processing onsite, the USACE does not consider these materials FUSRAP related. Therefore, the USACE will not investigate these radioactive materials as part of the FUSRAP response action.

4.3 DuPont Chemical Contaminants

Certain DuPont chemical contaminants have been identified to coexist with MED contamination.

Coal tar light nonaqueous phase liquid and certain aqueous-phase volatile organic compounds have been identified in MED areas. These chemical constituents were not used in MED processes but are instead associated with the facility’s non-FUSRAP chemical manufacturing operations.

5.0 CONCLUSIONS

USACE conducted an evaluation to identify potential chemical and radioactive constituents of potential concern at the DuPont Chambers Works FUSRAP site and documented the constituents’ eligibility for FUSRAP investigation and possible remediation. Based on the knowledge of feedstock materials, MED manufacturing processes, products produced, and the evaluation results, USACE concluded that five radionuclides are eligible contaminants.

USACE identified five radionuclides as MED eligible contaminants by association with the 9 uranium compounds used in the uranium refinement processes and the potential impurities in the feedstock. The three uranium isotopes U-238, U-235 and U234 plus Ra-226 and Th-230 were determined to be eligible for FUSRAP investigation and cleanup.

Several chemical compounds were identified and screened for eligibility for FUSRAP investigation and cleanup activities. Five chemicals were identified as hazardous substances that were used in the MED refining processes. These substances were primarily acids or gases that are not persistent in the environment. These compounds are readily oxidized or neutralized in the environment. No chemical compounds or hazardous substances fit the criteria as FUSRAP eligible contaminants. Therefore, USACE determined that only the radionuclides associated with the uranium processing were to be considered during the FUSRAP response action.

6.0 REFERENCES

Ahmed, S., A. Mahmood, M. A. Awan, and U. ur Rehman, 1999. Single step conversion of UO2 and U3O8 into uranyl sulphate solution. Journal of Radioanalytical and Nuclear Chemistry. Volume 241, Number 1 / July 1999.

Bechtel National, Inc. (BNI). 1985. Radiological Survey of the E. I. DuPont De Nemours and Company, Chambers Works Plant, Deepwater, New Jersey. DOE/QR/20722-22. 143 pgs. Dames & Moore Record No. 1007.

DOE, 1997. Litigation Report – E.I. DuPont de Nemours and Company, Conoco, Inc., and Sporting Goods Properties, Inc. V. United States of America. Oak Ridge Operations Office, April 9, 1997.

Kesaris, Paul, 1977. Manhattan Project Official History and Documents. Washington, D.C.:

University Publications of America.

Oak Ridge National Laboratory (ORNL). 1978. U.S. Department of Energy, Formerly Utilized MED/AEC Sites Remedial Action Program, Radiological Survey of the E.I. DuPont de Nemours Company, Deepwater, New Jersey. DOE.EV-0005/8. December.

U.S. Army Corps of Engineers (USACE). 2003. Formerly Utilized Sites Remedial Action Program (FUSRAP) – Site Designation, Remediation Scope, and Recovering Costs.

USACE Environmental Regulation (ER) 200-1-4.

Weston Solutions Inc. (Weston) 2001. Final Technical Project Planning Meeting Brief, Phase I Records Review, DuPont Chambers Works, Deepwater, New Jersey (an update from an original document prepared by URS Corporation, 13 June 2000).

Weston, 2004. Final Remedial Investigation Report, Remedial Investigation OU 1: AOC 1, Former Building 845 Area and AOC 2, F Parking Corral, DuPont Chambers Works Site, Deepwater, New Jersey.

FIGURES

FINAL – June 2011

TABLES

U.S. ARMY CORPS

OF ENGINEERS

Memorandum Determination of FUSRAP

Eligible Contaminants

June 2011

Location of DuPont Chambers Works

CARNEY'S POINT WORKS

CHAMBERS WORKS SITE

DuPont Chambers

Works

New Jersey

Miles 0 20 40 60 8010

Carney's Point Works

Chambers Works Site

DuPont Property Boundary

Background Reference Area

OU1

OU2

OU3

AOC 1

AOC 2

AOC 3

AOC 5

AOC 4

AOC 6

FUSRAP Areas q

Note:

Source: USGS 7.5'' Series Quads., Wimington South & Penns Grove, NJ, DEL 1967, photorevised respectively 1987 & 1988

0 740 1,480 2,220 2,960370 Feet

Figure 1

Cabrera Services 1106 N. Charles St Suite 300

June 2011 Figure 2

Scrap/Slag

700 C Sulfuric Acid then Lime

Filter Cake Disposal

Liquor Hydrogen Peroxide

Liquor to Sewer

Slurry

Rotary Calciner

Nitric Acid

To Ether Recovery

Precipitation Tank

Precipitation Tanks

Ether Extracting Columns

Ethyl Ether

Purified Uranium Nitrate

Solution

Nitric Acid Fumes Recovery

Powdered Orange Oxide

UO3

Uranium Feedstock*

Hydrofluoric Acid

Brown Oxide

UO2

Carbon or Magnesium Tray

580 C

Heat

Excess Acid to Recovery

Green Salt

UF4

Uranium Tetraflouride

Flourine Gas

Green Salt

UF4

Nickle Tray

200 - 300 C

Heat

Condenser/ Distiller

Uranium Hexaflouride UF6

Storage Cylinder

Hexafluoride Process

Magnesium and Green Salt UF4

Mixture

Reaction Bomb Placed in Furnance

1360 C

Uranium Metal Billets

Recovery Process

Metal Process

Metal Biscuits

After Reaction

Slag to Recovery Process**

Biscuits Moved to Furnace

Biscuits

Formed in Molds in Electric Furnace

Filters

Nitric Acid Removal

&R &R&R

Pure Brown Oxide UO2

Reduction of U03

Nitric Acid Removal

Heat

Dissolve and Boil Down

Uranium Peroxide Dihydrate

UO42H2O

Uranium Nitrate

Solution

Brown Oxide Process

Green Salt Process

Pure Brown Oxide UO2

U.S. ARMY CORPS

OF ENGINEERS

Memorandum Determination of FUSRAP

Eligible Contaminants

Simplified Diagram of Uranium Refinement Processes

*Feedstock in Brown Oxide process at Chambers Works:

Black Oxide (U3O8), Uranium Peroxide Dihydrate (UO42H20) or Sodium Diuranate (Na2U2O76H2O)

**Slag refers to uranium metal sludge or uranium metal residues

Cabrera Services 1106 N Charles St

Figure 3

U.S. ARMY CORPS

OF ENGINEERS

Memorandum Determination of FUSRAP

Eligible Contaminants

OU3 AOC 4

June 2011 q

OU3 AOC 6

FUSRAP MED-related Operable Units (OUs) and Areas of Concern (AOCs)

OU1 AOC 2

OU1 AOC 1

OU2 AOC 3

vOU3

OU2 AOC 5 0 750 1,500375 Feet

Note: Aerial Photo taken in September 2005

OU1

OU2

OU3

AOC 1

AOC 2

AOC 3

AOC 5

AOC 4

AOC 6

Cabrera Services 1106 N. Charles St

Table 1: Materials Produced under MED Contracts DuPont Project/Contract No. Contracted Materials Approximate

Amount (lbs) Project 9595 Contract No. W-7412-Eng. 2

N-Perfluoroheptane (C7F16) 117,032 Fluorolube 15,447

Project 9634 Contract No. W-7412-Eng. 3

Brown Oxide (UO2), 3,940,000 Green Salt (UF4), 1,216,000 Uranium Metal (U) 464,000

Project 9757 Contract No. W-7412-Eng. 6

Hexadecafluorodimethylcyclohexane 3,888,219 Monochlorohexadecafluorodimethylcyclohexane 286,416 Fluorolube 8,216 N-Perfluoroheptane (C7F16) unknown

Project 9233 Contract No. W-7412-Eng. 8

Hydrofluoric Acid 300,000 lbs/month

Project 9803 Contract No. W-7412-Eng.22

Black Oxide 1,964,000

Contract No. W-7412-Eng.151 Research and Development – Laboratory Scale unknown Contract No. W-7412-Eng. 161 Freon 113 79,850

Source: Weston, 2001. Final Technical Project Planning Meeting Brief, Phase I Records Review.

Table 2: Constituents Screened for CERCLA Hazardous Substances, Association with Uranium Processing Onsite, and Environmental Persistence

Constituent Name

CERCLA

Hazardous Substance

Associated with Uranium

Refinement Onsite

Persistent in Environment

Ethyl Ether Yes Yes No Fluorine Yes Yes No Fluorolube No No --- Freon 113 Yes No --- Gyp cake No Yes --- Hexadecafluorodimethylcyclohexane Yes No --- Hydrofluoric Acid Yes Yes No Hydrogen Gas No Yes --- Hydrogen Peroxide No Yes --- Lime No Yes --- Magnesium No Yes --- Magnesium Fluoride No Yes --- Monochlorohexadeca-fluorodimethylcyclohexane

Yes No ---

Monochlorohexafluoroxylene Yes No --- Nitric Acid Yes Yes No N-perfluoroheptane Yes No --- Radium-226 Yes Yes Yes Sulfuric Acid Yes Yes No Thorium-230 Yes Yes Yes Uranium-234* Yes Yes Yes Uranium-235* Yes Yes Yes Uranium-238* Yes Yes Yes

* includes uranium compounds

Table 3: FUSRAP Eligible Contaminants

Eligible Contaminant Justification for Inclusion

U-238 MED radionuclide/CERCLA Hazardous Substance

U-235 MED radionuclide/ CERCLA Hazardous Substance

U-234 MED radionuclide/ CERCLA Hazardous Substance

Ra-226 A possible contaminant in feedstock and U-238 daughter/ CERCLA Hazardous Substance

Th-230 A possible contaminant in feedstock and U-238 daughter/ CERCLA Hazardous Substance

Table A-1: Uranium Compounds and Chemical Compounds Identified for Potential FUSRAP Eligibility

Compound Name Formula

MED Process Related?

Y/N

MED

Radioactive

Material Mentioned in

MED Contract DuPont

Project No. Specific MED Process

Production Quantities Contractual

Documentation?

Uranium Compounds Triuranium Octoxide (Black Oxide) U3O8 Yes Yes No 9634 Input Product for Brown Oxide

Production Yes

Sodium Diuranate (chemical found in yellow oxide) Na2U2O7· 6H2O Yes Yes No 9634 Input Product for Brown Oxide

Production No

Uranium nitrate (solution) UO2(NO3)2*6H2O Yes Yes No 9634 Intermediary Product for Brown Oxide Production No

Uranium Peroxide Dihydrate UO4·2(H2O) Yes Yes No 9803 Input product for Brown Oxide Process Unknown

Uranium Trioxide (Orange Oxide) UO3 Yes Yes No 9634 Brown Oxide Unknown

Uranium Dioxide (Brown Oxide) UO2 Yes Yes No 9634 Brown Oxide Yes

Uranium Tetrafluoride (Green Salt) UF4 Yes Yes No 9634 Metal Process Unknown

Uranium Hexafluoride UF6 Yes Yes No 9634 Metal Process Unknown

Uranium Metal U Yes Yes No 9634 Metal Process Unknown

Chemical Compounds

Ethyl Ether C2H5OC2H5 Yes No No 9634 Brown Oxide No

Fluorine Gas F2 Yes No No 9634 Hexafluoride Process Unknown

Fluorolube C4Cl4F6 Yes No Yes 9595, 9757 Fluorinated Lubricant Yes

Freon C2Cl3F3

Calcium Sulfate Sludge (Gyp Cake) (predominantly gypsum sludge) CaSO4 2(H2O) Yes No No 9634

Waste formed during Uranium Recovery Process; hydrofluoric acid production

Unknown

Hydrofluoric Acid HF Yes No No 9634 Green Salt Yes

Hydrogen Gas H2 Yes No No 9634 Brown Oxide Unknown

Hydrogen Peroxide H2O2 Yes No No 9803 Recovery Process Unknown Hexadecafluorodimethyl-cyclohexane C6F10(CF3)2 Yes No Yes 9757 Fluorinated Solvent Yes

Lime (Calcium oxide) CaO Yes No No 9803 Recovery Process Unknown

Magnesium Mg Yes No No 9634 Metal Process Unknown

Magnesium Fluoride MgF2 Yes No No 9634 Metal Process Unknown Monochlorohexadecafluoro-dimethylcyclohexane C6ClF9(CF3)2 Yes No Yes 9757 Fluorinated Solvent Yes monochlorohexafluoroxylene C6H3Cl(CF3)2 Yes No Yes 9757 Fluorinated Solvent No

Nitric Acid HNO3 Yes No No 9634 Brown Oxide Unknown n-perfluoroheptane C7F16 Yes No Yes 9595, 9757 Produced for Oak Ridge, TN facility; used as sealant, coolant and "dummy" gas

Yes/No

Sulfuric Acid H2SO4 Yes No No 9803 Recovery Process Unknown

Table A-2: Potentially FUSRAP Eligible Radionuclides

Radionuclide Name

MED

Process

Related?

Possible use onsite for non- MED DuPont

Processes?

Radiological Half

Life Within Decay Chain of Reason Reported/Identified

Refined Uranium (Total Uranium with short-lived1 daughters) Yes No Multiple

Refined U decay chain consists of U-234, U- 235, U-238 and their short-lived progeny Potential MED contaminant

Uranium-234 (U-234) Yes Yes 2.4x105 yrs Refined U, Natural U (parent radionuclide) Member of Natural Uranium and Refined Uranium decay chains

Uranium-235 (U-235) Yes No 7.0x108 yrs Refined U, Natural U (parent radionuclide) Member of Natural Uranium and Refined Uranium decay chains

Uranium-238 (U-238) Yes Yes 4.5x109 yrs Refined U, Natural U (parent radionuclide) Member of Natural Uranium and Refined Uranium decay chains

Thorium-230 (Th-230) Possible Yes 7.5x104 yrs Natural U, Thorium-230 (parent radionuclide) Member of Natural Uranium decay chain;

Potential MED co-contaminant

Thorium-234 (Th-234) Yes Yes 24.1 days Refined U, Natural U Member of Natural Uranium and Refined Uranium decay chains

Protactinium-234m (Pa-234m) Yes Yes 1.2 min Refined U, Natural U Member of Natural Uranium and Refined Uranium decay chains

Radium-226 (Ra-226) Possible Yes 1600 yrs Natural U, Th-230, Ra-226 (parent radionuclide)

Member of Natural Uranium decay chain;

Potential MED co-contaminant; member of Th- 230 decay chain

Radon-222 (Rn-222) Possible Yes 3.8 days Natural U, Th-230, Ra-226 Member of Natural Uranium decay chain; Member of Th-230/Ra-226 decay chain

Lead-214 (Pb-214) Possible Yes 27 min Natural U, Th-230, Ra-226 Member of Natural Uranium decay chain; Member of Th-230/Ra-226 decay chain

Bismuth-214 (Bi-214) Possible Yes 20 min Natural U, Th-230, Ra-226 Member of Natural Uranium decay chain; Member of Th-230/Ra-226 decay chain