Document X7DdngNBxa0ZYdjeepwK9zXgg
ENFORCEMENT CONFIDENTIAL
NEICVP1508E01
NEIC CIVIL INVESTIGATION REPORT Calgon Carbon - Big Sandy Plant Catlettsburg, Kentucky 41129
Investigation Dates: March 21-29, 2023
TRENT
Digitally signed by TRENT RAINEY
RAINEY
Date: 2024.02.22 12:22:08 -07'00'
Mike Solter
Project Manager, NEIC
Daniel Hurlbut
Digitally signed by Daniel Hurlbut Date: 2024.02.22 12:28:37 -07'00'
Daniel Hurlbut
Analytical Project Manager, NEIC
Authorized for Release by: Digitally signed by LAWRENCE LUTZ Date: 2024.02.22 15:10:33 -07'00'
Craig Lutz, Acting Field Branch Manager, NEIC
Report Prepared for: EPA OCE-WED and WCED 1200 Pennsylvania Avenue NW Washington, D.C. 20460
and EPA Region 4 61 Forsyth Street SW Atlanta, Georgia 30303
NATIONAL ENFORCEMENT INVESTIGATIONS CENTER P.O. Box 25227
Building 25, Denver Federal Center Denver, Colorado 80225
Page 1 of 46
ENFORCEMENT CONFIDENTIAL
CONTENTS
INVESTIGATION OVERVIEW ............................................................................................................ 4 PROJECT OBJECTIVE .................................................................................................................... 4 FACILITY CONTACT INFORMATION ............................................................................................. 5 FACILITY OVERVIEW .................................................................................................................... 5 FACILITY OPERATIONS SUMMARY .............................................................................................. 6 FIELD ACTIVITIES SUMMARY....................................................................................................... 9 Measurement and Sampling Activities ................................................................................. 10 LABORATORY ACTIVITIES SUMMARY........................................................................................ 16 ANALYTICAL RESULTS................................................................................................................ 18 Targeted PFAS Analysis ......................................................................................................... 20 Semi-Targeted PFAS Analysis ............................................................................................... 27
INVESTIGATION OBSERVATIONS................................................................................................... 30
TABLES
Table 1. PROJECT TEAM MEMBERS ................................................................................................ 4 Table 2. FACILITY CONTACT INFORMATION ................................................................................... 5 Table 3. KYPDES Permit No. KY0022276 Outfalls ........................................................................... 6 Table 4. FIELD MEASUREMENT AND FIELD SAMPLING ACTIVITIES .............................................. 11 Table 5. ANALYTICAL OBJECTIVE, TECHNIQUE, AND METHOD; ANALYST; AND DATE PERFORMED ....................................................................................................................................................... 17 Table 6. SUMMARY OF SAMPLE IDENTIFICATION AND DESCRIPTION ......................................... 19 Table 7. TARGETED PFAS.............................................................................................................. 20 Table 8. RESULTS FOR VP1508-07 THROUGH VP1508-11, AND REPORTING LIMITS .................. 22 Table 9. RESULTS FOR VP1508-12 THROUGH VP1508-16, AND REPORTING LIMITS .................. 23 Table 10. RESULTS FOR VP1508-17, VP1508-18, VP1508-20, AND REPORTING LIMITS ............. 24 Table 11. RESULTS FOR VP1508-21 THROUGH VP1508-24, AND REPORTING LIMITS ................ 25 Table 12. SEMI-TARGETED PFAS, NEIC ACRONYM, FORMULAS and EXACT MASS VALUES......... 27 Table 13. SEMI-TARGETED PFAS RESULTS .................................................................................... 28
APPENDICES (*NEIC-created documents)
A Calgon Carbon Big Sandy Plant Final Permit KY0022276 (27 pages)
B Wastewater Flow Diagram (2 pages)
C Calgon Carbon RCRA Permit (126 pages)
D Prime Lines Process Diagram (3 pages)
E
Acid Wash Process Diagram (1 page)
F
FluePAC Process Diagram (1 page)
G Reactivation Process Diagram (1 page)
H VP1508 Calgon Carbon- Big Sandy Plant - Photographs (91 pages)*
I
Calgon Carbon ERG Sampling Report (28 pages)
J
Sample Chain of Custody Record (2 pages)*
K Calgon Carbon - Big Sandy Plant - Laboratory Photos (6 pages)*
L
Calgon Carbon-SWPPP-BMP (259 pages)
M REACT Trench Photographs (1 page)
N 3-22-23 Spent Carbon Spill (1 page)
O Calgon Carbon RCRA Permit Application (1527 pages)
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Calgon Carbon - Big Sandy Plant Catlettsburg, Kentucky
ENFORCEMENT CONFIDENTIAL P REACT Dike Cleanup Photograph (1 page)
These Contents pages shows all the sections contained in this report and provides a clear indication of the end of this report.
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Calgon Carbon - Big Sandy Plant Catlettsburg, Kentucky
ENFORCEMENT CONFIDENTIAL
INVESTIGATION OVERVIEW
PROJECT OBJECTIVE
U.S. Environmental Protection Agency (EPA) Office of Civil Enforcement (OCE) Water Enforcement Division (WED) and Waste and Chemical Enforcement Division (WCED), and Region 4 (Region), requested EPA's National Enforcement Investigations Center (NEIC) to conduct a multimedia compliance investigation of the Calgon Carbon - Big Sandy Plant (Calgon) facility located at 15024 Old United States Route 23 South, in Catlettsburg, Kentucky, 41129.
The primary purpose of the inspection was to conduct a comprehensive compliance evaluation inspection of the facility under the Clean Water Act (CWA) and the Resource Conservation and Recovery Act (RCRA). NEIC inspectors also conducted an evaluation of per and polyfluoroalkyl substances (PFAS) wastewater generation, management, treatment, and effluent discharge. Appropriate samples of effluent wastewater were collected for analysis by the NEIC laboratory for PFAS and submission to EPA Office of Research and Development (ORD) for non-targeted analysis of PFAS compounds. Soil and sediment samples were collected by CWA team members for analysis at the ORD laboratory in Narragansett, Rhode Island. NEIC inspectors also evaluated the facility's RCRA compliance including compliance with the requirement to make hazardous waste determinations, evaluation of waste management practices including inspections of process areas, satellite hazardous waste accumulation areas, and less-than-90-day hazardous waste accumulation areas and tanks. RCRA team members also conducted an evaluation of waste management practices of solid and hazardous wastes containing PFAS.
Table 1 lists the project team members.
Team Member Mike Solter
Alex Flevarakis
Craig Lutz
Trent Rainey Zach Schlachter Daniel Hurlbut
Jessica Krank Daya Mitchell
Scott Gerstner
Laurence Libelo Robert Nakamoto
Nikki Radford Ben Walter Justin Young
Table 1. PROJECT TEAM MEMBERS
Organization
NEIC NEIC
NEIC
NEIC NEIC NEIC NEIC NEIC REGIONAL AND OTHER CONTACTS Kentucky Department for Environmental Protection (KY-DEP) EPA-OCE-WED EPA Region 4 EPA Region 4 KY-DEP EPA-OCE-WCED
Project Role Project manager (PM) Field team - CWA inspector Field team - RCRA team lead and
inspector Field team - CWA inspector Field team - RCRA inspector Analytical project manager (APM)
Laboratory analyst Laboratory analyst
RCRA team member
CWA team member RCRA team member CWA team member RCRA team member RCRA team member
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Calgon Carbon - Big Sandy Plant Catlettsburg, Kentucky
ENFORCEMENT CONFIDENTIAL
Figure 1
FACILITY CONTACT INFORMATION Table 2 lists the primary facility contacts.
Table 2. FACILITY CONTACT INFORMATION
Name, Title
Phone No.
Email Address
Eric Nash, Regional EH&S manager
606-471-4233
eric.nash@kuraray.com
Marvin Church, Director, EH&S
412-787-6724
mchurch@calgoncarbon.com
Brian Lauerman, Plant manager
606-739-2326
blauerman@calgoncarbon.com
Charles Brown, Assistant plant manager
606-739-2308
charles.brown@kuraray.com
FACILITY OVERVIEW
Calgon is an activated carbon manufacturing and regeneration facility located on the west bank of the Big Sandy River, on the border between Kentucky and West Virginia. The total site is approximately 157 acres in size, and the active operation occupies approximately 40 acres. There is an additional 7-acre landfill located on the western side of U.S. Highway 23. The landfill is active but has not received waste since approximately 2002. The facility has been operating at its current location since the 1960s and has expanded several times over its operational life. Calgon has a staff of approximately 210 personnel and operates in three shifts, 24 hours per day, 7 days per week. The facility produces roughly 100 million pounds per year of virgin activated carbon products and an additional 35 million pounds per year of reactivated carbon products.
CWA Applicability
Calgon is authorized to discharge process wastewater, stormwater, and non-contact cooling water to the Big Sandy River and White's Creek under National Pollutant Discharge Elimination System (NPDES) issued by the State of Kentucky as the Kentucky Pollutant Discharge Elimination System (KYPDES) permit No. KY0022276 (Appendix A). The permit does not contain any requirements to monitor for PFAS compounds in the discharges. According to EPA's Enforcement and Compliance History Online (ECHO) website, Calgon was last inspected for CWA requirements on September 14, 2021, as a state-conducted base program evaluation. The facility has received seven CWA notices of violation from the state of Kentucky since October 2019.
Table 3 summarizes the outfalls authorized by the permit.
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Calgon Carbon - Big Sandy Plant Catlettsburg, Kentucky
Outfall
001
002 003 004
ENFORCEMENT CONFIDENTIAL
Table 3. KYPDES Permit No. KY0022276 Outfalls
PFAS
Direct/Internal Receiving Water Compound
Description of Discharge
Monitoring
Boiler blowdown and backwash
Prime line bakers wet scrubbers
Acid wash / neutralization
wastewater
Direct
Big Sandy River
No Wash down Non-contact Cooling
Stormwater
Reactivation (REACT) wastewater
(Outfall 004)
Direct Direct Internal
Big Sandy River White's Creek
Outfall 001
No Domestic sanitary wastewater
No Stormwater runoff from closed and capped landfill
No Motive water from REACT Stormwater from REACT area
The outfalls listed in Table 3 are depicted in the site wastewater flow diagram attached as Appendix B. The KYPDES permit expands on the monitoring requirements to specify that the monthly average discharge concentration for total recoverable selenium of 0.179 milligrams per liter (mg/L) is a trigger. If exceeded, the permit requires the permittee to collect and analyze fish tissue for selenium residue., If the fish tissue analysis results in a selenium concentration less than or equal to 8.6mg/Kg dry weight, then there is no permit violation.
RCRA Applicability
Calgon (EPA RCRA ID No. KYD005009923) is a hazardous waste treatment and storage facility and a large quantity generator of hazardous waste. Calgon has been permitted by the Kentucky Department of Environmental Protection (KY-DEP) to receive, store, consolidate, and treat a variety of hazardous and non-hazardous waste streams associated with receiving and reactivating spent carbon. A RCRA permit renewal was issued on December 19, 2019 (Appendix C). Typical waste streams generated on-site include wastewater fines, wastewater sludge, spent soda, furnace slag, paint residues, solvents, and lab packs.
FACILITY OPERATIONS SUMMARY
Calgon operations consist of three prime line (virgin) activated carbon manufacturing lines, one flue gas powdered activated carbon or "FluePAC" line, one fine mesh line, one acid wash line, and the reactivation (REACT) line. The facility also operates an on-site wastewater treatment plant and a domestic wastewater treatment package plant.
Prime Lines
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ENFORCEMENT CONFIDENTIAL The prime lines, labeled as B, D, and E, are the primary production lines for newly manufactured activated carbon products. With slight variations noted in the production flow diagrams, all three of the prime lines consist of similar processes. Raw coal or other carbon is added to bakers and heated before shifting into afterburners for additional heating in a spiral furnace. Once the carbon is fully activated, it is cooled in a cooler drum before being routed to other lines or for sale to customers. Non-contact cooling water is used in the prime lines to cool the carbon products after activation. A process flow diagram of the prime lines is included in Appendix D.
Fine Mesh Line
The fine mesh manufacturing process consists of a series of screens intended to screen the activated carbon product into various sizes based on customer specifications for the finished product. The fine mesh process does not use any process water.
Acid Wash Line
The acid wash product line takes finished activated carbon from the D or E prime lines and turns it into an acid washed product. The primary purpose of acid washing carbon is to remove water soluble ash and other materials so the product may be used in drinking water and other food-grade applications.
The carbon is first introduced into charge bins before being added to reactor vessels where it is exposed to a hydrochloric acid solution. Once the reaction is complete, the product is moved to dewatering bins before being dried and prepared for packaging. Water from the process is discharged to the on-site wastewater treatment system through the on-site sewers. A process flow diagram of the acid wash line is included in Appendix E.
FluePAC Line
The FluePAC process consists of proprietary additions of material to the activated carbon from the D and E lines to make specialty products for industrial applications. No water is used in the FluePACproduction process, and dehumidifiers are used to minimize the moisture in the processing areas. Water from the dehumidifiers is routed to the on-site sewers. A process flow diagram of the FluePACline is included in Appendix F.
Reactivation Line
The reactivation area consists of hazardous waste storage tanks, associated lines, and process units to treat spent activated carbon for reuse. The main treatment unit is a regeneration furnace that removes the organics from the spent carbon. The furnace and associated pollution control equipment are regulated under a Clean Air Act permit (not reviewed as part of this
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ENFORCEMENT CONFIDENTIAL inspection). The hazardous waste storage tanks and associated piping are regulated under the RCRA permit. A process flow diagram of the reactivation line is included in Appendix G.
Water Treatment
The facility obtains its process water from an intake structure located on the Big Sandy River (Appendix H, photo 34). The approximate daily intake is 3.2 million gallons, to which chemical flocculants are first added to help precipitate solids out of the water in the clarifiers (Appendix H, photos 35 and 36). Water is then sent to the process areas for use. Additional sand filters, ultra filtration, reverse osmosis, and water softening may occur depending on the process for which the water is intended. Water for domestic purposes is provided by the Big Sandy Water District.
Wastewater Treatment Systems
Calgon has two primary wastewater treatment systems including a main system for process wastewater and a package wastewater treatment plant for domestic wastewater.
Process Wastewater Treatment System
The process wastewater treatment system consists of a fines collection system using a fines pit and fines box (Appendix H, photos 30 and 31), a clarifier tank, mix tank, and filter press (Appendix H, photo 32). After the treatment works, wastewater is directed through a series of three settling ponds (lagoons) in sequence. At the time of the inspection, only two of the settling ponds were in use as the first pond in the sequence was being dredged and rehabilitated. Overflows from the fines pit and clarifier tanks are directed into lagoon 2 (Appendix H, photo 27). Final effluent is discharged through an outlet structure in lagoon 3 (Appendix H, photo 24). There is also a spillway overflow on lagoon 3 (Appendix H, photo 25) and Calgon representatives stated the sandbags that were observed by NEIC inspectors are to prevent inflow from the Big Sandy River in the event of flooding.
Settled material removed from the settling ponds are sent to either the Boyd County sanitary landfill or the Big Run landfill and may be used as coal industry bed material. Eastern Research Group (ERG) was contracted by EPA OCE-WCED to collect waste stream samples for hazardous waste and PFAS analysis and this material. ERG collected samples of the settled material. The sample are SP-4 and SP-5 and the analysis results are in Appendix I.
A process flow diagram of the wastewater treatment system, with estimated water usage, is included in Appendix B.
Domestic Wastewater Treatment Package Plant
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ENFORCEMENT CONFIDENTIAL Domestic wastewater for the entire facility is treated by a secondary treatment plant (Appendix H, photo 33). Calgon uses a steel package plant rated at 20,000 gallons per day. Treatment process units include a lift station equipped with two grinder pumps, an equalization basin, an aeration tank with solids recirculation, a rectangular clarifier, and ultraviolet disinfection. Diffused air is provided for aeration and mixing. The aeration system operates intermittently. During the summer months, it is on for 45 minutes out of every hour and off for 15 minutes. During the winter, the operation cycle is 30 minutes on and 30 minutes off each hour. Solids in the clarifier are not continuously wasted. When the blanket depth reaches 3 feet above the bottom of the clarifier, the solids are pumped down into a holding tank until the blanket depth is within 1 foot of the clarifier bottom. Effluent from the clarifier is disinfected and then discharged through Outfall 002. AZ Septic is contracted by Calgon to remove the sanitary waste sludge.
FIELD ACTIVITIES SUMMARY
NEIC conducted the inspection from March 21-29, 2023. NEIC, OCE-WED, OCE-WCED, EPA Region 4, and State of Kentucky inspectors, arrived at the facility at 9:00 a.m. on March 21, 2023, at which time credentials were presented to the facility staff listed in Table 2 of this report. NEIC conducted an opening conference that explained the purpose and scope of the inspection.
During the inspection of Calgon, NEIC inspectors conducted the following activities:
Evaluated on-site processes with an emphasis on waste management and PFAS wastewater generation, management, treatment, and effluent discharge, including meeting with facility personnel to discuss facility operations;
Inspected and observed facility process operations, wastewater generation sources, treatment facilities, outfall locations, and sampling and monitoring locations;
Photographed and documented site conditions;
Reviewed facility documents, including operating plans, records, monitoring reports, and analytical data;
Collected samples of stormwater and wastewater effluent discharges for PFAS compound analysis, including storm water runoff samples;
Collected duplicate samples of wastewater for analysis by EPA ORD;
Collected samples of soil/sediments for analysis by EPA ORD;
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ENFORCEMENT CONFIDENTIAL Reviewed hazardous waste determinations;
Inspected hazardous and solid waste management and storage practices;
Performed leak detection and repair (LDAR) monitoring using a flame ionization detector of tank openings and closed vent systems;
Surveyed for volatile organic compound emissions with an infrared camera;
Performed analysis of a portion of collected samples at the NEIC laboratory in Denver, Colorado.
At the request of EPA OCE-WED, duplicate samples were not collected from locations that were determined to be hazardous because EPA ORD is unable to process samples that meet the definition of RCRA hazardous waste. NEIC's investigation did not include sampling of groundwater wells or sampling in surface waters.
ERG was contracted by EPA OCE-WCED to collect waste stream samples for hazardous waste and PFAS analysis. ERG's sampling report and analytical results can be found in Appendix I. ERG collected samples from four locations. Samples SP-1 and SP-2 were from drums with the waste profiles of 3551N and 4012N respectively. Sample SP-3 was collected from a filter press in the reactivation area. Sample SP-4was collected from a pile of material dredged from the wastewater lagoons. As described above, this is the material removed from the settling ponds and sent to either the Boyd County sanitary landfill or the Big Run landfill where it may be used as coal industry bed material.
Measurement and Sampling Activities
The NEIC field team provided support to this investigation by collecting samples of process wastewater and stormwater runoff. Samples were provided to the NEIC laboratory for PFAS analysis and the ORD laboratory for non-targeted PFAS analysis. All samples were screened in the field for radionuclide levels to ensure no radioactive materials were sent to the NEIC laboratory. The NEIC field team also provided support to this investigation by conducting LDAR monitoring of regulated process areas and equipment. Table 4 summarizes field measurement and field sampling activities. A copy of the chain of custody record is provided in Appendix J.
All environmental measurement activities were performed in accordance with the NEIC quality system. All field sampling, field measurements/monitoring, and laboratory measurements described in this report are within the scope of NEIC's ISO/IEC 17025 accreditation issued by the ANSI National Accreditation Board (certificate No. FT-0303). Sampling performed by ERG and
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ENFORCEMENT CONFIDENTIAL analysis performed by Eurofins Lancaster Laboratories are not within the scope of NEIC's ISO/IEC 17025 accreditation.
On March 24, 2023, conditions were rainy and overcast. This allowed for the collection of stormwater runoff samples.
Location Identifier
MSA Altair used to screen location for safety
Table 4. FIELD MEASUREMENT AND FIELD SAMPLING ACTIVITIES
Dates
Method, and/or Procedure1, and Equipment
3-24-23 and
3-27-23
MEASUREMENTS
NEIC procedure: Safety and Sample Screening Instruments, NEICPROC/17-002 Instrument guide:
MSA Altair 5X Multi-Gas Monitoring Equipment
Equipment: MSA Altair 5X (SN2420)
Radeye used to screen samples for radiation
3-24-23 and
3-27-23
NEIC procedure: Safety and Sample Screening Instruments, NEICPROC/17-002 Instrument guide:
RadEye B20-ER - Radiation Detection Equipment
Equipment: Radeye B20-ER (SN84634)
Measurer Name
Mike Solter Craig Lutz
Trent Rainey
Tank farm B Unloading sump
3-27-23
Method: EPA Method 21: Determination of Volatile Organic Compound Leaks NEIC procedure: Toxic Vapor Analyzer (TVA), NEICPROC/00-016
Close vent system
Station No. and Sample Tag No.
S01 - Trip Blank VP1508-01
S01 - Trip Blank VP1508-02
S01 - Trip Blank VP1508-03
S01 - Low Spike VP1508-04
S01 - Mid Spike VP1508-05
Appendix H Photo
Nos.
N/A
S01 - High Spike VP1508-06
Equipment: Thermo Scientific TVA 2020 (B24256)
SAMPLING
Date and Time Sampling Technique
Method, and/or Procedure, and
Equipment
Received on 3- Prepared by NEIC 15-2023 at 0931 laboratory
Trip blanks and
field spikes Sample containers: 1-liter high density polyethylene (HDPE) plastic container (without TeflonTM -lined lids); nitric acid preservative
Zach Schlachter
Sampler Name
Prepared by Dan Hurlbut, NEIC Chemist in advance of
the inspection
and provided to Mike
Solter, NEIC Project manager to bring to the field
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Calgon Carbon - Big Sandy Plant Catlettsburg, Kentucky
S02 - Outfall 003
VP1508-07
S03 - Field Blank
VP1508-08
S04 - Staging area north of thaw building
runoff VP1508-09
S05 - Retention basin north and east of REACT
VP1508-10
ENFORCEMENT CONFIDENTIAL
Table 4. FIELD MEASUREMENT AND FIELD SAMPLING ACTIVITIES
NEIC procedure: Water and Wastewater Sampling, NEICPROC/00-051
44 and 45
03-24-2023 at 0855
Grab sample using direct fill into sample container
Equipment: None
Sample container: 1-liter HDPE plastic container (without TeflonTM -lined lids); nitric acid preservative
NEIC procedure: Water and Wastewater Sampling, NEICPROC/00-051
46 03-24-2023 at Grab sample using direct fill into sample Equipment: None
0905
container
Sample container:
1-liter HDPE plastic
container (without
TeflonTM -lined lids);
nitric acid
preservative
NEIC procedure: Water and Wastewater Sampling, NEICPROC/00-051
47 and 48
03-24-2023 at 0953
Grab sample using direct fill into sample
container
Equipment: None
Sample container: 1-liter HDPE plastic container (without TeflonTM -lined lids); nitric acid preservative
NEIC procedure: Water and Wastewater Sampling, NEICPROC/00-051
49 and 50
03-24-2023 at 1004
Grab sample using direct fill into sample
container
Equipment: None
Sample container: 1-liter HDPE plastic container (without TeflonTM -lined lids); nitric acid preservative
Mike Solter Trent Rainey
Mike Solter
Trent Rainey
Mike Solter Trent Rainey
Mike Solter Trent Rainey
NEICVP1508E01
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Calgon Carbon - Big Sandy Plant Catlettsburg, Kentucky
S06 - Equipment rinse blank outside of
001 VP1508-11
S07 - Outfall 001
VP1508-12
S08 - Outfall 002
VP1508-13
S09 - Raw water intake VP1508-14 S09 - Raw water intake VP1508-15 S09 - Raw water intake VP1508-16
ENFORCEMENT CONFIDENTIAL
Table 4. FIELD MEASUREMENT AND FIELD SAMPLING ACTIVITIES
NEIC procedure: Water and Wastewater Sampling, NEICPROC/00-051
03-24-2023 at
Grab sample using Equipment:
51
direct fill into sample Telescoping rod
1039
container
Sample container:
1-liter HDPE plastic
container (without
TeflonTM -lined lids);
nitric acid
preservative
NEIC procedure: Water and Wastewater Sampling, NEICPROC/00-051
52 and 53
03-24-2023 at 1044
Grab sample using direct fill into sample
container
Equipment: Sample container affixed to telescoping rod
55 and 56 57 and 58
03-24-2023 at 1120
03-24-2023 at 1402
03-24-2023 at 1403
03-24-2023 at 1404
Grab sample using direct fill into sample
container
Grab sample using direct fill into sample
container
Sample container: 1-liter HDPE plastic container (without TeflonTM -lined lids); nitric acid preservative
NEIC procedure: Water and Wastewater Sampling, NEICPROC/00-051
Equipment: None
Sample container: 1-liter HDPE plastic container (without TeflonTM -lined lids); nitric acid preservative
NEIC procedure: Water and Wastewater Sampling, NEICPROC/00-051
Equipment: None
Sample containers: 1-liter HDPE plastic container (without TeflonTM -lined lids); nitric acid preservative
Mike Solter Trent Rainey
Mike Solter Trent Rainey
Mike Solter Trent Rainey
Mike Solter Trent Rainey
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S10 - City water inlet
VP1508-17
S11 - Tank 707 VP1508-18
S12 - Tank 361 VP1508-19
S13 - Frac box VP1508-20
S14 - Equivalent to 004 after the 7
tanks VP1508-21
ENFORCEMENT CONFIDENTIAL
Table 4. FIELD MEASUREMENT AND FIELD SAMPLING ACTIVITIES
NEIC procedure: Water and Wastewater Sampling, NEICPROC/00-051
59 and 60
03-24-2023 at 14354
Grab sample using direct fill into sample
container
Equipment: None
Sample container: 1-liter HDPE plastic container (without TeflonTM -lined lids); nitric acid preservative
NEIC procedure: Water and Wastewater Sampling, NEICPROC/00-051
61 and 62
3-27-2023 at 1108
Grab sample using direct fill into sample
container
Equipment: None
Sample container: 1-liter HDPE plastic container (without TeflonTM -lined lids); nitric acid preservative
NEIC procedure: Water and Wastewater Sampling, NEICPROC/00-051
63 and 64
3-27-2023 at 1121
Grab sample using direct fill into sample
container
Equipment: None
Sample container: 1-liter HDPE plastic container (without TeflonTM -lined lids); nitric acid preservative
NEIC procedure: Water and Wastewater Sampling, NEICPROC/00-051
65 and 66
3-27-2023 at 1127
Grab sample using direct fill into sample
container
Equipment: None
Sample container: 1-liter HDPE plastic container (without TeflonTM -lined lids); nitric acid preservative
67 and 68
3-27-2023 at 1135
Grab sample using direct fill into sample
container
NEIC procedure: Water and Wastewater Sampling, NEICPROC/00-051
Mike Solter Trent Rainey
Mike Solter Trent Rainey
Mike Solter Trent Rainey
Mike Solter Trent Rainey
Mike Solter Trent Rainey
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Calgon Carbon - Big Sandy Plant Catlettsburg, Kentucky
S14 - Equivalent to 004 after the 7
tanks VP1508-22,
S14 - Equivalent to 004 after the 7
tanks VP1508-23
S15 - Field blank
VP1508-24
VP1508-01-Soils (Retention Basin near REACT area)
VP1508-02-Soils (Field Blank)
ENFORCEMENT CONFIDENTIAL
Table 4. FIELD MEASUREMENT AND FIELD SAMPLING ACTIVITIES
3-27-2023 at 1136
3-27-2023 at 1138
Equipment: None
Sample containers: 1-liter HDPE plastic container (without TeflonTM -lined lids); nitric acid preservative
NEIC procedure:
Water and
Wastewater
Sampling,
NEICPROC/00-051
Mike
69 3-27-2023 at Grab sample using direct fill into sample Equipment: None Solter
1146
container
Sample container:
Trent Rainey
1-liter HDPE plastic
container (without
TeflonTM -lined lids);
nitric acid
preservative
Method: ASTM
D5633-21:
Standard Practice
for Sampling with a
3-27-2023 at
Grab sample using Scoop
Mike Solter
N/A
direct fill into sample
1326
container
Equipment: Grab
Trent
samples using
Rainey
scoops/containers
provided by the
analyzing
laboratory.
Method: ASTM
D5633-21:
Standard Practice
for Sampling with a
3-27-2023 at
Grab sample using Scoop
Mike Solter
N/A
direct fill into sample
1346
container
Equipment: Grab
Trent
samples using
Rainey
scoops/containers
provided by the
analyzing
laboratory.
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ENFORCEMENT CONFIDENTIAL
Table 4. FIELD MEASUREMENT AND FIELD SAMPLING ACTIVITIES
VP1508-03-Soils
(Spillway near
N/A
lagoon 3)
3-27-2023 at 1347
Grab sample using direct fill into sample
container
Method: ASTM D5633-21: Standard Practice for Sampling with a Scoop
Equipment: Grab samples using scoops/containers provided by the analyzing laboratory.
VP1508-04-Soils (Mike Taylor N/A Lute Memorial Park)
3-27-2023 at 1413
Off-site background soil Grab sample using direct fill into sample
container
Method: ASTM D5633-21: Standard Practice for Sampling with a Scoop
Equipment: Grab samples using scoops/containers provided by the analyzing laboratory.
1 The current version of each procedure, at the time of the investigation, was followed.
Mike Solter Trent Rainey
Mike Solter Trent Rainey
LDAR monitoring was performed on tank openings in Tank Farm B and the associated closed vent system along with the unloading sumps. No emissions above 500 ppm were detected. Valves were not monitored because the valves are in heavy liquid service and not subject to Method 21 monitoring.
Site conditions and activities were documented in field records, and field photographs are attached as Appendix H. Samples collected during the field activities for analysis by NEIC were driven by Trent Rainey to the NEIC laboratory in Denver, Colorado. Water and soil/sediment samples collected for analysis by ORD were shipped to the ORD laboratories via FedEx. The ORD analytical results are not included in this report.
LABORATORY ACTIVITIES SUMMARY
The field samples were delivered to the NEIC laboratory by Trent Rainey on March 31, 2023, and were placed in a secured walk-in cooler. Sample custody was relinquished by Trent Rainey to NEIC analyst Daniel Hurlbut on April 3, 2023. Tag information for each sample was compared to the accompanying chain of custody records in Appendix J. The NEIC laboratory team analyzed the samples for the presence of selected PFAS compounds.
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ENFORCEMENT CONFIDENTIAL Table 5 summarizes the analytical objective, technique, and methods followed, as well as the analysts and dates of the analyses. Data quality summaries, including uncertainty statements for all laboratory measurements, are maintained in the project file.
Table 5. ANALYTICAL OBJECTIVE, TECHNIQUE, AND METHOD; ANALYST; AND DATE PERFORMED
Analytical Objective, Technique, and Method
NEIC Analyst
Samples Analyzed
by Method (Station
Nos.)
Date(s) Performed
Short Chain PFAS Analysis:
Restek application note, "A Novel Approach
for Ultrashort-Chain PFAS Analysis in Water
Samples," by Dr. Shun-Hsin Liang
(www.restek.com). Methanol diluted samples analyzed by
liquid chromatography/mass
Daya Mitchell
S01-S18. S20-S24
August 9 to September 18,
2023
spectrometry (LC/MS) using a triple-
quadrupole (QQQ) mass spectrometer
for identification of targeted, short
chain PFAS.
Long Chain PFAS Analysis:
Filtration and sample loading
May 3 to 9, 2023
Improved Method for Extraction and Analysis of Perfluorinated Compounds (PFCs) from Surface Waters and Well
on cartridge: Daya Mitchell Jessica Krank
Water by Ultra-High Performance Liquid
Chromatography (UPLC)-Tandem Mass
Spectrometry (MS/MS). SOP ID: D-
EMMDPHCB043-SOP-03, August 2016.
Method for Extraction and Analysis of Perfluoroethercarboxylic acids (PFECAs)
July 19, 2023
from Surface Water, Well Water and Waste Water by Ultra-High
Sample elution and concentration:
S01-S18, S20-S24
Performance Liquid Chromatography (UPLC)-Tandem Mass Spectrometry
Daya Mitchell Jessica Krank
(MS/MS). SOP ID:D-EMMD-PHCB-062-
SOP-01, July 2017.
Both of these methodologies require
filtration followed by loading the
sample on a cartridge. At a later date,
the samples were eluted off the
cartridge and concentrated by
evaporation for sample extracts.
Long chain PFAS sample extracts
analyzed by liquid
chromatography/mass spectrometry (LC/MS) using a triple-quadrupole (QQQ) mass spectrometer for identification and quantitation of
Daya Mitchell
S01-S18, S20-S24
August 9 to September 18,
2023
targeted, long chain PFAS.
Long chain PFAS sample extracts
analyzed by LC/MS using a quadrupole time of flight (QTOF) high resolution mass spectrometer for identification of
Jessica Krank
S01-S18, S20-S24
July 26 to August 21, 2023
semi-target PFAS.
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ENFORCEMENT CONFIDENTIAL
Table 5. ANALYTICAL OBJECTIVE, TECHNIQUE, AND METHOD; ANALYST; AND DATE PERFORMED
Analytical Objective, Technique, and Method
NEIC Analyst
Samples Analyzed
by Method (Station
Nos.)
Date(s) Performed
1 Data quality summaries, including uncertainty measurements, for all laboratory measurements are maintained in the
project file.
The mass spectrometers listed in Table 6 use electrospray ionization to detect negatively charged mass ions. The triple quadrupole (QQQ) mass spectrometer also incorporates analyte specific parameters (retention time, precursor and fragment mass ions, etc.), along with certified reference materials in order to identify and quantify targeted PFAS. The quadrupole time of flight (QTOF) high resolution mass spectrometer collects accurate mass data for all negatively charged mass ions detected (PFAS and non-PFAS) for a specified mass range during the analysis run, and analyte identifications were based on comparing observed accurate mass values of precursor mass ions to the exact mass values of the semi-targeted PFAS, along with other mass ions (fragments, adducts, etc.), and if available, retention time and accurate mass value comparisons to reference materials. Therefore, reported results will differ based on the functionality of the mass spectrometer being used.
In addition, some PFAS are available in various chemical forms, and each form has its own associated Chemical Abstract Services (CAS) number. For example, perfluorobutanesulfonic acid (CAS No. 375-73-5) and perfluorobutanesulfonate potassium salt (CAS No. 29420-49-3) have unique CAS numbers, and both chemicals produce the same negative mass ion. The mass spectrometer cannot determine which chemical form (acid, potassium salt, etc.) produced the observed PFBS response. Therefore, if applicable, results from the short chain and long chain analyses were based on the acid form of the reported PFAS.
ANALYTICAL RESULTS
Table 6 contains the station number, NEIC sample tag, station location, photograph file name and physical description of the samples collected by the NEIC field team. Photographs of the samples as observed in the NEIC laboratory are in Appendix K. Three trip blanks (NEIC sample tag Nos. VP1508-01 to VP1508-03) and three trip spike samples (NEIC sample tag Nos. VP150804 to VP1508-06) were prepared by the NEIC laboratory and given to the NEIC field team who transported them to the facility and back to NEIC. The extraction and analysis methods described in Table 5 were developed and validated by EPA analysts at the ORD National Exposure Research Laboratory for PFAS determinations in water matrices similar to the samples described in Table 7. The project file contains additional laboratory activities information, including sample description, preparation, filtration, extraction spike recoveries, and reporting
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ENFORCEMENT CONFIDENTIAL limits, along with notable observations, method modifications, and comments. The analytical
results presented apply to the samples as received.
Station No.
S01
S02 S03 S04 S05 S06 S07 S08 S09 S10 S11
S12 S13 S14 S15
NEIC Tag No.
VP1508-01 VP1508-02 VP1508-03 VP1508-04
VP1508-05
VP1508-06 VP1508-07 VP1508-08 VP1508-09
VP1508-10 VP1508-11 VP1508-12
VP1508-13 VP1508-14 VP1508-15 VP1508-16 VP1508-17
VP1508-18
VP1508-19
VP1508-20 VP1508-21 VP1508-22 VP1508-23 VP1508-24
Table 6. SUMMARY OF SAMPLE IDENTIFICATION AND DESCRIPTION
Station Location/ Description of Sample
Appendix K
Location
File Name
Physical Description
NEIC laboratory/Trip Blanks
DSC_0247.JPG
Colorless, non-viscous, liquid
NEIC laboratory/ Low Trip Spike
NEIC laboratory/ Mid Trip Spike
NEIC laboratory/ High Trip Spike Outfall 003 Field blank
Staging area north of thaw building-lot runoff Retention basin north
and east of REACT. Equipment rinse blank
Outfall 001
DSC_0248.JPG
DSC_0249.JPG DSC_0250.JPG DSC_0251.JPG DSC_0252.JPG DSC_0253.JPG DSC_0254.JPG
Outfall 002
DSC_0255.JPG
Colorless, non-viscous, liquid
Non-viscous liquid, light brown in color Colorless, non-viscous, liquid
Colorless, non-viscous, liquid with black sediment present
Non-viscous liquid, light brown in color, with black sediment present Colorless, non-viscous, liquid
Colorless, non-viscous, liquid with black sediment present
Non-viscous liquid, light brown color with sediment present
Raw water intake
DSC_0256.JPG
Colorless, non-viscous, liquid
City water inlet Tank 707
Tank 361
Frac box Equivalent to 004 after 7
tanks Field blank
DSC_0257.JPG DSC_0258.JPG
DSC_0259.JPG DSC_0260.JPG
Colorless, non-viscous, liquid Colorless, non-viscous liquid with a layer of black sediment on container bottom and adhering to inner container walls and cap.
Black, semi-viscous liquid containing a substantial amount of black material ,
opaque liquid and solid layers. Colorless, non-viscous, liquid containing a
substantial amount of black sediment.
DSC_0261.JPG
Colorless, non-viscous, liquid
DSC_0262.JPG
Colorless, non-viscous, liquid
Prior to analysis, a 750 milliliter (mL) volume from each sample was passed through a glass fiber filter to remove any particulates present, except for sample VP1508-19 which was mainly comprised of a black, opaque solid material, and could not be analyzed using the methods shown in Table 6. Samples VP1508-09, VP1508-18 and VP1508-20 were passed through multiple filters because of the particulate amount present in these samples. A diluted aliquot from each filtrate was analyzed for the targeted short chain PFAS using the LC/MS QQQ
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ENFORCEMENT CONFIDENTIAL methodology shown in Table 6. A 500-mL volume from each filtrate was passed through a solid phase extraction (SPE) cartridge, and the resulting extract was analyzed for the long chain PFAS using the LC/MS QQQ and LC/MS QTOF methods shown in Table 6.
Targeted PFAS Analysis
Table 7 contains the targeted PFAS analytes along with their NEIC acronym, CAS number, and molecular formula. The SPE extracts were analyzed for the long chain targeted PFAS while the diluted aliquots were analyzed for the short chain target PFAS, using the LC/MS-QQQ methods shown in Table 5.
Table 7. TARGETED PFAS
Analyte
NEIC Acronym
Long Chain
Perfluorobutyric acid Perfluorodecanoic acid Perfluorododecanoic acid Perfluoroheptanoic acid Perfluorohexanoic acid Perfluorononanoic acid Perfluorooctanoic acid Perfluoropentanoic acid Perfluorotridecanoic acid Perfluoroundecanoic acid
Hexafluoropropylene oxide dimer acid
(a.k.a. Undecafluoro-2-methyl-3-oxahexanoic acid)
Butanoic acid, 2,2,3,3,4,4-hexafluoro-4(trifluoromethoxy)Acetic acid, 2,2-difluoro-2-[1,1,2,2-tetrafluoro-2(trifluoromethoxy)ethoxy]Butanoic acid, 2,2,3,3,4,4-hexafluoro-4-[1,2,2,2tetrafluoro-1-(trifluoromethyl)ethoxy]N-ethylperfluoro-1-octanesulfonamide N-methylperfluoro-1-octanesulfonamide Perfluorooctanesulfonamide N-ethyl perfluorooctanesulfonamidoacetic acid
(a.k.a. N-ethyl-N-((heptadecafluorooctyl)sulfonyl)glycine)
N-methyl perfluorooctanesulfonamidoacetic acid
( a.k.a. N-(Heptadecafluorooctylsulfonyl)-N-methylglycine)
Perfluorobutanesulfonic acid Perfluorodecanesulfonic acid Perfluorododecanesulfonic acid
PFBA PFDA PFDoA PFHpA PFHxA PFNA PFOA PFPeA PFTrA PFUnA HFPO-DA (a.k.a. GenX) PFECA A (a.k.a. PFMBA) PFECA B (a.k.a. NFDHA)
PFECA G
EtFOSA MeFOSA PFOSA
NEtFOSAA
NMeFOSAA
PFBS PFDS PFDoS
Perfluoroheptanesulfonic acid
PFHpS
Perfluorohexanesulfonate
PFHxSTotal3
Perfluorononanesulfonic acid
PFNS
CAS No.
375-22-4 335-76-2 307-55-1 375-85-9 307-24-4 375-95-1 335-67-1 2706-90-3 72629-94-8 2058-94-8
13252-13-6
863090-89-5
151772-58-6
801212-59-9
4151-50-2 31506-32-8
754-91-6 2991-50-6
2355-31-9 375-73-5 335-77-3 79780-39-5 375-92-8 355-46-4 68259-12-1
Formula
C4HF7O2 C10HF19O2 C12HF23O2 C7HF13O2 C6HF11O2 C9HF17O2 C8HF15O2 C5HF9O2 C13HF25O2 C11HF21O2
C6HF11O3
C5HF9O3
C5HF9O4
C7HF13O3
C10H6F17NO2S C9H4F17NO2S C8H2F17NO2S C12H8F17NO4S
C11H6F17NO4S C4F9O3SH C10F21O3SH C12F25O3SH C7F15O3SH C6F13O3SH C9F19O3SH
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ENFORCEMENT CONFIDENTIAL
Table 7. TARGETED PFAS
Analyte Perfluorooctanesulfonic acid
NEIC Acronym PFOSTotal3
CAS No. 1763-23-1
Formula C8F17O3SH
Perfluoropentanesulfonic acid
PFPeS
2706-91-4
C5F11O3SH
4:2 Fluorotelomer sulfonic acid
4:2 FTS
757124-72-4 C6H5F9O3S
6:2 Fluorotelomer sulfonic acid
6:2 FTS
27619-97-2 C8H5F13O3S
8:2 Fluorotelomer sulfonic acid
8:2 FTS
39108-34-4 C10H5F17O3S
10:2 Fluorotelomer sulfonic acid
10:2 FTS
120226-60-0 C12H5F21O3S
Short Chain
2,3,3,3-Tetrafluoropropionic acid
2,3,3,3-TPrA
359-49-9
C3H2O2F4
3H-Tetrafluoropropionic acid
2,2,3,3-TPrA
756-09-2
C3H2O2F4
Lithium bis(trifluoromethanesulfonyl)amide1
HQ-115
90076-65-6 C2F6S2O4NLi
Pentafluoropropionic acid
PFPA
422-64-0
C3HO2F5
Perfluoro-4-ethylcyclohexanesulfonic acid
PFECHS
646-83-3
C8F15SO3H
Perfluoroethanesulfonic Acid
PFES
354-88-1
C2F5SO3H
Potassium Bis(perfluorobutanesulfonyl)imide2
DBI
129135-87-1 C8F18S2O4NK
Trifluoroacetic acid
TFAA (or TFA)
76-05-1
C2HO2F3
Trifluoromethanesulfonic Acid
TFMS
1493-13-6
CF3SO3H
1- Reported results are based on bis(trifluoromethanesulfonyl)amide form. 2- Reported results are based on bis(perflurorobutanesulfonyl)imide form. 3- Analyte contains linear (L) and branched (B) isomers. Therefore, reported "Total" results = (L+B) isomer results.
As shown in Table 8, perfluoroethanesulfonic acid (PFES) was included in the short chain targeted PFAS list, however, reference materials for this analyte were not readily available, therefore, the diluted filtrates were not analyzed for PFES. The SPE extracts were analyzed for perfluorododecanesulfonic acid (PFDoS) but these results were not reported since PFDoS was not observed in the quality control samples that were prepared and analyzed.
Tables 8 through 11 contain the observed targeted PFAS concentrations in nanograms per liter (ng/L), and the corresponding reporting limits (RL), for samples VP1508-07 through VP1508-24, excluding VP1508-19. Four additional targeted PFAS (PFDS, PFECA-B, PFECA-G and PFNS) are not reported in Tables 9 through 12, as these analytes were not observed in any site samples analyzed. . The RL value for each analyte was based on the lowest standard solution in its calibration curve, along with the sample preparation technique used (i.e., methanol diluted aliquot or SPE). If the analyte was identified in any of the blank samples, the analyte response of the lowest standard solution was greater than the observed responses from the blank samples. These RL criteria were applied to all but seven of the reported PFAS. Low analyte recoveries from spike samples resulted in the significantly higher RL values for 10:2 FTS, PFDoA, TFAA, PFPA, 2,2,3,3-TFPA and 2,3,3,3-TPrA. An RL value could not be determined for PFTrA since this analyte was not recovered from any of the spike samples, although it was identified in
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ENFORCEMENT CONFIDENTIAL sample VP1508-18. As mentioned previously, samples VP1508-01, VP1508-02 and VP1508-03 (trip blanks) and samples VP1508-04, VP1508-05, VP1508-06 (trip spikes) were prepared at the NEIC laboratory. The PFAS results for the trip blanks were less than the RL value for each target PFAS. The trip spike results were included in determining the expanded measurement uncertainty (EMU) ranges that are shown as a footnote in Tables 9 through12.
Table 8. RESULTS FOR VP1508-07 THROUGH VP1508-11, AND REPORTING LIMITS
Analyte Concentration (ng/L)
Analyte
Outfall 003
(VP1508-07)
Field blank Staging area Ret. basin
(VP1508-08) (VP1508-09) (VP1508-10)
Equip. rinse
(VP1508-11)
Reporting Limit (RL)
Long Chain
10:2 FTS1
< RL
< RL
< RL
< RL
< RL
50.0
4:2 FTS
< RL
< RL
< RL
< RL
< RL
2.07
6:2 FTS
< RL
< RL
34.0
< RL
< RL
2.10
8:2 FTS
< RL
< RL
< RL
< RL
< RL
2.12
HFPO-DA
< RL
< RL
4750
2990
< RL
5.53
N-EtFOSA
< RL
< RL
< RL
< RL
< RL
2.21
N-EtFOSAA
< RL
< RL
< RL
< RL
< RL
2.21
N-MeFOSA
< RL
< RL
< RL
< RL
< RL
2.21
N-MeFOSAA
< RL
< RL
< RL
< RL
< RL
2.21
PFBA
6.22
< RL
110
61.3
< RL
2.21
PFBS
< RL
< RL
86.9
79.7
< RL
1.96
PFDA
< RL
< RL
< RL
< RL
< RL
2.21
PFDoA
< RL
< RL
< RL
< RL
< RL
50.0
PFECA-A
< RL
< RL
< RL
< RL
< RL
2.21
PFHpA
< RL
< RL
9.74
24.7
< RL
2.21
PFHpS
< RL
< RL
< RL
< RL
< RL
2.10
PFHxA
< RL
< RL
36.1
57.4
< RL
2.21
PFHxSTotal
< RL
< RL
< RL
6.61
< RL
2.02
PFNA
< RL
< RL
< RL
6.24
< RL
2.21
PFOA
< RL
< RL
74.4
871
< RL
2.21
PFOSTotal
< RL
< RL
14.3
19.2
< RL
2.05
PFOSA
< RL
< RL
< RL
< RL
< RL
2.21
PFPeA
< RL
< RL
78.0
71.0
< RL
22.1
PFPeS
< RL
< RL
< RL
< RL
< RL
2.08
PFTrA2
NA
NA
NA
NA
NA
NA
PFUnA
< RL
< RL
< RL
< RL
< RL
2.21
Short Chain
2,2,3,3-TPrA
< RL
< RL
< RL
< RL
< RL
1000
2,3,3,3-TPrA
< RL
< RL
< RL
DET
< RL
200
DBI
< RL
< RL
< RL
< RL
< RL
10.0
HQ-115
< RL
< RL
11.8
< RL
< RL
10.0
PFECHS
< RL
< RL
< RL
< RL
< RL
10.0
PFPA
< RL
< RL
DET
< RL
< RL
800
TFAA
< RL
< RL
DET
DET
< RL
600
TFMS
< RL
< RL
12.0
9.943
< RL
10.0
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ENFORCEMENT CONFIDENTIAL
Table 8. RESULTS FOR VP1508-07 THROUGH VP1508-11, AND REPORTING LIMITS Analyte Concentration (ng/L)
Outfall 003 Field blank Staging area Ret. basin Equip. rinse Reporting
Analyte
(VP1508-07) (VP1508-08) (VP1508-09) (VP1508-10) (VP1508-11) Limit (RL)
1 Results are estimated due to low spike recovery.
2 PFTrA was not detected in the spike samples, thus is reported as NA (Not Applicable).
3 Response within calibration curve response range, but concentration calculates as less than lowest calibrator.
DET - Analytes are detected above the stated RL but could not be quantified due to poor calibration and/or QC results or significant ion suppression.
interfering with the MassHunter software's ability to quantify the result.
EMU- Expanded measurement uncertainty range for reported PFAS concentration values: 64% to 170%, except for:
N-EtFOSAA, N-MeFOSAA, EtFOSA, PFHxA: EMU range: 36% to 230%
10:2 FTS, DBI: EMU range: 51% to 1100%
2,2,3,3-TPrA, 2,3,3,3-TPrA, PFPA, TFAA, PFTrA: No EMU range calculated due to insufficient quality control data.
(Using a coverage probability of 95% and coverage factor of 2.09 for short chain PFAS, or 2.57 for long chain PFAS.)
Table 9. RESULTS FOR VP1508-12 THROUGH VP1508-16, AND REPORTING LIMITS Analyte Concentration (ng/L)
Analyte
Outfall 001
(VP1508-12)
Outfall 002
(VP1508-13)
Raw water intake
(VP1508-14) (VP1508-15) (VP1508-16)
Reporting Limit (RL)
Long Chain
10:2 FTS1
< RL
< RL
< RL
< RL
< RL
50.0
4:2 FTS
< RL
< RL
< RL
< RL
< RL
2.07
6:2 FTS
< RL
< RL
< RL
< RL
< RL
2.10
8:2 FTS
< RL
< RL
< RL
< RL
< RL
2.12
HFPO-DA
< RL
< RL
< RL
< RL
< RL
5.53
N-EtFOSA
< RL
< RL
< RL
< RL
< RL
2.21
N-EtFOSAA
< RL
< RL
< RL
< RL
< RL
2.21
N-MeFOSA
< RL
< RL
< RL
< RL
< RL
2.21
N-MeFOSAA
< RL
< RL
< RL
< RL
< RL
2.21
PFBA
169
< RL
< RL
< RL
< RL
2.21
PFBS
< RL
< RL
< RL
< RL
< RL
1.96
PFDA
< RL
< RL
< RL
< RL
< RL
2.21
PFDoA
< RL
< RL
< RL
< RL
< RL
50.0
PFECA-A
< RL
< RL
< RL
< RL
< RL
2.21
PFHpA
< RL
< RL
< RL
< RL
< RL
2.21
PFHpS
< RL
< RL
< RL
< RL
< RL
2.10
PFHxA
< RL
6.89
< RL
< RL
< RL
2.21
PFHxSTotal
< RL
< RL
< RL
< RL
< RL
2.02
PFNA
< RL
< RL
< RL
< RL
< RL
2.21
PFOA
< RL
< RL
2.99
< RL
< RL
2.21
PFOSTotal
< RL
< RL
< RL
< RL
< RL
2.05
PFOSA
< RL
< RL
< RL
< RL
< RL
2.21
PFPeA
< RL
< RL
< RL
< RL
< RL
22.1
PFPeS
< RL
< RL
< RL
< RL
< RL
2.08
PFTrA2
NA
NA
NA
NA
NA
NA
PFUnA
< RL
< RL
< RL
< RL
< RL
2.21
Short Chain
2,2,3,3-TPrA
< RL
< RL
< RL
DET
< RL
1000
2,3,3,3-TPrA
DET
< RL
< RL
< RL
< RL
200
DBI
< RL
< RL
< RL
< RL
< RL
10.0
NEICVP1508E01
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ENFORCEMENT CONFIDENTIAL
Table 9. RESULTS FOR VP1508-12 THROUGH VP1508-16, AND REPORTING LIMITS
Analyte Concentration (ng/L)
Analyte
Outfall 001 Outfall 002
Raw water intake
Reporting
(VP1508-12) (VP1508-13) (VP1508-14) (VP1508-15) (VP1508-16) Limit (RL)
HQ-115
< RL
< RL
< RL
< RL
< RL
10.0
PFECHS
< RL
< RL
< RL
< RL
< RL
10.0
PFPA
DET
< RL
< RL
DET
< RL
800
TFAA
DET
< RL
< RL
DET
< RL
600
TFMS
21.0
< RL
< RL
< RL
< RL
10.0
1 Results are estimated due to low spike recovery.
2 PFTrA was not detected in the spike samples, thus is reported as NA (Not Applicable).
DET - Analytes are detected above the stated RL but could not be quantified due to poor calibration and/or QC results or significant ion suppression
interfering with the MassHunter software's ability to quantify the result.
EMU- Expanded measurement uncertainty range for reported PFAS concentration values: 64% to 170%, except for:
N-EtFOSAA, N-MeFOSAA, EtFOSA, PFHxA: EMU range: 36% to 230%
10:2 FTS, DBI: EMU range: 51% to 1100%
2,2,3,3-TPrA, 2,3,3,3-TPrA, PFPA, TFAA, PFTrA: No EMU range calculated due to insufficient quality control data.
(Using a coverage probability of 95% and coverage factor of 2.09 for short chain PFAS, or 2.57 for long chain PFAS.)
Table 10. RESULTS FOR VP1508-17, VP1508-18, VP1508-20, AND REPORTING LIMITS Analyte Concentration (ng/L)
Analyte
City water inlet
(VP1508-17)
Tank 707
(VP1508-18)2
Frac Box
(VP1508-20)
Reporting Limit (RL)
Long Chain 10:2 FTS1 4:2 FTS
< RL
62.8
< RL
50.0
< RL
19.3
< RL
2.07
6:2 FTS
< RL
DET
275
2.10
8:2 FTS HFPO-DA
< RL
810
< RL
2.12
< RL
> 55003
> 55003
5.53
N-EtFOSA
< RL
647
< RL
2.21
N-EtFOSAA
< RL
2780
< RL
2.21
N-MeFOSA
< RL
840
< RL
2.21
N-MeFOSAA
< RL
2130
< RL
2.21
PFBA
< RL
30,400
1220
2.21
PFBS
< RL
7020
597
1.96
PFDA
< RL
2110
15.4
2.21
PFDoA
< RL
745
< RL
50.0
PFECA-A
< RL
313
< RL
2.21
PFHpA
< RL
3590
37.2
2.21
PFHpS
< RL
8290
< RL
2.10
PFHxA
< RL
4720
59.5
2.21
PFHxSTotal
< RL
29,000
40.7
2.02
PFNA
< RL
10,400
62.9
2.21
PFOA PFOSTotal
< RL
DET
1350
2.21
< RL
> 55003
157
2.05
PFOSA
< RL
6950
< RL
2.21
PFPeA
< RL
3270
186
22.1
PFPeS PFTrA4
< RL
189
3.85
2.08
NA
DET
NA
NA
NEICVP1508E01
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Calgon Carbon - Big Sandy Plant Catlettsburg, Kentucky
ENFORCEMENT CONFIDENTIAL
Table 10. RESULTS FOR VP1508-17, VP1508-18, VP1508-20, AND REPORTING LIMITS Analyte Concentration (ng/L)
Analyte
City water inlet
(VP1508-17)
Tank 707
(VP1508-18)2
Frac Box
(VP1508-20)
Reporting Limit (RL)
PFUnA
< RL
24,500
48.5
2.21
Short Chain
2,2,3,3-TPrA
< RL
< RL
< RL
1000
2,3,3,3-TPrA
< RL
DET
DET
200
DBI
< RL
50.3
< RL
10.0
HQ-115
< RL
5280
27.8
10.0
PFECHS
< RL
288
< RL
10.0
PFPA
< RL
DET
DET
800
TFAA
< RL
DET
DET
600
TFMS
< RL
534
3480
10.0
1 Results are estimated due to low spike recovery.
2 Significant ion suppression of internal standards was seen in multiple compounds in VP1508-18. Due to low internal
standard recovery of their corresponding internal standards, some PFAS compounds did not quantify via the
Masshunter software and are thus reported as detected (DET).
3 Reported as a "greater than" value because analyte response was above the response of the highest calibrator.
4 PFTrA was not detected in the spike samples but was detected in VP1508-18 at above the 250 ng/L equivalent
calibrator, thus is reported as DET in VP1508-18 and NA (Not Applicable) in all other samples.
DET - Analytes are detected above the stated RL but could not be quantified due to poor calibration and/or QC results.
or significant ion suppression interfering with the MassHunter software's ability to quantify the result.
EMU- Expanded measurement uncertainty range for reported PFAS concentration values: 64% to 170%, except for:
N-EtFOSAA, N-MeFOSAA, EtFOSA, PFHxA: EMU range: 36% to 230%
10:2 FTS, DBI: EMU range: 51% to 1100%
2,2,3,3-TPrA, 2,3,3,3-TPrA, PFPA, TFAA, PFTrA: No EMU range calculated due to insufficient quality control
data.
(Using a coverage probability of 95% and coverage factor of 2.09 for short chain PFAS, or 2.57 for long chain
PFAS )
Table 11. RESULTS FOR VP1508-21 THROUGH VP1508-24, AND REPORTING LIMITS
Analyte Concentration (ng/L)
Analyte
Equivalent to 004 after 7 tanks
(VP1508-21) (VP1508-22) (VP1508-23)
Field blank
(VP1508-24)
Reporting Limit (RL)
Long Chain
10:2 FTS1
< RL
< RL
< RL
< RL
50.0
4:2 FTS
< RL
< RL
< RL
< RL
2.07
6:2 FTS
< RL
< RL
< RL
< RL
2.10
8:2 FTS
< RL
< RL
< RL
< RL
2.12
HFPO-DA
< RL
< RL
41.9
< RL
5.53
N-EtFOSA
< RL
< RL
< RL
< RL
2.21
N-EtFOSAA
< RL
< RL
< RL
< RL
2.21
N-MeFOSA
< RL
< RL
< RL
< RL
2.21
N-MeFOSAA
< RL
< RL
< RL
< RL
2.21
PFBA
4450
4410
4390
< RL
2.21
PFBS
< RL
< RL
< RL
< RL
1.96
PFDA
< RL
< RL
< RL
< RL
2.21
PFDoA
< RL
< RL
< RL
< RL
50.0
PFECA-A
< RL
< RL
< RL
< RL
2.21
PFHpA
< RL
2.66
< RL
< RL
2.21
PFHpS
< RL
< RL
< RL
< RL
2.10
NEICVP1508E01
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Calgon Carbon - Big Sandy Plant Catlettsburg, Kentucky
ENFORCEMENT CONFIDENTIAL
Table 11. RESULTS FOR VP1508-21 THROUGH VP1508-24, AND REPORTING LIMITS
Analyte Concentration (ng/L)
Analyte
Equivalent to 004 after 7 tanks
(VP1508-21) (VP1508-22) (VP1508-23)
Field blank
(VP1508-24)
Reporting Limit (RL)
PFHxA
< RL
3.77
< RL
< RL
2.21
PFHxSTotal
< RL
< RL
< RL
< RL
2.02
PFNA
< RL
< RL
< RL
< RL
2.21
PFOA
< RL
12.6
14.6
< RL
2.21
PFOSTotal
< RL
< RL
< RL
< RL
2.05
PFOSA
< RL
< RL
< RL
< RL
2.21
PFPeA
< RL
< RL
< RL
< RL
22.1
PFPeS
< RL
< RL
< RL
< RL
2.08
PFTrA2
NA
NA
NA
NA
NA
PFUnA
< RL
< RL
< RL
< RL
2.21
Short Chain
2,2,3,3-TPrA
< RL
< RL
< RL
DET
1000
2,3,3,3-TPrA
DET
DET
DET
< RL
200
DBI
< RL
< RL
< RL
< RL
10.0
HQ-115
< RL
< RL
< RL
< RL
10.0
PFECHS
< RL
< RL
< RL
< RL
10.0
PFPA
DET
DET
DET
< RL
800
TFAA
DET
DET
DET
< RL
600
TFMS
3140
2990
3000
< RL
10.0
1 Results are estimated due to low spike recovery.
2 PFTrA was not detected in the spike samples, thus is reported as NA (Not Applicable).
DET - Analytes are detected above the stated RL but could not be quantified due to poor calibration and/or QC results or
significant ion suppression interfering with the MassHunter software's ability to quantify the result.
EMU- Expanded measurement uncertainty range for reported PFAS concentration values was 64% to 170%, except for:
N-EtFOSAA, N-MeFOSAA, EtFOSA, PFHxA: EMU range: 36% to 230%
10:2 FTS, DBI: EMU range: 51% to 1100%
2,2,3,3-TPrA, 2,3,3,3-TPrA, PFPA, TFAA, PFTrA: No EMU range calculated due to insufficient quality control data.
(Using a coverage probability of 95% and coverage factor of 2.09 for short chain PFAS, or 2.57 for long chain PFAS.)
EMU ranges were calculated for each PFAS shown in Tables 9 through 12 and were based on their quality control (QC) data, including analyte recoveries from the trip and laboratory spike samples. For 2,2,3,3-TPrA, 2,3,3,3-TPrA, PFPA, TFAA, and PFTrA, EMU ranges could not be determined due to insufficient QC data. EMU ranges were calculated for the remaining PFAS and each were placed into one of the range groupings shown in Tables 9 through 12, depending on the accuracy and precision of their QC data. For example, the accuracy of the QC data for 10:2 FTS, and DBI were either much lower than expected, or the precision was highly variable which placed them in the 51% to 1100% EMU range grouping.
NEICVP1508E01
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Calgon Carbon - Big Sandy Plant Catlettsburg, Kentucky
ENFORCEMENT CONFIDENTIAL Semi-Targeted PFAS Analysis
The SPE extracts were also analyzed using the LC/MS QTOF method from Table 6, for the semitargeted PFAS shown in Table 12, which includes the NEIC acronyms, molecular formula, and exact mass values.
Table 12. SEMI-TARGETED PFAS, NEIC ACRONYM, FORMULAS and EXACT MASS VALUES
Analyte
NEIC Acronym
Formula
Exact Mass Value (Dalton)1
4,8-Dioxa-3H-perfluorononanoic acid
ADONA
C7H2F12O4
377.9762
4,8-Dioxa-3H-perfluorononanoate sodium salt
NaDONA
C7HF12O4Na
399.9581
Perfluorobutane sulfonamide (C4 amide)
1,1,2,2,3,3,4,4,4-Nonafluorobutane-1-
FBSA
C4H2F9NO2S
298.9663
sulfonamide
Perfluorobutyl sulfonamido acetic acid
FBSAA (1)
C6H4F9NO4S
356.9717
Nonafluoro-N-(2-hydroxyethyl)butane-1sulfonamide
FBSE = HFBSE Alcohol
C6H6F9NO3S
342.9925
[(Nonafluorobutane-1-sulfonyl)carboxymethylamino] acetic acid
FBSEE diacid
C8H6F9NO6S
414.9772
Nonafluoro-N,N-bis(2-hydroxyethyl)butane1- sulfonamide
FBSEE diol
C8H10F9NO4S
387.0187
N-methyl-perfluorobutane sulfonamide or
1,1,2,2,3,3,4,4,4-nonafluoro-N-methyl-1-
MeFBSA
C5H4F9NO2S
312.9819
Butanesulfonamide
Perfluorobutyl-methyl sulfonamido acetic acid
MeFBSAA
C7H6F9NO4S
370.9874
Nonafluoro-N-(2-Hydroxyethyl)-N-methyl-1butanesulfonamide
MeFBSE
C7H8F9NO3S
357.0081
2-(N-ethylperfluoro-1-octanesulfonamido)ethanol
N-EtFOSE
C12H10F17NO3S
571.0110
2-(N-methylperfluoro-1octanesulfonamido)-ethanol
N-MeFOSE
C11H8F17NO3S
556.9953
Perfluorobutanesulfinic Acid
PFBSi
C4HF9O2S
283.9554
2,2,3,3-tetrafluoro-3-(trifluoromethoxy)propanoic acid
PFECA F or PMPA
C4HF7O3
229.9814
Perfluoro(2-ethoxyethane) sulfonic acid
PFEESA
C4HF9O4S
315.9452
2-[1-[difluoro(1,2,2,2-
tetrafluoroethoxy)methyl]-1,2,2,2tetrafluoroexthoxy]-1,1,2,2-tetrafluoro-
PFESA BP2 (Nafion)
C7H2F14O5S
463.9399
ethanesulfonic acid
Perfluoro-3,6-dioxa-4-methyl-7-octene-1sulfonic acid
PFESA BP1
C7HF13O5S
443.9337
2,2-difluoro-2-(trifluoromethoxy) acetic acid
PFMOAA
C3HF5O3
179.9846
Perfluoro-3,5-dioxahexanoic acid
PFO2HxA
C4HF7O4
245.9763
Perfluoro-3,5,7-trioxaoctanoic acid
PFO3OA
C5HF9O5
311.9680
Perfluoro-3,5,7,9-tetraoxadecanoic acid
PFO4DA
C6HF11O6
377.9597
Perfluoro-3,5,7,9,11-pentaoxadodecanoic acid
PFO5OA or TAFN4
C7HF13O7
443.9515
Overlap targeted analytes for confirmation of spikes and samples.
NEICVP1508E01
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Calgon Carbon - Big Sandy Plant Catlettsburg, Kentucky
ENFORCEMENT CONFIDENTIAL
Table 12. SEMI-TARGETED PFAS, NEIC ACRONYM, FORMULAS and EXACT MASS VALUES
Analyte
NEIC Acronym
Formula
Exact Mass Value (Dalton)1
Perfluorooctanesulfonic Acid2
PFOS
C8HF17O3S
499.9375
Perfluorooctanoic Acid2
PFOA
C8HF15O2
413.9737
1 - Exact mass value is the summation of the principal isotope for each element that make up the compound.
2 - PFOA and PFOS were also analyzed and quantified using the LC/MS QQQ analysis.
Reference materials for 13 of the semi-targeted PFAS were used to prepare calibration standards that were analyzed with the SPE extracts. The identifications of these analytes were based on comparing responses (retention time, accurate mass value, etc.) from the extracts and calibration standards. Once identified, calibration data was used to approximate these analyte concentrations in the samples. Tentative identifications of the remaining semi-targeted PFAS in the extracts were based solely on observed accurate mass value from precursor, fragment and adducts ions, and comparing these to their exact mass values, as no reference material was readily available for these analytes.
Table 13 contains the semi-targeted PFAS results. Samples not shown in this table indicate that none of the semi-targeted PFAS were identified.
Table 13. SEMI-TARGETED PFAS RESULTS NEIC Tag Number
Compound Acronym
VP1508-04 VP1508-05 VP1508-06 VP1508-07 VP1508-09 VP1508-10 VP1508-14 VP1508-15 VP1508-17 VP1508-18 VP1508-20 VP1508-21 VP1508-22 VP1508-23 VP1508-28 VP1508-29 VP1508-30
Semi-Targeted Identifications (ng/L)1
PFECA F
--- --- --- --- --- --- --- --- --- >240 --- >65 --- --- --- --- ---
PFBSi
--- --- --- --- --- --- --- --- --- >800 X --- --- --- --- --- ---
FBSA
--- --- --- --- --- --- --- --- --- X X --- --- --- --- --- ---
PFESA BP2
--- --- --- --- X --- --- X X X X --- --- --- --- --- ---
MeFBSA
--- --- --- --- --- --- --- --- --- >680 X --- --- --- --- --- ---
Tentative Identifications
PFO5OA
--- --- --- --- --- --- --- --- --- O --- --- --- --- --- --- ---
PFO2HxA
--- --- --- --- --- --- --- --- --- O O --- --- --- --- --- ---
PFO3OA
--- --- --- --- --- --- --- --- --- O O --- --- --- --- --- ---
PFMOAA
--- --- --- --- --- --- --- --- --- O O --- --- --- --- --- ---
PFOA
--- ---
PFOS
--- --- --- --- --- ---
6H-Perfluorohex-1-ene --- --- --- --- O O --- --- --- O O --- --- --- --- --- ---
Perfluoro-3(1H-perfluoroethoxy)
--- --- --- --- --- O --- --- --- --- --- --- --- --- --- --- ---
NEICVP1508E01
Page 28 of 46
Calgon Carbon - Big Sandy Plant Catlettsburg, Kentucky
VP1508-04 VP1508-05 VP1508-06 VP1508-07 VP1508-09 VP1508-10 VP1508-14 VP1508-15 VP1508-17 VP1508-18 VP1508-20 VP1508-21 VP1508-22 VP1508-23 VP1508-28 VP1508-29 VP1508-30
Compound Acronym
ENFORCEMENT CONFIDENTIAL Table 13. SEMI-TARGETED PFAS RESULTS
NEIC Tag Number
propane
2-Vinylperfluorobutane --- --- --- --- --- --- --- --- --- O O --- --- --- --- --- ---
3-(Perfluoro-2-
--- --- --- --- --- --- --- --- --- O --- --- --- --- --- --- ---
butyl)propane-1,2-diol
3-(Perfluoropropyl) propanol
--- --- --- --- --- --- --- --- --- O --- --- --- --- --- --- ---
Allyl perfluoroisopropyl --- --- --- --- --- --- --- --- --- O --- --- --- --- --- --- --ether
FDEA
--- --- --- --- --- --- --- --- --- O --- --- --- --- --- --- ---
Methyl perfluorohexanoate
--- --- --- --- --- --- --- --- --- O --- --- --- --- --- --- ---
PFecHS
O O O --- --- --- --- --- --- O --- --- --- --- O O O
Perfluorohexane sulfonamide
--- --- --- --- --- --- --- --- --- O --- --- --- --- --- --- ---
1 - Identification based on reference material comparison.
"X" - observed response was less than the lowest calibration standard response.
">" - observed response was within calibration standard response range and the reported concentration value in
nanograms per liter (ng/L) is a minimal value, as the extraction efficiency for these analytes were not evaluated
during the semi-targeted analysis.
O - Tentative identification based on the accurate mass value of observed precursor, fragment and adduct ions.
No calibration standard was analyzed as reference material was not readily available.
- Calibration standards for PFOA and PFOS were not analyzed with these samples, but these analytes were identified and
quantified in the SPE extracts using the LC/MS QQQ method shown in Table 6.
--- Indicates analyte was not observed.
NEICVP1508E01
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Calgon Carbon - Big Sandy Plant Catlettsburg, Kentucky
ENFORCEMENT CONFIDENTIAL
INVESTIGATION OBSERVATIONS
NEIC made the following observations during the multimedia compliance inspection. NEIC field team members discussed all observations with facility representatives during the closeout meeting unless otherwise noted in the observation description below. Additional observations were made based on the analytical results of the samples collected during the inspection that were not discussed with the facility representatives.
These observations are not final compliance determinations. OCE-WED, OCE-WCED, and Region 4 will make the final compliance determinations based on their review of this report and other technical, regulatory, and facility information.
Observation: 1 CWA Observation Summary: Analytical results provided by NEIC laboratory for the wastewater samples collected by NEIC during the inspection at outfall 001, 002, 003, and internal outfall 004 show the discharge of several PFAS that are not listed in the KYPDES permit and are not monitored in the discharge. Citation: 40 Code of Federal Regulations (CFR) 122.1(b) - Scope of the NPDES permit requirement. (1) The NPDES program requires permits for the discharge of "pollutants" from any "point source" into "waters of the United States." The terms "pollutant", "point source" and "waters of the United States" are defined at 122.2.
Kentucky Revised Statutes (KRS) 224.70-110 - No person shall, directly or indirectly, throw, drain, run or otherwise discharge into any of the waters of the Commonwealth, or cause, permit or suffer to be thrown, drained, run or otherwise discharged into such waters any pollutant, or any substance that shall cause or contribute to the pollution of the waters of the Commonwealth in contravention of the standards adopted by the cabinet or in contravention of any of the rules, regulations, permits, or orders of the cabinet or in contravention of any of the provisions of this chapter.
Evidence: Appendix A - Calgon Carbon Big Sandy Plant Final Permit KY0022276 Appendix H - VP1508 Calgon Carbon- Big Sandy Plant - Photographs Description of Observation: Calgon is authorized to discharge boiler blowdown and backwash water, prime line bakers wet scrubbers, acid wash/neutralization wastewater, wash down, non-contact cooling, stormwater, REACT wastewater (including motive water from REACT and stormwater from the REACT area (Outfall 004)) domestic sanitary wastewater, and stormwater runoff from closed and capped landfill through outfalls 001, 002, and 003 per its KYPDES permit (Appendix A)
NEIC collected wastewater samples from outfalls 001, 002, 003, and equivalent to outfall 004 identified as sample tag numbers VP1508-07, VP1508-12, VP1508-13, VP1508-21, VP1508-22, and VP1508-23 (Appendix H, photos 45, 53, 56, and 68).
NEICVP1508E01
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Calgon Carbon - Big Sandy Plant Catlettsburg, Kentucky
ENFORCEMENT CONFIDENTIAL Observation: 1 CWA The table below displays the quantitative analytical results for samples VP1508-07, VP150812, VP1508-21, VP1508-22, and VP1508-23 reported in ng/L (equivalent to parts per trillion [ppt]).
Analyte
Outfall 001
(VP150812)
Outfall 002
(VP150813)
10:2 FTS1
< RL
< RL
4:2 FTS
< RL
< RL
6:2 FTS
< RL
< RL
8:2 FTS
< RL
< RL
HFPO-DA
< RL
< RL
N-EtFOSA
< RL
< RL
N-EtFOSAA
< RL
< RL
N-MeFOSA
< RL
< RL
N-MeFOSAA < RL
< RL
PFBA
169
< RL
PFBS
< RL
< RL
PFDA
< RL
< RL
PFDoA
< RL
< RL
PFECA-A
< RL
< RL
PFHpA
< RL
< RL
PFHpS
< RL
< RL
PFHxA
< RL
6.89
PFHxSTotal
< RL
< RL
PFNA
< RL
< RL
PFOA
< RL
< RL
PFOSTotal
< RL
< RL
PFOSA
< RL
< RL
PFPeA
< RL
< RL
PFPeS
< RL
< RL
PFTrA2
NA
NA
PFUnA
< RL
< RL
2,2,3,3-TPrA < RL
< RL
2,3,3,3-TPrA DET
< RL
DBI
< RL
< RL
HQ-115
< RL
< RL
PFECHS
< RL
< RL
PFPA
DET
< RL
TFAA
DET
< RL
TFMS
21.0
< RL
Analyte Concentration (ng/L)
Outfall 003
Equivalent to 004 after 7 tanks
(VP1508-07)
(VP1508- (VP1508- (VP1508-
21)
22)
23)
Long Chain
< RL
< RL
< RL
< RL
< RL
< RL
< RL
< RL
< RL
< RL
< RL
< RL
< RL
< RL
< RL
< RL
< RL
< RL
< RL
41.9
< RL
< RL
< RL
< RL
< RL
< RL
< RL
< RL
< RL
< RL
< RL
< RL
< RL
< RL
< RL
< RL
6.22
4450 4410 4390
< RL
< RL
< RL
< RL
< RL
< RL
< RL
< RL
< RL
< RL
< RL
< RL
< RL
< RL
< RL
< RL
< RL
< RL
2.66
< RL
< RL
< RL
< RL
< RL
< RL
< RL
3.77
< RL
< RL
< RL
< RL
< RL
< RL
< RL
< RL
< RL
< RL
< RL
12.6
14.6
< RL
< RL
< RL
< RL
< RL
< RL
< RL
< RL
< RL
< RL
< RL
< RL
< RL
< RL
< RL
< RL
NA
NA
NA
NA
< RL
< RL
< RL
< RL
Short Chain
< RL
< RL
< RL
< RL
< RL
DET
DET
DET
< RL
< RL
< RL
< RL
< RL
< RL
< RL
< RL
< RL
< RL
< RL
< RL
< RL
DET
DET
DET
< RL
DET
DET
DET
< RL
3140 2990 3000
Reporting Limit (RL)
50.0 2.07 2.10 2.12 5.53 2.21 2.21 2.21 2.21 2.21 1.96 2.21 50.0 2.21 2.21 2.10 2.21 2.02 2.21 2.21 2.05 2.21 22.1 2.08 NA 2.21
1000 200 10.0 10.0 10.0 800 600 10.0
NEICVP1508E01
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Calgon Carbon - Big Sandy Plant Catlettsburg, Kentucky
ENFORCEMENT CONFIDENTIAL Observation: 1 CWA
1 Results are estimated due to low spike recovery. 2 PFTrA was not detected in the spike samples, thus is reported as NA (Not Applicable). DET - Analytes are detected above the stated RL but could not be quantified due to poor calibration and/or QC results or significant ion
suppression interfering with the MassHunter software's ability to quantify the result. EMU- Expanded measurement uncertainty range for reported PFAS concentration values was 64% to 170%, except for:
N-EtFOSAA, N-MeFOSAA, EtFOSA, PFHxA: EMU range: 36% to 230% 10:2 FTS, DBI: EMU range: 51% to 1100% 2,2,3,3-TPrA, 2,3,3,3-TPrA, PFPA, TFAA, PFTrA: No EMU range calculated due to insufficient quality control data. (Using a coverage probability of 95% and coverage factor of 2.09 for short chain PFAS, or 2.57 for long chain PFAS.)
None of the above analytes are subject to monitoring requirements in the permit.
In addition to the quantitative analysis, the semi- targeted and tentative identifications show the presence of PFECA F in the outfall 004 equivalent samples.
Observation: 2 CWA Observation Summary: NEIC inspectors observed evidence that unmonitored stormwater discharges were occurring at multiple locations in the southeast portion of the facility during rain events. These locations are not included in the KPDES permit as locations for allowable stormwater discharges. Citation:
KPDES Permit - KY0022276
Pursuant to Authority in KRS 224,...
Calgon Carbon Corporation...is authorized to discharge from a facility located at Calgon Carbon Corporation - Big Sandy Plant, 15025 US Route 23 S, Catlettsburg, Boyd County, Kentucky to receiving waters named: Big Sandy River and White's Creek in accordance with effluent limitations, monitoring requirements and other conditions set forth in this permit.
Section 1.1 - 1.1. Compliance Monitoring Locations (Outfalls)
The following table lists the outfalls authorized by this permit, the location and description of each, and the DOW assigned KPDES outfall number:
Outfall No. 001
Outfall Type External
Latitude (N) 38.337500
Longitude (W) 82.587500
Receiving Water Big Sandy River
Description
Boilers blowdown and backwash Prime Line Bakers Wet Scrubbers Acid Wash / Neutralization wastewater Wash Down Non-Contact Cooling Stormwater
NEICVP1508E01
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Calgon Carbon - Big Sandy Plant Catlettsburg, Kentucky
ENFORCEMENT CONFIDENTIAL
Observation: 2 CWA
REACT Wastewater (Outfall
004)
002 External 38.337500 82.587500 Big Sandy Domestic Sanitary
River
Wastewater
003 External 38.336138 82.598799 White's Stormwater runoff from
Creek
closed and capped landfill
004 Internal 38.337682 82.588372 Outfall
Motive water from REACT
001
Stormwater from REACT area
CWA 301(a): except as in compliance with this section and sections 302, 306, 307, 318, 402 and 404 of this Act, the discharge of any pollutant by any person shall be unlawful.
40 CFR 122.1(b)(1): The NPDES program requires permits for the discharge of "pollutants" from any "point source" into "waters of the United States."
40 CFR 122.2: Pollutant: means dredged spoil, solid waste, incinerator residue, filter backwash, sewage, garbage, sewage sludge, munitions, chemical wastes, biological materials, radioactive materials (except those regulated under the Atomic Energy Act of 1954, as amended (42 U.S.C. 2011 et seq.)), heat, wrecked or discarded equipment, rock, sand, cellar dirt and industrial, municipal, and agricultural waste discharged into water. It does not mean: (a) Sewage from vessels; or (b) Water, gas, or other material which is injected into a well to facilitate production of oil or gas, or water derived in association with oil and gas production and disposed of in a well, if the well used either to facilitate production or for disposal purposes is approved by authority of the State in which the well is located, and if the State determines that the injection or disposal will not result in the degradation of ground or surface water resources.
40 CFR 122.26(b)(14): Storm water discharge associated with industrial activity means the discharge from any conveyance that is used for collecting and conveying storm water and that is directly related to manufacturing, processing or raw materials storage areas at an industrial plant. The term does not include discharges from facilities or activities excluded from the NPDES program under this part 122. For the categories of industries identified in this section, the term includes, but is not limited to, storm water discharges from industrial plant yards; immediate access roads and rail lines used or traveled by carriers of raw materials, manufactured products, waste material, or by-products used or created by the facility; material handling sites; refuse sites; sites used for the application or disposal of process waste waters (as defined at part 401 of this chapter); sites used for the storage and maintenance of material handling equipment; sites used for residual treatment, storage, or disposal; shipping and receiving areas; manufacturing buildings; storage areas (including tank farms) for raw materials, and intermediate and final products; and areas where industrial activity has taken place in the past and significant materials remain and are exposed to storm water. For the purposes of this paragraph, material handling activities include storage, loading and unloading, transportation, or conveyance of any raw material, intermediate product, final product, by-product or waste product. The term excludes areas located on plant lands separate from the plant's industrial activities, such as office buildings and accompanying parking lots as long as the drainage from the excluded areas is not mixed with storm water
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Calgon Carbon - Big Sandy Plant Catlettsburg, Kentucky
ENFORCEMENT CONFIDENTIAL Observation: 2 CWA drained from the above described areas. Industrial facilities (including industrial facilities that are federally, State, or municipally owned or operated that meet the description of the facilities listed in paragraphs (b)(14)(i) through (xi) of this section) include those facilities designated under the provisions of paragraph (a)(1)(v) of this section. Evidence: Appendix H - VP1508 Calgon Carbon- Big Sandy Plant - Photographs
Description of Observation: During the walkthrough of the site, NEIC inspectors observed evidence of stormwater discharges along the southeast side of the property. Photos 38, 39, 40, 42, and 43 (Appendix H) display evidence of stormwater flow leaving the industrial containment areas and running down the banks of the Big Sandy River. The apparent flow paths of the storm water indicate that coal may have been present in the discharges.
Calgon is only authorized to discharge industrial stormwater through outfalls 001, 003, and 004.
The facility started remediation efforts during NEIC's inspection to stop future discharges (Appendix H, photos 70, 71, 72, and 73) and was developing a plan to fully resolve the issue.
Observation: 3 CWA Observation Summary: Best Management Practices (BMP) inspection reports did not include stormwater assessments on the southeast portion of the facility where NEIC inspectors found evidence of unmonitored stormwater discharges. Citation: KYPDES Permit KY0022276 - 3.5 Specific Requirements - The plan shall be consistent with the general guidance contained in the publication entitled "NPDES Best Management Practices Guidance Document" and shall include the following baseline BMPs as a minimum:... (7) Good Housekeeping.
BMP Plan Section 4.1.3 - ...Any material with the potential to contaminate storm water is stored on an impervious surface with drainage to the treatment facility or secondary containment will be utilized.
BMP Plan Section 4.1.6 - Monthly and quarterly visual inspections are conducted to audit that all elements of the SWP3/BMP Plan are in place and working properly. The Big Sandy Plant Pollution Prevention Team is responsible for conducting and recording the results of all visual inspections. Appendix D, or Section J of the Comprehensive Environmental BMP include the Inspection Report Forms that are used to record inspection findings. Periodic housekeeping audits are also performed to assist with each area's compliance.
Evidence: Appendix L - Calgon Carbon-BMP-SWPPP
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Calgon Carbon - Big Sandy Plant Catlettsburg, Kentucky
ENFORCEMENT CONFIDENTIAL Observation: 3 CWA Description of Observation: In the Calgon Carbon BMP/Storm Water Pollution Prevention Plan (SWPPP), there are inspection forms available for facility representatives to conduct monthly and quarterly monitoring of the site (Appendix L, pages 35 - 41). The inspection forms do not include monitoring for stormwater discharges on the southeast portion of the property and the monthly form appears focused on the "oil storage and loading/unloading areas," "oil-filled electrical equipment areas," and "chemical storage tanks." The only language on the quarterly form addressing stormwater states, "Is storm water in areas around mobile fueling vehicle, diesel fuel pumps, and above ground storage tanks adequately addressed?"
During the inspection, NEIC inspectors observed evidence of unmonitored stormwater discharges occurring along the bank of the Big Sandy River on the southeastern portion of the site. The KYPDES permit only allows for the discharge of stormwater through the permitted outfalls.
Observation: 4 CWA Observation Summary: The BMP/SWPPP plan refers to sheet flows leaving the industrial material storage areas. NEIC inspectors observed evidence of industrial stormwater discharges occurring in the material storage areas. Citation: 40 CFR 122.26(b)(14): Storm water discharge associated with industrial activity means the discharge from any conveyance that is used for collecting and conveying storm water and that is directly related to manufacturing, processing or raw materials storage areas at an industrial plant...
Evidence: Appendix L - Calgon Carbon-BMP-SWPPP Appendix H - VP1508 Calgon Carbon- Big Sandy Plant - Photographs Description of Observation: Page 6 of Calgon's BMP/SWPPP plan (Appendix L) states:
Small portions of the extreme southern and eastern areas of the property which drain by sheet flow to the Big Sandy River. These areas total less than 1.5 acres and are made up primarily of the raw material storage area outside slope and the southern edge of the property, which naturally slopes in that direction. No oils are stored or utilized in this area.
Discharges from the industrial processing areas that are exposed to stormwater are to be prevented unless the water is discharged through the approved existing outfalls. The specific reference to sheet flows occurring and discharging from the industrial areas indicates that the facility must control the stormwater flows and eliminate discharges.
The facility had conducted some remedial actions by the close of the NEIC inspection to prevent additional run off from the storage areas to the Big Sandy River (Appendix H, photos 70, 71, 72, and 73).
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ENFORCEMENT CONFIDENTIAL
Observation: 5 CWA Observation Summary: The collection drain between the REACT area and the north staging area was clogged. Citation: None Evidence: Appendix H - VP1508 Calgon Carbon- Big Sandy Plant - Photographs Appendix M - REACT Trench Photographs
Description of Observation: NEIC inspectors observed that the collection drain on the border of the REACT area adjacent to the north staging area was clogged with, what appeared to be, spent carbon (Appendix H, photo 17). The clogged drain would prevent the collection of water and might allow the discharge of materials outside of the REACT containment area. This issue was corrected before the end of the inspection (Appendix M).
Observation: 6 CWA Observation Summary: A small spill of carbon was observed by NEIC inspectors outside of the REACT containment area. Citation: None Evidence: Appendix H - VP1508 Calgon Carbon- Big Sandy Plant - Photographs Appendix N - 3-22-23 Spent Carbon Spill
Description of Observation: NEIC inspectors observed evidence of a small spill of untreated, used, activated carbon extending from the north side of the REACT area into the north staging area (Appendix H, photo 15 and 16). This spill was cleaned up before the end of the inspection (Appendix N).
Observation: 1 RCRA Observation Summary: Calgon stored hazardous waste in four frac tanks in the REACT area. Calgon did not have a written assessment, reviewed, and certified by a qualified Professional Engineer, attesting that the four tank systems have sufficient structural integrity and are acceptable for the storing and treating of hazardous waste. The assessment is required before placing the tanks into service. Citation: 401 Kentucky Administrative Regulations (KAR) 39:090. Hazardous waste permit program.
Section 1. Owners and Operators of Hazardous Waste Treatment, Storage, and Disposal Facilities. Except as established in subsections (1) through (7) of this section and Sections 5 through 9 of this administrative regulation, standards for owners and operators of hazardous waste treatment, storage, and disposal facilities shall be as established in 40 C.F.R. Part 264, except 40 C.F.R. 264.1(f), 40 C.F.R. 264.1(g)(12), 40 C.F.R. 264.15(b)(5), 40 C.F.R. 264.149, 40 C.F.R. 264.150, 40 C.F.R. 264.301(l), 40 C.F.R. 264.1030(d), 40 C.F.R. 264.1050(g), and 40 C.F.R. 264.1080(e) through (g).
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Calgon Carbon - Big Sandy Plant Catlettsburg, Kentucky
ENFORCEMENT CONFIDENTIAL Observation: 1 RCRA 401 KAR 39:060, Section 3(1) [40 CFR 261.3] Definition of hazardous waste.
(a) A solid waste, as defined in 261.2, is a hazardous waste if: (2) It meets any of the following criteria: (iv) It is a mixture of solid waste and one or more hazardous wastes listed in subpart D of this part and has not been excluded from paragraph (a)(2) of this section under 260.20 and 260.22,
401 KAR 39:005, Section 1 [40 CFR 260.10] Definitions Tank means a stationary device, designed to contain an accumulation of hazardous waste which is constructed primarily of non-earthen materials (e.g., wood, concrete, steel, plastic) which provide structural support.
401 KAR 39:090, Section 1 [40 CFR 264.192] Design and installation of new tank systems or components.
(a) Owners or operators of new tank systems or components must obtain and submit to the Regional Administrator, at time of submittal of part B information, a written assessment, reviewed and certified by a qualified Professional Engineer, in accordance with 270.11(d) of this chapter, attesting that the tank system has sufficient structural integrity and is acceptable for the storing and treating of hazardous waste. The assessment must show that the foundation, structural support, seams, connections, and pressure controls (if applicable) are adequately designed and that the tank system has sufficient structural strength, compatibility with the waste(s) to be stored or treated, and corrosion protection to ensure that it will not collapse, rupture, or fail.
Evidence: Appendix H - VP1508 Calgon Carbon- Big Sandy Plant - Photographs Appendix O - Calgon Carbon RCRA Permit Application Interviews Description of Observation: At the time of the inspection, Calgon was storing hazardous waste in four frac tanks (Appendix H, photo 5). The frac tanks were labeled as hazardous waste and contained water from the sumps and secondary containment area that was in contact with motive water generated during storm events. The rainwater in the secondary containment is channeled by trenches into the main sump mixing with motive water. The excess water is stored in storage tanks because the volume is too much for the wastewater treatment system to process at one time.
Motive water is used to move spent carbon from the loading sumps into the hazardous waste tanks and, ultimately, to the regeneration furnace. Calgon mixes non-hazardous and hazardous spent carbons (including listed hazardous waste carbon) when received, which, per the mixture rule, would make all spent carbon handled by Calgon a listed hazardous waste. A full list of the hazardous waste codes received by Calgon is in the RCRA permit application (Appendix O, pages 153-185). The list includes F, K, P and U-listed hazardous wastes. Motive water that is mixed with the listed spent carbon is also a listed hazardous waste. As more water is needed in the motive water system to make up for lost water, the hazardous waste stored in the frac tanks is returned to main sump and transferred to permitted hazardous waste tank D-707, the carbon motive water tank.
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Calgon Carbon - Big Sandy Plant Catlettsburg, Kentucky
ENFORCEMENT CONFIDENTIAL Observation: 1 RCRA Frac tanks are designed for use as stationary tanks. Frac tanks are not designed to transport material when material is stored in the tanks. Because the tanks are designed and intended for use when stationary, frac tanks meet the definition of a tank in 40 CFR 260.10.
According to Calgon representatives, the frac tanks were placed into service two or three years before the NEIC inspection. At the time of the inspection, Calgon could not provide a written assessment, reviewed, and certified by a qualified Professional Engineer, in accordance with 40 CFR 270.11(d), attesting that the four tank systems have sufficient structural integrity and is acceptable for the storing and treating of hazardous waste. Calgon representatives stated that such an assessment has not been performed.
Observation: 2 RCRA Observation Summary: Calgon stored listed hazardous waste sludge from the motive water system in a secondary containment system. The containment system meets the definition of a tank. This unit is not included as a hazardous waste management unit in Calgon's hazardous waste permit and did not have an engineering assessment performed before the unit was placed into service. Citation:
401 KAR 39:090. Hazardous waste permit program.
Section 1. Owners and Operators of Hazardous Waste Treatment, Storage, and Disposal Facilities. Except as established in subsections (1) through (7) of this section and Sections 5 through 9 of this administrative regulation, standards for owners and operators of hazardous waste treatment, storage, and disposal facilities shall be as established in 40 C.F.R. Part 264, except 40 C.F.R. 264.1(f), 40 C.F.R. 264.1(g)(12), 40 C.F.R. 264.15(b)(5), 40 C.F.R. 264.149, 40 C.F.R. 264.150, 40 C.F.R. 264.301(l), 40 C.F.R. 264.1030(d), 40 C.F.R. 264.1050(g), and 40 C.F.R. 264.1080(e) through (g).
401 KAR 39:060, Section 3(1) [40 CFR 261.3] Definition of hazardous waste. (a) A solid waste, as defined in 261.2, is a hazardous waste if: (2) It meets any of the following criteria: (iv) It is a mixture of solid waste and one or more hazardous wastes listed in subpart D of this part and has not been excluded from paragraph (a)(2) of this section under 260.20 and 260.22,
401 KAR 39:005, Section 1 [40 CFR 260.10] Definitions Tank means a stationary device, designed to contain an accumulation of hazardous waste which is constructed primarily of non-earthen materials (e.g., wood, concrete, steel, plastic) which provide structural support.
401 KAR 39:090, Section 1 [40 CFR 264.192] Design and installation of new tank systems or components.
(a) Owners or operators of new tank systems or components must obtain and submit to the Regional Administrator, at time of submittal of part B information, a written assessment, reviewed and certified by a qualified Professional Engineer, in accordance with 270.11(d) of this chapter, attesting that the tank system has sufficient structural
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Calgon Carbon - Big Sandy Plant Catlettsburg, Kentucky
ENFORCEMENT CONFIDENTIAL Observation: 2 RCRA
integrity and is acceptable for the storing and treating of hazardous waste. The assessment must show that the foundation, structural support, seams, connections, and pressure controls (if applicable) are adequately designed and that the tank system has sufficient structural strength, compatibility with the waste(s) to be stored or treated, and corrosion protection to ensure that it will not collapse, rupture, or fail.
Evidence: Appendix H - VP1508 Calgon Carbon- Big Sandy Plant - Photographs Appendix O - Calgon Carbon RCRA Permit Application Appendix P - REACT Dike Interviews
Description of Observation: Calgon was storing sludge from storm water that fell within the carbon activation process area containment in the secondary containment of a tank that was removed (Appendix H, photo 74). Calgon refers to the area as the dike north of the old hose-in sump (Appendix P), and the area has a secondary containment system that was constructed for a tank that has since been removed. The sludge-containing secondary containment system is located next to a small container unloading sump. The sludge in the containment system observed by NEIC inspectors consisted of spent carbon particles from inside the reactivation process area.
Calgon mixes non-hazardous and hazardous spent carbons (including listed hazardous waste carbon) when received, which, per the mixture rule, would make all spent carbon handled by Calgon a listed hazardous waste. A full list of the hazardous waste codes received by Calgon is in the RCRA permit application (Appendix O, pages 153-185). The list includes F, K, P and Ulisted hazardous wastes. The sludge managed in the secondary containment system described above is also a listed hazardous waste because it consists of particles of spent activated carbon.
Calgon representatives stated that the sludge was the residual solids from storing storm water from process drains and the process area. This is the same material that was stored in the frac tanks in RCRA observation 1 that is managed as hazardous waste.
The containment system is constructed with concrete sides and floor that meets the definition of a tank. At the time of the inspection, a written assessment, reviewed and certified by a qualified Professional Engineer, in accordance with 270.11(d) of this chapter, attesting that the tank system has sufficient structural integrity and is acceptable for the storing and treating of hazardous waste was not available. Calgon representatives stated that such an assessment has not been performed.
The facility provided a picture showing the sludge was removed from the dike area before the end of NEIC's inspection (Appendix P).
Observation: 3 RCRA Observation Summary: The closed vent system for Calgon's hazardous waste tanks contained one open-ended line that operates as a bypass of the activated carbon control device. A closed vent system bypass must be equipped with a flow indicator or a locking device to ensure that it remains closed when the control device is in operation.
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Calgon Carbon - Big Sandy Plant Catlettsburg, Kentucky
Observation: 3 RCRA Citation:
ENFORCEMENT CONFIDENTIAL
401 KAR 39:090. Hazardous waste permit program.
Section 1. Owners and Operators of Hazardous Waste Treatment, Storage, and Disposal Facilities. Except as established in subsections (1) through (7) of this section and Sections 5 through 9 of this administrative regulation, standards for owners and operators of hazardous waste treatment, storage, and disposal facilities shall be as established in 40 C.F.R. Part 264, except 40 C.F.R. 264.1(f), 40 C.F.R. 264.1(g)(12), 40 C.F.R. 264.15(b)(5), 40 C.F.R. 264.149, 40 C.F.R. 264.150, 40 C.F.R. 264.301(l), 40 C.F.R. 264.1030(d), 40 C.F.R. 264.1050(g), and 40 C.F.R. 264.1080(e) through (g).
Hazardous Waste Permit No. KYD-005-009-923 Part VII.C.1.3, Table VII.1: Hazardous Waste Management Units and Control Devices Subject to 40 CFR Part 264 - Subpart CC:
Hazardous Waste Management Unit Tank Farm Area B Thirteen (13) storage and process tanks Including covers, closure devices, closed-vent systems, and control devices
Unit Type
40 CFR Part 264 Subpart J Tank System
Brief Description
Hazardous Waste Storage Tanks: Spent activated carbon/motive water, carbon fines. Design capacities from individual tanks vary from 37 to 20,000 Gallons. Total design capacity all units: 192,077 Gallons
VII.C.7.3 All Tank Farm Area B tanks shall meet the Level 2 requirements discussed in 40 CFR 264.1084(d)(3). The tanks shall be vented directly through a closed-vent system to a control device in accordance with the requirements specified in 40 CFR 264.1084(g).
VII.C.7.3.1 All Tank Farm Area B tanks shall be in compliance with 40 CFR 264.1084(g)(1). Tanks shall be covered by a fixed roof; the fixed roof and its covers and closure devices shall be designed to form a continuous barrier over the entire surface area of the hazardous waste; closure devices shall be designed to operate with no detectable organic emissions; fixed roof and closure devices shall be made of suitable materials that will minimize exposure of the hazardous waste to the atmosphere and maintain their integrity; and the control-vent system and closure device shall be designed and operated in accordance with the requirements of 40 CFR 264.1087. The fixed roof shall be installed with each closure devices secured in the closed position and the vapor headspace underneath the fixed roof vented to the control device except as provided in 40 CFR 264.1084(g)(2).
40 CFR 264 Subpart CC: Emission Standards for Tanks, Surface Impoundments and Containers. 401 KAR 39:090, Section 1 [40 CFR 264.1081] Definitions.
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Calgon Carbon - Big Sandy Plant Catlettsburg, Kentucky
ENFORCEMENT CONFIDENTIAL Observation: 3 RCRA
As used in this subpart, all terms shall have the meaning given them in 40 CFR 265.1081, the Act, and parts 260 through 266 of this chapter.
401 KAR 39:090, Section 1 [264.1031] Definitions. Open-ended valve or line means any valve, except pressure relief valves, having one side of the valve seat in contact with hazardous waste and one side open to the atmosphere, either directly or through open piping.
401 KAR 39:090, Section 1 [40 CFR 264.1087] Standards: Closed-vent systems and control devices.
(a) This section applies to each closed-vent system and control device installed and operated by the owner or operator to control air emissions in accordance with standards of this subpart. (b) The closed-vent system shall meet the following requirements:
(3) In the case when the closed-vent system includes bypass devices that could be used to divert the gas or vapor stream to the atmosphere before entering the control device, each bypass device shall be equipped with either a flow indicator as specified in paragraph (b)(3)(i) of this section or a seal or locking device as specified in paragraph (b)(3)(ii) of this section. For the purpose of complying with this paragraph, low leg drains, high point bleeds, analyzer vents, open-ended valves or lines, spring loaded pressure relief valves, and other fittings used for safety purposes are not considered to be bypass devices.
(i) If a flow indicator is used to comply with paragraph (b)(3) of this section, the indicator shall be installed at the inlet to the bypass line used to divert gases and vapors from the closed-vent system to the atmosphere at a point upstream of the control device inlet. For this paragraph, a flow indicator means a device which indicates the presence of either gas or vapor flow in the bypass line. (ii) If a seal or locking device is used to comply with paragraph (b)(3) of this section, the device shall be placed on the mechanism by which the bypass device position is controlled (e.g., valve handle, damper lever) when the bypass device is in the closed position such that the bypass device cannot be opened without breaking the seal or removing the lock. Examples of such devices include, but are not limited to car-seal or a lock-and-key configuration valve. The owner or operator shall visually inspect the seal or closure mechanism at least once every month to verify that the bypass mechanism is maintained in the closed position. Evidence: Appendix C - Calgon Carbon RCRA Permit Appendix H - VP1508 Calgon Carbon- Big Sandy Plant - Photographs Description of Observation: As required by Section VII.C.G of the hazardous waste permit (Appendix C, page 107), vapors from the tanks in Calgon's Tank Farm Area B are vented through a closed vent system to activated carbon control devices. NEIC inspectors observed one open-ended valve on the closed vent system (Appendix H, Photo 83). The valve was located in the vicinity of white LDAR tags 58-63. Tag 58 is visible on the right-hand side of photo 83. The open-ended valve is a bypass device that could divert the gas or vapor stream to the atmosphere before the
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Calgon Carbon - Big Sandy Plant Catlettsburg, Kentucky
ENFORCEMENT CONFIDENTIAL Observation: 3 RCRA control device. The bypass device is required to be equipped with a flow indicator or a seal or locking device. This valve was not equipped with one of the required devices.
Observation: 4 RCRA Observation Summary: Calgon has not made a hazardous waste determination for the partially activated carbon that is removed from the baker furnaces during process upsets and placed in lagoon 1. Citation: 401 KAR 39:080. Hazardous waste handlers.
Section 1. Generators of Hazardous Waste. (1) Except as established in subsections (2) through (11) of this section and Section 5 of this administrative regulation, the requirements for standards applicable to generators of hazardous waste shall be as established in 40 C.F.R. Part 262, except 40 C.F.R. 262.10(k).
401 KAR 39.080, Section 1(1) [40 CFR 262.11] Hazardous waste determination and recordkeeping. A person who generates a solid waste, as defined in 40 CFR 261.2, must make an accurate determination as to whether that waste is a hazardous waste in order to ensure wastes are properly managed according to applicable RCRA regulations. A hazardous waste determination is made using the following steps:
(a) The hazardous waste determination for each solid waste must be made at the point of waste generation, before any dilution, mixing, or other alteration of the waste occurs, and at any time in the course of its management that it has, or may have, changed its properties as a result of exposure to the environment or other factors that may change the properties of the waste such that the RCRA classification of the waste may change. Evidence: Interviews Description of Observation: When manufacturing virgin activated carbon in the prime lines, coal is placed in the baker furnaces and heated to a high temperature to convert all the hydrocarbons into activated carbon. Process upsets can occur that require the contents of the baker furnaces to be dumped on the pad below the furnace before the coal is completely converted to activated carbon. When this occurs, Calgon sprays the material with water to cool it and then discharges the mixture into the lagoon 1.
During the carbon activation process, the high temperatures in the baker furnaces have the potential to crack long hydrocarbons in the coal into shorter hydrocarbon chains, including benzene. Calgon has not made a hazardous waste determination for the partially activated carbon material that is removed from the baker furnaces during process upsets to determine if the benzene levels in the material are high enough to be classified as a hazardous waste. If the material is a hazardous waste, the act of washing the material into lagoon 1, which is an earthen impoundment, would constitute hazardous waste land disposal. Lagoon 1 is not permitted to receive hazardous waste.
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Calgon Carbon - Big Sandy Plant Catlettsburg, Kentucky
ENFORCEMENT CONFIDENTIAL
Observation: 5 RCRA Observation Summary: Calgon had open-ended lines on the 700-series tanks in Tank Farm Area B. Citation:
Hazardous Waste Permit No. KYD-005-009-923
VII.B AIR EMISSION STANDARDS FOR EQUIPMENT LEAKS VII.B.1 40 CFR Part 264 - Subpart BB contains air emission standards for equipment leaks and applies to all equipment that contains or contacts hazardous wastes with organic concentrations of at least ten (10) percent by weight.
VII.B.1.2 The Permittee, as part of its reactivation process of spent activated carbon through thermal treatment, operates the Area B Tank Farm tanks D-701 through D710 and D-901 through D-903, and the Carbon Regeneration Unit and Feed System, along with their ancillary equipment. This ancillary equipment is identified in Attachment B - Facility Description: Sub-Section B-8 -Equipment Leak Standards: Table B-3, of the Approved Permit Application ("Attachment B-Table B-3"), and contains or contacts hazardous waste with organic concentrations greater than ten (10) percent and less than twenty (20) percent by weight for greater than 300 hours per calendar year. The hazardous waste streams managed in this equipment are not in the gaseous state and have total concentrations, of the organic components, less than 20 percent by weight, making the equipment managing these hazardous waste streams equipment in heavy liquid service. This equipment is subject to 40 CFR Part 264 Subpart BB and Permit Condition VII.B.
401 KAR 39:090, Section 1 [40 CFR 264.1031] Definitions. Open-ended valve or line means any valve, except pressure relief valves, having one side of the valve seat in contact with hazardous waste and one side open to the atmosphere, either directly or through open piping.
401 KAR 39:090, Section 1 [40 CFR 264.1056] Standards: Open-ended valves or lines. (a)(1) Each open-ended valve or line shall be equipped with a cap, blind flange, plug, or a second valve.
(2) The cap, blind flange, plug, or second valve shall seal the open end at all times except during operations requiring hazardous waste stream flow through the openended valve or line. Evidence: Appendix H - VP1508 Calgon Carbon- Big Sandy Plant - Photographs Interviews Description of Observation: In Tank Farm Area B Calgon maintains the 700-series of permitted hazardous waste tanks, identified as D-701 through D-710. As stated in the Calgon hazardous waste permit, tanks D701 through D-710 are subject to the air emissions requirements in 40 CFR Part 264, Subpart BB.
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Calgon Carbon - Big Sandy Plant Catlettsburg, Kentucky
ENFORCEMENT CONFIDENTIAL Observation: 5 RCRA During the inspection, NEIC inspectors observed open-ended lines associated with the following tanks:
Tank
D-701 D-702 D-703 D-704 D-705 D-706
Component Tag Number 966 961 959
Not in the inventory 960 963
According to Calgon representatives, the components identified above are clean-out ports for the water overflow line on each corresponding tank. A photograph of the clean out port for Tank D-704 is shown in Appendix H, photo 82. However, even if the components are clean-out ports, they are also open-ended lines and must be equipped with a cap, plug, blind flange, or second valve to seal the open end.
Observation: 6 RCRA Observation Summary: Calgon operates the intensive screener to separate the motive water from the spent carbon before treatment in the carbon regeneration furnace. The intensive screener is not included in the RCRA permit as a hazardous waste management unit. Citation: 401 KAR 39:005. Definitions for 401 KAR Chapter 39. RELATES TO: KRS 224.1, 224.10, 224.46, 224.50-545(2)(a), 322.010, 40 C.F.R. Parts 260, 261, 262, 268, 270.
Section 1. Definitions. Except as established in this section, definitions for 401 KAR Chapter 39 shall be as established in 40 C.F.R. 260.10.
401 KAR 39:005, Section 1 [40 CFR Section 260.10] Definitions. Ancillary equipment means any device including, but not limited to, such devices as piping, fittings, flanges, valves, and pumps, that is used to distribute, meter, or control the flow of hazardous waste from its point of generation to a storage or treatment tank(s), between hazardous waste storage and treatment tanks to a point of disposal onsite, or to a point of shipment for disposal off-site.
Treatment means any method, technique, or process, including neutralization, designed to change the physical, chemical, or biological character or composition of any hazardous waste so as to neutralize such waste, or so as to recover energy or material resources from the waste, or so as to render such waste non-hazardous, or less hazardous; safer to transport, store, or dispose of; or amenable for recovery, amenable for storage, or reduced in volume.
Evidence: Appendix H - VP1508 Calgon Carbon- Big Sandy Plant - Photographs Appendix O - Calgon Carbon RCRA Permit Application
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Calgon Carbon - Big Sandy Plant Catlettsburg, Kentucky
ENFORCEMENT CONFIDENTIAL Observation: 6 RCRA Description of Observation: The intensive screener (Appendix H, photo 90) removes motive water from the carbon before the carbon is treated in the regeneration furnace. Calgon's RCRA permit application (Appendix O, page 245), lists the intensive screener as ancillary equipment to the carbon regeneration unit. The intensive screener does not meet the definition of ancillary equipment because its primary purpose is not to transport hazardous waste, but rather to remove motive water to make the carbon waste more amenable to treatment by the carbon regeneration unit. Reducing the volume of waste through the removal of motive water constitutes treatment under the definition. Units that treat hazardous waste must be regulated under the permit and have specific permit requirements, either as a tank or a miscellaneous unit.
Observation: 7 RCRA Observation Summary: Calgon operates units that manage motive water. Motive water is water that was mixed with spent carbon that is listed hazardous waste. These units, which include the motive water sumps, motive water trenches, and the diester sump, are not included in the Calgon RCRA permit as hazardous waste management units. Citation: 401 KAR 39:005. Definitions for 401 KAR Chapter 39. RELATES TO: KRS 224.1, 224.10, 224.46, 224.50-545(2)(a), 322.010, 40 C.F.R. Parts 260, 261, 262, 268, 270.
Section 1. Definitions. Except as established in this section, definitions for 401 KAR Chapter 39 shall be as established in 40 C.F.R. 260.10.
401 KAR 39:005, Section 1 [40 CFR Section 260.10] Definitions. Storage means the holding of hazardous waste for a temporary period, at the end of which the hazardous waste is treated, disposed of, or stored elsewhere.
Sump means any pit or reservoir that meets the definition of tank and those troughs/trenches connected to it that serve to collect hazardous waste for transport to hazardous waste storage, treatment, or disposal facilities; except that as used in the landfill, surface impoundment, and waste pile rules, "sump" means any lined pit or reservoir that serves to collect liquids drained from a leachate collection and removal system or leak detection system for subsequent removal from the system.
Tank means a stationary device, designed to contain an accumulation of hazardous waste which is constructed primarily of non-earthen materials (e.g., wood, concrete, steel, plastic) which provide structural support.
Evidence: Appendix O - Calgon Carbon RCRA Permit Application Appendix H - VP1508 Calgon Carbon- Big Sandy Plant - Photographs Description of Observation: Calgon operates units that manage motive water or a mixture of motive water and hazardous waste that are not permitted as RCRA storage units. Motive water is used to move spent carbon from the loading sumps into the hazardous waste tanks and, ultimately, to the regeneration furnace. Calgon mixes non-hazardous and hazardous spent carbon wastes
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Calgon Carbon - Big Sandy Plant Catlettsburg, Kentucky
ENFORCEMENT CONFIDENTIAL Observation: 7 RCRA (including listed hazardous waste carbon) when received which, per the mixture rule, would make all spent carbon handled by Calgon a listed hazardous waste. A full list of the hazardous waste codes received by Calgon is in the RCRA permit application (Appendix O, pages 153185). The list includes F, K, P and U listed hazardous wastes. Any motive water mixed with the listed spent carbon is also a listed hazardous waste. The units that are managing motive water and are not in the Calgon permit as hazardous waste management units include the motive water main sumps and trench collection system, and the diester sump.
The collection and transfer sumps (main sumps) (Appendix H, photo 84) and trench collection system are identified as "other identified equipment" in the RCRA permit application (Appendix O, pages 266-267). The main sumps receive water flows from the trench system within the carbon regeneration area. This includes water from the cleanup of spent activated carbon that is washed into the trenches. The water in the main sump is returned to permitted tank D-707, the spent carbon motive water tank (Appendix O, page 250). According to Calgon representatives, the hazardous waste stored in the frac tanks in Observation 1 RCRA is also returned to the main sump. The diester sump receives a mixture of motive water and spent carbon generated by the intensive screener (Appendix H, photos 87, 88, and 89). The water from the diester is also returned to permitted tank D-707, the spent carbon motive water tank (Appendix O, page 250).
Units that store hazardous waste must be regulated under the permit and have specific permit requirements.
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Calgon Carbon - Big Sandy Plant Catlettsburg, Kentucky