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HomeMy WebLinkAboutNC0000272_2008 Dioxin Monitoring Fish Tissue_20081212 [ kph IS l� Lr as ! DEC 1 2200 , II IT n_ s Blue Ridge Paper Products Inc dba Evergreen Packaging Canton, NC f.evergreeff packaging Blue Ridge Paper Products Inc. - Canton Mill 10 December 2008 CERTIFIED MAIL Return Receipt Requested Roger C.Edwards Regional Supervisor North Carolina Department of Environment And Natural Resources Division of Water Quality Asheville Regional Office 2090 US Highway 70 Swannanoa,NC 28778 Subject: NPDES NC0000272 2008 Dioxin Monitoring in Fish Tissue Blue Ridge Paper Products Inc. dba Evergreen Packaging Canton,NC Dear Mr.Edwards: Enclosed is the 2008 Dioxin in Fish Tissue Report for the Canton Mill. The 2008 report is the 19s'annual fish tissue study submitted by the mill. Field sampling at Waterville Lake in August 2008 and the report were completed by scientists with the Department of Forestry,Wildlife and Fisheries of the University of Tennessee. The fish tissue analyses were performed by Test America West Sacramento. The field sampling and analyses followed the March 2006 study plan approved by the Division. The fish collected in 2008 met the target species and target size and weight distribution criteria of the study plan. The analytical results for 2008 are consistent previous sampling years. TCDD and related isomers in catfish tissue samples were at or below analytical detection limits, continuing the trend seen since 2002. The calculated TEQs for catfish and common carp tissue fillet samples were all below fish advisory levels established by the NC Department of Health and Human Services. Paul Dickens Nick McCracken Manager,Environmental Affairs Water Compliance Coordinator 828-646-6141 828-646-2874 dickep@bluerideepaMr.com mccran@blueridgepapgr.com Enclosure: 2008 Blue Ridge Paper Products Dioxin in Fish Tissue Report C.File—Water; Engr.File—River Studies Blue Ridge Paper Products Inc.—Canton Mill 175 Main Street • PO Box 4000 Canton, North Carolina 28716 • 828-646-2000 Division of Evergreen Packaging Roger Edwards, NC DWQ ARO 12/10/2008 Page 2 Distribution with enclosure: NC Division of Water Quality(two copies) Certified Mail Receipt Central Files 7004 0750 0000 0865 6400 1617 Mail Service Center Raleigh,NC 27699-1617 John Cruchfield Progress Energy 410 South Wilmington Street PEB 4A Raleigh,NC 27602-1551 Bryn Tracy Environmental Biologist North Carolina Department of Environment And Natural Resources Division of Water Quality 1617 Mail Service Center Raleigh,North Carolina 27699-1617 Jeff Engel Chief, Epidemiology Section NC Department of Health and Human Services 1912 Mail Service Center Raleigh,NC 27699-1912 Paul Davis TDEC—Water Pollution Control 401 Church Street 6'"Floor Annex Nashville,TN 37243 Jonathan Burr TDEC—Water Pollution Control Knoxville EAC 2700 Middlebrook Pike State Plaza Building, Suite 220 Knoxville,TN 37921 Sergei Chernikov Engineer, NPDES Permits Section North Carolina Department of Environment and Natural Resources Division of Water Quality 1617 Mail Service Center Raleigh, North Carolina 27699-1617 Blue Ridge Paper Products Inc.—Canton Mill 175 Main Street • PO Box 4000 Canton, North Carolina 28716 • 828-646-2000 Division of Evergreen Packaging RESULTS OF 2008 DIOXIN MONITORING IN FISH TISSUE Prepared for: Blue Ridge Paper Products Inc., dba Evergreen Packaging Canton Mill Canton,North Carolina Prepared by: Theodore B. Henry,Ph.D. Center for Environmental Biotechnology and Departments of Forestry, Wildlife and Fisheries University of Tennessee Knoxville,Tennessee J. Larry Wilson,Ph.D. Departments of Forestry, Wildlife and Fisheries University of Tennessee Knoxville,Tennessee November 2008 TABLE OF CONTENTS Page List of Tables . . . . . . . . . . . . . . . . . ii List of Figures. . . . . . . . . . . . . . . . . iti EXECUTIVE SUMMARY . . . . . . . . . . . . . iv 1. INTRODUCTION . . . . . . . . . . . . . . . 1 2. SAMPLING LOCATIONS . . . . . . . . . . . . . 2 3. SAMPLING OBJECTIVES . . . . . . . . . . . . . 6 4. FISH COLLECTION TECHNIQUES AND LEVEL OF EFFORT . . . 7 5. SAMPLE PREPARATION . . . . . . . . . . . . . 12 6. ANALYTICAL RESULTS . . . . . . . . . . . . . 14 7. REFERENCES . . . . . . . . . . . . . . . 25 8. APPENDICES . . . . . . . . . . . . . . . 28 APPENDIX A: CHAIN OF CUSTODY FORM APPENDIX B: TESTAMERICA WEST SACRAMENTO ANALYTICAL REPORT APPENDIX C: BLUE RIDGE PAPER CANTON MILL FISH FILLET TISSUE ANALYSIS RESULTS 1990-2004 APPENDIX D: 2006 REVISIONS TO DIOXIN MONITORING PLAN - i LIST OF TABLES Number Title Page 2-1 Pigeon River sampling station information . . . . . . . . . 3 4-1 Fish collection techniques and level of effort . . . . . . . . 8 4-2 Summary of fish composites collected in the Pigeon River, August 2008 . . . . . . . . . . . . . . 9 6-1 Summary of Pigeon River fish tissue analysis results—2008 . . . . 16 6-2 Toxicity equivalence factors for CDD/F isomers. . . . . . . . 17 6-3 Summary of CDD/F isomer analyses, toxicity equivalent factors, and toxicity equivalent values for the 2008 Pigeon River fish tissue composites . . . . . . . . . . . . . 19 6-4 Blue Ridge Paper Canton Mill fish fillet tissue analysis results 2005—2008 . . . . . . . . . . . . . . . . 21 ii LIST OF FIGURES Number Title Page ES-1 TCDD concentrations in carp fillets collected from the Pigeon River, 1990-2008. . . . . . . . . . . . . . . . . . v ES-2 TCDD concentrations in catfish fillets collected from the Pigeon River, 1997-2008. . . . . . . . . . . . . . . . . . vi 2-1 Historical sampling station locations on the Pigeon River . . . . . 4 2-2 Sampling Stations 4A and 4B on the Pigeon River . . . . . . 5 4-1 Lengths and weights of fish collected from Waterville Lake for tissue analysis, 2004-2008 . . . . . . . . . . . . . 11 6-1 TCDD concentrations in carp fillets collected from the Pigeon River, 1990-2008 (Stations 4A and 4B) . . . . . . . . . . . 23 6-2 TCDD concentrations in catfish fillets collected from the Pigeon River, 1997-2008 (Stations 4A and 4B) . . . . . . . . . . . . 24 iii EXECUTIVE SUMMARY The Blue Ridge Paper Products Inc., dba Evergreen Packaging, Canton Mill contracted the Department of Forestry, Wildlife and Fisheries of the University of Tennessee, Knoxville (UTK) to collect dioxin fish tissue samples from the Pigeon River during the summer of 2008 in accordance with NPDES permit conditions. UTK field personnel followed the March 2006 revision (Wilson 2006) to the December 2001 Fish Tissue Sampling Plan prepared by EA Engineering, Science and Technology, Inc., (EA Engineering 2001a) of Chicago, Illinois. UTK prepared this 2008 fish tissue sampling report using the revised protocol of 2006. Bottom feeding species (channel catfish and common carp) were collected in August 2008 from two locations (Stations 4A and 4B) in the Pigeon River (Waterville Lake) and analyzed for 2,3,7,8-tetrachlorodibenzo-p-dioxin (TCDD), 2,3,7,8-tetrachlorodibenzofuran (TCDF), and other CDD and CDF isomers. Concentrations of 2,3,7,8-TCDD and 2,3,7,8-TCDF were below the level of detection in channel catfish fillet composites at both Station 4A and Station 4B. In common carp, 2,3,7,8-TCDD was detected (1.2 ppt) in fillet composites collected at Station 4A, but was not detected at Station 4B (detection limit 0.36 ppt). In the common carp whole body composite collected at Station 4B, the concentration of 2,3,7,8-TCDD was estimated at 0.78 ppt. The concentration of 2,3,7,8- TCDF was 2.2 ppt in common carp fillets at Station 4A, 0.84 ppt was estimated at Station 4B, and 2.7 ppt was the concentration in the common carp whole body sample collected at Station 4B. The mean weights of common carp collected from Stations 4A and 4B (4.727 kg, Station 4A; 4.067 kg, Station B) were lower than those collected in 2007 (6.490 kg, Station 4A; 6.552 kg, Station 413), but consistent with weights of common carp collected in previous years (2006, 4.505 kg, Station 4A, 5.637 kg, Station 413; 2005, 3.667 kg - Station 4A, 4.695 kg - Station 413; 2004, 3.771 kg - Station 4A, 3.900 kg - Station 4B; 1999-2003, 3.193 kg, Station 4A, 5.042 kg, Station 4B). Lipid concentrations in common carp fillets in 2008 were 4.5-14% and were lower than observed in 2007 (12-29%). In January 2007, the NC DHHS lifted the fish advisory for common carp in Waterville Lake and requested two additional years of fish tissue sampling and surveillance. All catfish samples collected from Waterville Lake since 2002 have been at or below detection levels for TCDD, TCDF, and related isomers. ! iv Figure ES-1. TCDD Concentrations in Carp Fillets Collected from the Pigeon River, 1990- 2008 (Stations 4A and 46). 70 60 \ \ 50 / \ 0 Station 4A p \\ / \ —t-Station 4B 40 `m \ a \ r 30 R 2 \ p 20 U \ 10 Z ` b 0 1990 1991 1992 1993 1994 1995 1996 1997 1998 1999 2000 2001 2002 2003 2004 2005 2006 2007 2008 YEAR b) TCDD concentrations at Station 4B were not detected, therefore, the values plotted represent the detection limit for those samples. The detection limit for 2,3,7,8-TCDD was elevated in the 2007 carp fillet for Station 4B because of a 10 fold-dilution of the sample which was required to overcome sample matrix effects (high lipid concentration) during analysis. Consequently, reporting the detection limit for this sample can give a misleading impression that the concentration of 2,3,7,8-TCDD increased that year. v Figure ES-2. TCDD Concentrations in Catfish Fillets Collected from the Pigeon River, 1997-2008 (Stations 4A and 4B). 2.50 — — -- 1 2.00 —• f —Station 4A ■ Station 4B 0 1.50 y CL 1.00 — b b c • a: ■ b A ■ • ■ ■ b \ s F 0.50 a ■ a a a 0.00 T T 1997 1998 1999 2000 2001 2002 2003 2004 2005 2006 2007 2008 YEAR a)TCDD concentrations were not detected at Station 4A, therefore the values plotted represent the detection limit for the sample. b) TCDD concentrations were not detected at Station 413, therefore, the values plotted represent the detection limit for the sample. vi 1. INTRODUCTION The Blue Ridge Paper Products Inc., dba Evergreen Packaging, Canton Mill contracted the Department of Forestry, Wildlife and Fisheries of the University of Tennessee, Knoxville (UTK) to collect dioxin fish tissue samples from the Pigeon River during the summer of 2008 in accordance with NPDES permit conditions. UTK field personnel followed the March 2006 revision (Wilson 2006) to the December 2001 Fish Tissue Sampling Plan prepared by EA Engineering, Science and Technology, Inc. (EA Engineering 2001a) of Chicago, Illinois. This report details the results of a study conducted during August 2008 to determine the concentrations of 2,3,7,8-TCDD (dioxin) and 2,3,7,8-TCDF (furan) in bottom-feeding fish collected from the Pigeon River near Canton, North Carolina. The report follows the template developed by EA Engineering for prior reporting years. The 2008 fish tissue study is number 19 in a series of fish tissue surveys designed and conducted to be responsive to the requirements of A.(9.) Dioxin Monitoring Special Condition in Blue Ridge Paper's current NPDES permit for the Canton Mill (Permit No. NC0000272). Sampling locations, selection of target species, sampling methods, and sample preparation/preservation techniques are in accordance with the study plan. The approved study methods and scope detailed herein generally follow those used since 1990 (EA 1990, 1991, 1992, 1993a, 1993b, 1994, 1995, 1996, 1997, 1998, 2000, 2001b, 2001c, 2003, 2004, Wilson 2006, Henry and Wilson 2007, and Henry and Wilson 2008). However, selected project details were modified to be responsive to the suggestions/recommendations of the North Carolina Department of Environment and Natural Resources (NC DNR), the Tennessee Wildlife Resources Agency, U.S. EPA Region IV, and the North Carolina Department of Health and Human Services (NC DHHS). The principal change in the program was that the collection and analysis of sportfish composite samples have not been required since 2000. In 2006, project details were modified again to be responsive to the North Carolina Division of Water Quality (NC DWQ) and these modifications were adhered to in the present investigation(i.e., 2008). The principal changes to the program in 2006 were the elimination of sampling of the main stem of the Pigeon River beginning in 2006 and the collection of at least one whole body bottom feeder sample from Waterville Lake (Stations 4A or 4B). These changes are included in more detail in Appendix D. The 2008 study was conducted during August, during which time biologists from UTK collected and prepared fish tissue samples from the two Waterville Lake sampling locations (Stations 4A and 4B) on the Pigeon River. Details relevant to the location of Pigeon River sampling stations and fish tissue sampling objectives follow in Sections 2 and 3, respectively. Fish collection techniques and level of effort are detailed in Section 4; methods of sample preparation and shipment are presented in Section 5. Analytical results are summarized in Section 6 and references are provided in Section 7. 1 2.SAMPLING LOCATIONS In accordance with the study plan(Wilson 2006) that was implemented in 2006 and 2007 (Henry and Wilson 2007, 2008), fish were collected from two sampling locations on the Pigeon River. For this sampling period two sites (Stations 4A and 4B) were sampled. Detailed sampling station information for both sites is provided in Table 2-1 and Figure 2-2. Monitoring Stations 4A and 4B are located in Waterville Lake at RM 41.5 and 39.0, respectively (Figure 2-1). Station 4A is located approximately 21.8 RM downstream from the Mill outfall, near the Messer Branch-Pigeon River confluence (Figure 2-2). Monitoring Station 4B is in the vicinity of the Wilkins Creek-Pigeon River confluence, approximately 24.3 RM downstream from the Canton Mill outfall (Figure 2-2). Appropriate habitats were sampled within each study reach in an effort to collect the desired complement of fishes. Fish sampling was conducted in the vicinity of each location described above; however, the distance or effort at each station depended on how difficult it was to collect fish at that station. The Station 4B study area consisted of an approximate 1.0 RM reach of Waterville Lake located from the dam to the confluence of Wilkins Creek. Sampling at Stations 4A and 4B included electrofishing and gillnetting near the shore along both the left and right banks of Waterville Lake. Reservoir water level in 2008 was approximately 30 feet below full pool and was similar to water levels in 2007. The Station 4A sample area covered less surface area than water levels in 2004-2006; however, it was similar to the level in 2007. Station 4B was shallower in coves, but the remainder of Station 4B sample area was not significantly reduced in surface area. 2 Table 2-1. Pi eon River sampling stations. Station Station Location and Site Description/Habitat Type Fish Community Number RM Distance from Outfall 4A 41.5 Upper Waterville Lake Characterized by deep-water lentic There are no dominant species. Bluegill,black (21.8 RM downstream from habitat with bedrock covered by crappie, flathead and channel catfish, small mouth the Canton Mill outfall) loose, unconsolidated bottom bass,and largemouth bass are common. Common sediments. Maximum depth carp are present but not common. sampled approximately 3 in. 4B 39.0 Lower Waterville Lake Characterized by deep-water lentic There are no dominant species. Bluegill,black from the dam to confluence habitat,bedrock, and soft crappie,flathead and channel catfish, small mouth with Wilkins Creek(24.3 'sediments. Maximum depth bass,and largemouth bass are common. Common RM downstream from the sampled approximately 12 in. Very carp are present but not common. Canton Mill outfall) stee banks with little cover. 3 Figure 2-1. Fish tissues.were collected from two sites (4A and 4B)for dioxin analyses in 2008. More precise geographical locations of each site are presented in Figure 2-2. Bleglo0.TN NaeNoN,TN 09.a) NW pro'Fn5 Bud, 12IL5) TENNESSEE N Near ttmtd)tul �''•••�...� —..` (19�7 ..... OANROOUNA �+�..(2� ,eh Qlq fjae .j NOTE: Rlvsr mNoa of ma Instem sampling I.A.or Hydro PI bbulary mouth sb.in parentheses. (t45} 1 9 B � A Fish and Benllms Sampling S Uon �i WaNa.e Dam pFGemSofeAa cemmeehod 4B ((=I) Na 4A 4zc 16) � (4zz) oaa x.wwpeeenaeo Nnsrslao (ad49 s) MT.stl nbow c.emne (szd) �,rcow (MG)./ MAVIP TNckety (460) W.W.fJYd. (S(SJ.1) Fag nBddge (551) Above OlYde F@o Mse . (59.0) Flbarvula W swills WN!(P Elul OUVO Oantaq N6 am lux) 13 (w37 Wayne 1. ONde•NO aut (54.E) (SIy) 4. 'OV f Grassy Knob + Illy' op 4� W�. WATERVILLE LAKE C '44C 4j Y Figure 2-2. Sampling Stations 4A(indicated by A) and 4B (indicated by B) on the Pigeon River. 5 3. SAMPLING OBJECTIVES In accordance with the study plan (Wilson 2006), the goal of the fish collection effort was to collect one composite bottom feeder fillet sample at both sampling stations 4A and 4B. Each composite consisted of 3 to 5 similarly-sized (shortest specimen within 75% of the length of the longest) adult individuals of the target species. Common carp and channel catfish (Ictalurus punctatus) were the targeted species at sites 4A and 4B. In addition to fillet samples, one whole body common carp was collected from Station 4B. In summary fish were collected as follows: • Bottom feeder fillet composite—one sample at both locations • Catfish fillet composite—one sample at both locations • Common carp whole body composite—one sample from Station 4B Every reasonable effort was made to collect the desired size, species and/or number of fish; however,the outcome of the sampling effort each year is dependent on physical river conditions and the natural diversity and abundance of target fishes at each sampling location. The 2008 Pigeon River collections yielded the desired species at each location. In addition, the number of specimens collected made it possible to composite individuals of similar weight and length (with larger/adult specimens preferred), and the 75% rule was met for all samples. 6 4. FISH COLLECTION TECHNIQUES AND LEVEL OF EFFORT Sampling was conducted during 4-5 August 2008. Notes were recorded at each sampling station with regard to the type of sampling gear, level of effort(time), and habitat(Tables 2-1 and 4-1). All fish submitted for tissue analysis (including whole body specimen) were measured to the nearest millimeter (total length) and weighed to the nearest gram (wet weight). These data are summarized in Table 4-2. For 2008, the mean total length of carp was 663 mm and fish ranged from 630-686 mm. In 2007, the mean total length for carp was 721 mm and fish ranged from 672-775 mm. Previously, fish collections were conducted by EA Engineering, Science, and Technology (see References), and the mean for carp total length was 618 turn for fish submitted for analysis between 1993 and 2003. The field investigators were equipped with an array of collecting gear, which enabled sampling of all habitats regardless of river conditions. U.S. EPA recommends active methods of fish collection in the Sampling Guidance Manual (Versar 1984), such as electrofishing, trawling, angling, or seining. These are preferred over passive methods (e.g., gill nets, trap nets, trot lines) because samples are collected from more definable areas (Versar 1984). Gill nets were also necessary because of water depth. A boat electrofishing unit (pulsed direct current) was used at both stations. The boat electrofisher was equipped with a Smith Root Type VIA electrofisher, and powered by a 240-volt, 5000-watt generator. Electrofishing techniques followed those described in the National Dioxin Study(Versar 1984). Fish collection techniques and level of effort (time) expended at both stations are summarized in Table 4-1. Total study effort for collection of fish at Stations 4A/4B was 2.95 h electrofishing and 87.4 h gill netting. 7 Table 4-1. Fish collection techni ues and level of effort. Station Sampling Sampling Number RM Dates. Techniques Level of Effort Comments 4A 41.5 4-5 Aug 08 Gill nets 68.6 h An approximate 0.25 RM reach of river was sampled; sampling involved gill net sets just off shorelines and mid channel; the entire Boat 1.65 h area was electrofished. electrofishin 4B 39.0 5 Aug 08 Gill nets 18.8 h An approximate 1.0 RM reach was sampled; sampling involved gill nets and,electrofishing throughout the entire area. Nets were set off Boat 1.3 h the shoreline and included horizontal sets at near surface,midwater electrofishing and bottom. 8 Table 4-2. Summary of fish composites collected at two stations in Waterville Lake, August 2008. Total Total Length whole body Date Station Species (mm) (9) Sample type Composite 5 Aug 08 4A Channel catfish 500 1110 Fillet W (RM 41.5)Channel catfish 525 1330 Fillet R Channel catfish 475 900 Fillet R Channel catfish 502 1060 Fillet R Channel catfish 492 1010 Fillet R MEAN 499 1082 4A Common carp 684 4840 Fillet R (RM 41.5) Common carp 686 5060 Fillet R Common carp 653 4280 Fillet R MEAN 674 4727 5 Aug 08 4B Channel catfish 595 1730 Fillet R (RM 39.0)Channel catfish 480 860 Fillet R Channel catfish 505 1420 Fillet R Channel catfish 558 1780 Fillet R Channel catfish 459 880 Fillet R MEAN 519 1334 5 Aug 08 4B Common carp 665 4450 Fillet R (RM 39.0)Common carp 640 4200 Fillet R Common carp 630 3550 Fillet R MEAN 645 4067 5 Aug 08 4B Common carp 680 4620 Whole body WBb (RM 39.0) Ra right fillet composite WBb whole body composite 9 Target species were collected at both sampling stations in 2008. Common carp, the target bottom feeder at Stations 4A, and 4B, were collected (and prepared for fillet and/or whole body analysis) at those stations. Because of the physiography of the Waterville Lake Stations 4A and 4B, gill nets were used in addition to the electrofishing gear for the collection of bottom feeding species. All nets were pulled and examined on a regular basis to reduce stress or specimen mortality. All specimens submitted for analysis appeared healthy and in good condition. Lengths and weights for each fish making up each composite are provided in Table 4-2. Bottom feeder fillet composites samples consisted of five channel catfish and three common carp at Station 4A, and five channel catfish and three common carp at Station 4B. A single bottom feeder whole body common carp from Station 4B was submitted for analysis (Table 4-2). All 16 composites submitted for analysis in 2008 met the US EPA Region IV recommendation (Cunningham 1990) that the smallest specimen in each composite be equal to or greater than 75% of the total length of the largest specimen in that composite(Tables 4-2 and 6-4). Figure 4-1 illustrates the length and weight distribution of fish collected for tissue analysis from Waterville Lake since 2004. The size distribution of catfish remained similar between 2004 and 2008. The size of the carp taken for whole body tissue analysis from Station 4B in 2008 was similar to size of whole body fish collected in previous years. 10 Weight (g) Length (mm) rn jNW t 00 -4O0 4"C:6000O --1v0 000000000 OMO (}100000 000000000 000000000 0000000000 4A Cat o 4A Cat 4ACarp X N 4A Carp ?� No 4� 0 4B Cat • 0 46 Cat a p j' 4B Carp Whole 4A Cat =�ole 4A Cat N Q 4A Carp N 4A Car N N 0 4B Cat 0 4B Cat m m Carp y g 4 Whole g 4 Carp Who a p1 a 4A Cat 4A Carp o N 4A Carp :p N p N 9 O 4B Cat H tp' 0 4B Cat °' 4B Carp o 4B Carp CD Milk Whole A m4L Whole ■ CD;h. rt CD 4A Cat to sy 4A Cat r" 4ACarp o N 4A Carp ® m 0 co 4B Cat -, 0 4B Cat 4B Carp O J 4B Carp 0 y' Whole Whole i9 4A Cat '7'I 4A Cat -n w N 4A Carp y' N 4A Carp y 0 4B Cat 0 4B Cat IF, °D 4B Carp 00 4B Carp Whole ■ Whole ■ 5. SAMPLE PREPARATION All fish tissue samples were prepared in accordance with U.S. EPA Region IV recommendations (Cunningham 1990) as described in EA (2001a). To prevent cross-contamination between sampling stations, all sampling equipment likely to come into contact with the fish was rinsed extensively with site water between stations. Specimens collected at each station were sorted by size and species, and target species were identified. The objective was to obtain a 3- to 5-fish composite sample for channel catfish and common carp at both 4A and 4B sample locations, as well as a common carp whole body sample from either station in Waterville Lake which met the species and size objectives discussed in Section 3. From the target fishes collected, specimens of similar length and weight were selected for each composite sample. All specimens retained were immediately placed on ice for later processing. For each fish retained, length and weight data were recorded on the appropriate fisheries data sheet. Following identification of target organisms, selection of composite samples, and collection of length/weight data, each specimen was prepared for shipment and analysis. Bottom feeder fillet samples consisted of epaxial muscle tissue and skin from one side of the fish. Bottom feeder whole body samples consisted of the entire fish. Fillet samples were prepared by removing scales (or removing the skin from catfishes) and then making an incision behind the opercula (on both sides of the fish) from the base of the spine (behind the skull) to just below the pectoral fin. Care was taken to cut through the epaxial muscle without puncturing the rib cage or gut lining. A second incision was made along the length of the spine to the caudal fin on both sides of the fish. The epaxial muscle was then gently cut away from the rib cage to obtain a fillet. In this fashion, all flesh and skin was obtained from head to tail on both sides of the fish. Fillet knives were solvent rinsed (hexane and acetone) between fish from different stations. Each composite sample was wrapped in aluminum foil (dull side toward sample), labeled, and placed on ice in the field. Right side fillets were sent to TestAmerica West Sacramento (formerly Severn Trent Laboratories) for analysis; left side fillets were retained by Blue Ridge Paper Products Inc. as back-up fillets. The right side fillets and whole body sample sent to TestAmerica were frozen and shipped on dry ice. The left side back-up fillets were frozen and stored at the Canton Mill. All individual specimens (fillets) composing a single composite sample were placed in a water- tight plastic bag labeled with the station name, sample number, and species identification. A chain-of-custody form was filled out for each cooler of samples submitted for analysis. Each form included composite specific information and instructions. All chain-of-custody forms had the following information: • sample location and station identification, • sampling team initials, • date of collection, • species name, • sample type(i.e., fillet or whole body) A copy of the chain-of-custody record is provided in Appendix A. 12 All samples were frozen solid prior to shipment to the analytical laboratory. The frozen samples were packed on dry ice and shipped via overnight delivery, where they arrived on 8/14/08 at TestAmerica West Sacramento. The back-up fillets were retained in a freezer at the Canton Mill until laboratory analytical results for the right side fillets were received and verified. The backup fillets were then destroyed. 13 6. ANALYTICAL RESULTS The fish tissue samples were received in one shipment (8/14/08) at TestAmerica under chain-of- custody protocol. Once received at the laboratory, samples were compared to the chain-of- custody record to verify the content of each shipping container. Each individual fish or fillet within a composite was homogenized separately by TestAmerica personnel, and equal aliquots of the homogenate from each fish were removed to constitute the composite. Dioxin and furan analyses were performed using high resolution Gas Chromatography/Mass Spectrometry (GC/MS) as required by the U.S. EPA. Laboratory documentation of all chemical extractions and analyses are provided in Appendix B. All chemical analyses of the samples were conducted using EPA Method 8290 (U.S. EPA 1994) as specified in the Fish Tissue Sampling Study Plan (EA 2001 a). The quality of the analytical results was assured through reproducible calibration and testing of the extractions and GC/MS systems. A laboratory method blank was prepared along with each batch of samples. The laboratory also used precision and recovery standards for determination of initial and ongoing precision and accuracy. Laboratory reports for all 2008 Pigeon River fish tissue dioxin, furan, and lipid content analyses are provided in Appendix B. Each laboratory analysis report form lists the concentration of 2,3,7,8-tetrachlorodibenzo-p-dioxin (TCDD), 2,3,7,8,-tetrachlorodibenzofuran (TCDF), and all other CDD/CDF isomers. Results of the dioxin, furan, and lipid content analyses are summarized in Table 6-1. Detection limits are reported parenthetically on a sample-specific basis. Only fillet results are discussed below because North Carolina Department of Health and Human Services (NC DHHS) considers only fillet results when issuing health advisories. Concentrations of 2,3,7,8-TCDD and 2,3,7,8-TCDF were below the level of detection in channel catfish fillet composites at both Station 4A and Station 4B (Table 6-1). In common carp, 2,3,7,8- TCDD was detected (1.2 ppt) in fillet composites collected at Station 4A, but was not detected at Station 4B (detection limit 0.36 ppt). In the common carp whole body composite collected at Station 4B, the concentration of 2,3,7,8-TCDD was estimated at 0.78 ppt. The concentration of 2,3,7,8-TCDF was 2.2 ppt in common carp fillets at Station 4A, 0.84 ppt was estimated at Station 4B, and 2.7 ppt was the concentration in the common carp whole body sample collected at Station 4B (Table 6-1). Examination of the data in Table 6-1 indicates that all fish collected during this study had body burdens well below the FDA dioxin health advisory level (25 ppt) for fish tissue [as established and presented in FDA (1981, 1983) and Cordle(1983)]. The NC DHHS recommends an average dioxin toxicity equivalent(TEQ) level of 3 ppt or less in fish tissue fillets. The NC DHHS issues dioxin fish tissue advisories at an average toxicity equivalent of 4 ppt or greater (e-mail correspondence with Dr. Luanne Williams 18 January 2005). The TEQ of each chlorodibenzodioxin and furan(CDD/F) isomer is based on the toxicity equivalence factor(TEF) (WHO 2005 and Table 6-2) as described in the 2001 Study Plan (EA 2001b). The TEQ value is calculated assuming additivity of effects for the individual congeners of dioxin and furans and is expressed as an"equivalent amount of 2,3,7,8-TCDD" (NC DEHNR 1991). The measured concentration of each CDD/F isomer, when multiplied by its appropriate TEF, yields the TEQ of that isomer(the toxic concentration of that isomer relative to the toxicity of 2,3,7,8-TCDD). In cases where concentrations were below the level of detection, a value of 14 zero was used in the TEQ calculation. Based on an advisory by the World Health Organization (e-mail correspondence with Dr. Luanne Williams 20 September 2006), new TER were developed in 2005 by the WHO and are now being used instead of the 1997 TEFs. 15 Table 6-1. Summary of the Pigeon River fish tissue analysis results 2008. Percent Station Number Sample ID Composite/Sample Tyne 2,3,7,8-TCDD''l 2,3.7,8-TCDF(°' Lipid 4A SITE 4A channel catfish 5 fillet samples ND (DL=0.29) ND (DL=0.12) 3.7 SITE 4A common carp 3 fillet samples 1.2 2.2(b) 14 4B SITE 4B channel catfish 5 fillet samples ND (DL=0.34) ND (DL=Oct 2) 3.9 SITE 4B common carp 3 fillet samples ND (DL=0.36) 0.84 ' 4.5 SITE 4B common carp 1 whole body sample 0.78(`) 2.7(b) 13 (a)Units=ppt(parts per trillion) or pg/g(picogram/gram) (b) Analyte was positively identified,but the quantitation is an estimate. (c)Estimated results. Result is less than the reporting limit (ND)Not detected,concentrations below the instrument detection limit. 16 Table 6-2. Toxicity equivalence factors for CDD/F isomers. DIOXIN DIBENZOFURAN Isomer(') TEF1b) TEF(b) 2,3,7,8-TCDD 1 2,3,7,8-TCDF 0.1 1,2,3,7,8-PeCDD 1 1,2,3,7,8-PeCDF 0.03 2,3,4,7,8-PeCDF 0.3 1,2,3,4,7,8-HxCDD 0.1 1,2,3,4,7,8-HpCDF 0.1 1,2,3,7,8,9-HxCDD 0.1 1,2,3,7,8,9-HxCDF 0.1 1,2,3,6,7,8-HxCDD 0.1 1,2,3,6,7,8-HxCDF 0.1 2,3,4,6,7,8-HxCDF 0.1 1,2,3,4,6,7,8-HpCDD 0.01 1,2,3,4,6,7,8-HpCDF 0.01 1,2,3,4,7,8,9-HpCDF 0.01 OCDD 0.0003 OCDF 0.0003 (a) In each homologous group, the relative toxicity factor for the isomers not listed is 1/100 of the value listed for the other isomers in that homologous group. (b)TEF=toxic equivalence factor=relative toxicity assigned. 17 The TEQ calculation and summarization schemes presented in Table 6-3 followed methods used by NC DHHS (NC DEHNR 1991). All fish tissues analyzed had TEQ values below the NC DHHS advisory limit(3 ppt) and ranged from 0.002 for channel catfish fillets collected at Station 4B to 1.822 for common carp collected from Station 4B. The values reported in years 2005- 2007 for channel catfish are consistent with the results for 2008. Common carp TEQ results in 2007 were higher (Station 4A, 13.44; Station 4B, 5.35) than observed in previous years (2005- 2006), and the present results for 2008 (Station 4A, 1.822; Station 4B, 0.171) are further evidence that the 2007 results were anomalous. The whole body sample for common carp collected at Station 4B had a TEQ result of 1.547. Table 6-4 illustrates 2,3,7,8 TCDD concentrations in common carp fillet samples collected in 2005, 2006, 2007, 2009 and results for previous years (1990-2004) are in Appendix C. Between 1990 and 2006, 2,3,7,8-TCDD concentrations in carp fillets declined dramatically (94-99 %) at all sampling stations (Table 6-4, Appendix C,Figure 6-1). The mean weights of common carp collected from Stations 4A and 4B (4.727 kg, Station 4A; 4.067 kg, Station B) were lower than those collected in 2007 (6.490 kg - Station 4A; 6.552 kg -, Station 4B), but consistent with weights of common carp collected in previous years (2006, 4.505 kg- Station 4A, 5.637 kg - Station 4B; 2005, 3.667 kg- Station 4A, 4.695 kg - Station 4B; 2004, 3.771 kg- Station 4A, 3.900 kg - Station 4B; 1999-2003, 3.193 kg - Station 4A, 5.042 kg- Station 4B). Lipid concentrations in common carp fillets in 2008 were 4.5-14% and were lower than observed in 2007 (12-29%). 18 Table 6-3. Summary of CDD/F isomer analyses, toxicity equivalent factors, and toxicity equivalent values for the 2008 Waterville Lake fish. STATION 4A Channel catfish fillet Common carp fillet CDD/F isomers TEFt`' Results(-) TE01h, Results(') TFQIO Dibenzodioxin 2,3,7,8-TCDD 1.0 ND 0.000 1.2 1.2 1,2,3,7,8-PeCDD 1.0 ND 0.000 ND 0.000 1,2,3,4,7,8-HxCDD 0.1 ND 0.000 ND 0.000 1,2,3,6,7,8-HxCDD 0.1 ND 0.000 2.9(d) 0.29 1,2,3,7,8,9-HxCDD 0.1 ND 0.000 ND 0.000 1,2,3,4,6,7,8-HpCDD 0.01 96 0.96 10 0.10 OCDD 0.0003 510 0.153 39 0.012 Dibenzofuran 2,3,7,8-TCDF 0.1 ND 0.000 2.2 0.22 1,2,3,7,8-PeCDF 0.03 ND 0.000 ND 0.000 2,3,4,7,8-PeCDF 0.3 ND 0.000 ND 0.000 1,2,3,4,7,8-HxCDF 0.1 ND 0.000 ND 0.000 1,2,3,6,7,8-HxCDF 0.1 ND 0.000 ND 0.000 2,3,4,6,7,8-HxCDF 0.1 ND 0.000 ND 0.000 1,2,3,7,8,9-HxCDF 0.1 ND 0.000 ND 0.000 1,2,3,4,6,7,8-HpCDF 0.01 ND 0.000 ND 0.000 1,2,3,4,7,8,9-HpCDF 0.01 ND 0.000 ND 0.000 OCDF 0.0003 ND 0.000 ND 0.000 Total TEQ 1.113 1.822 19 Table 6-3 (cont). Summary of CDD/F isomer analyses,toxicity equivalent factors, and toxicity equivalent values for the 2008 Waterville Lake fish. STATION 4B Channel catfish fillet Common carp fillet Common Caro whole body CDD/F isomers TEF(C' Results(a) TEQT Results(') TEO"' Results(') TEQ!2 Dibenzodioxin 2,3,7,8-TCDD 1.0 ND 0.000 ND 0.000 0.78(d) 0.78 1,2,3,7,8-PeCDD 1.0 ND 0.000 ND 0.000 ND 0.000 1,2,3,4,7,8-HxCDD 0.1 ND 0.000 ND 0.000 ND 0.000 1,2,3,6,7,8-HxCDD 0.1 ND 0.000 ND 0.000 3.8(d) 0.38 1,2,3,7,8,9-HxCDD 0.1 ND 0.000 ND 0.000 ND 0.000 1,2,3,4,6,7,8-HpCDD 0.01 ND 0.000 7.8 0.078 11 0.11 OCDD 0.0003 5.1(d) 0.002 31 0.009 24 0.007 Dibenzofuran 2,3,7,8-TCDF 0.1 ND 0.000 0.84(d) 0.084 2.7(d) 0.27 1,2,3,7,8-PeCDF 0.03 ND 0.000 ND 0.000 ND 0.000 2,3,4,7,8-PeCDF 0.3 ND 0.000 ND 0.000 ND 0.000 1,22,3,4,7,8-HxCDF 0.1 ND 0.000 ND 0.000 ND 0.000 1;2,3,6,7,8-HxCDF 0.1 ND 0.000 ND 0.000 ND 0.000 2,3,4,6,7,8-HxCDF 0.1 ND 0.000 ND 0.000 ND 0.000 1,2,3,7,8,9-HxCDF 0.1 ND 0.000 ND 0,000 ND 0.000 1,2,3,4,6,7,8-HpCDF 0.01 ND 0.000 ND 0.000 ND 0.000 1,2,3,4,7,8,9-HpCDF 0.01 ND 0.000 ND 0.000 ND 0.000 OCDF 0.0003 ND 0.000 ND 0.000 ND 0.000 Total TEQ 0.002 0.171 1.547 (a)Units=ppt(parts per trillion) or pg/g(picogram per gram) (b)Dioxin Equivalent Concentration using methodology from U.S.EPA(1989) (c)Toxicity Equivalent Factors from World Health Organization(WHO 2005) (d)Estimated result. Result is less than reporting limit. 20 Table 6-4. Blue Ridge Paper Canton Mill fish fillet tissue analysis results, 2005 —2008 2005 Results(d) 2006 Results(e) Number Length Range Number Length Range Station Species of fish (mm) 2,3,7,8-TCDD Station Species of fish (mm) 2,3,7,8-TCDDt'b� 1 Black redhorse 5 359-384 ND(0.35) 4A Common carp 3 635-692 0.64(c) RM 64.5 RM 41.5 Channel catfish 5 430-500 ND(0.37) 2 Common carp 4 595-650 ND(0.45) 4B Common carp 3 650-745 0.73 (c) RM 59.0 Channel catfish 3 443-460 ND(0.29) RM 39.0 Channel catfish 4 510-590 0.77(c) 3 Common carp 4 605-630 ND(0.46) RM 52.3 4A Common carp 3 601-665 1.3 RM 41.5 Channel catfish 5 464-508 ND(0.36) 4B Common carp 4 595-736 2.8 RM 39.0 Channel catfish 5 513-603 0.76t`' 5 Black redhorse 4 440-501 ND(0.41) RM 19.0 Total fish filleted= 33 Total fish filleted= 15 (a)Dioxin analyses conducted by TestAmerica(formerly Severn Trent Laboratories). (b)Units=ppt(parts per trillion)or pgtg(picogram/gram) (c)Estimated result. Result is less than the reporting limit. (d)Survey conducted in August and September (e)Survey conducted in August ND=Non-detectable at the detection limit in parentheses 21 r Table 6-4 (cont). Blue Ridge Paper Canton Mill fish fillet tissue analysis results, 2005 —2008 2007 Results(d) 2008 Results(e) Number Length Range Number Length Range Station Species of fish (mm) 2,3,7,8-TCDD(�b) Station Species offish (mm) 2,3,7,8-TCDD(&b' 4A Common carp 4 680-775 6.4 4A Common carp 3 653-684 1.2 RM 41.5 Charnel catfish 4 490-593 0.57(`) RM 41.5 Channel catfish 5 475-525 ND(0.29) 413 Common carp 5 672-728 ND(6.9) 413 Common carp 3 630-665 ND(0.36) RM 39.0 Channel catfish 5 505-670 0.67t`) RM 39.0 Channel catfish 5 459-595 ND(0.34) Total fish filleted= 18 Total fish filleted= 16 (a)Dioxin analyses conducted by TestAmerica(formerly Severn Trent Laboratories). (b)Units=ppt(parts per trillion)or pg/g(picogram/gram) (c)Estimated result. Result is less than the reporting limit. (d)Survey conducted in August and September (e)Survey conducted in August ND=Non-detectable at the detection limit in parentheses 22 Figure 6-1. TCDD Concentrations in Carp Fillets Collected from the Pigeon River, 1990- 2008 (Stations 4A and 46). 70 60 \ 50 Station 4A i \ G \\ Station 46 40 c \ 30 R C. \ p 20 \ H \ \ 10 y b �►--y-- b 4 1990 1991 1992 1993 1994 1995 1996 1997 1998 1999 2000 2001 2002 2003 2004 2006 2006 2007 2008 YEAR b) TCDD concentrations at Station 4B were not detected, therefore, the values plotted represent the detection limit for those samples. The detection limit for 2,3,7,8-TCDD was elevated in the 2007 carp fillet for Station 4B because of a 10-fold dilution of the sample which was required to overcome sample matrix effects (high lipid concentration) during analysis. Consequently, reporting the detection limit for this sample can give a misleading impression that the concentration of 2,3,7,8-TCDD increased that year. 23 Figure 6-2. TCDD Concentrations in Catfish Fillets Collected from the Pigeon River, 1997-2008 (Stations 4A and 4B). 2.50 2.00 —� —Station 4A —f- Station 4B °e 1.50 d 1.00 � b b a � �a / \ ■ - -■ ■ A f p ■ ' b F0.50 a ----f, a a a _r. a b a 0.00 1997 1998 1999 2000 2001 2002 2003 2004 2005 2006 2007 2008 YEAR a)TCDD concentrations were not detected at Station 4A, therefore the values plotted represent the detection limit for the sample. b)TCDD concentrations were not detected at Station 4B, therefore, the values plotted represent the detection limit for the sample. 24 7. REFERENCES Cordle, F. 1983. Use of epidemiology in the regulation of dioxins in the food supply, in Accidental Exposure to Dioxins: Human Health Aspects (F. Coulston and F. Pocchiara, eds.), pp 245-256. Academic Press,New York. Cunningham, W.R. 1990. Letter to Paul Wiegand. 30 January. EA Engineering, Science, and Technology Inc. 1990. Study Plan for the Monitoring of Dioxin in Fish Tissue. EA Report No. 11370.01, prepared for Champion International Corporation, Canton, North Carolina. EA Engineering, Science, and Technology Inc. 1991. Results of the 1990 Dioxin Monitoring in Fish Tissue. EA Report No. 11370.02, prepared for Champion International Corporation, Canton, North Carolina. EA Engineering, Science, and Technology Inc. 1992. Results of the 1991 Dioxin Monitoring in Fish Tissue. EA Report No. 11370.03, prepared for Champion International Corporation, Canton, North Carolina. EA Engineering, Science, and Technology Inc. 1993a. Results of the 1992 Dioxin Monitoring in Fish Tissue. EA Report No. 11370.05, prepared for Champion International Corporation, Canton, North Carolina. April. EA Engineering, Science, and Technology Inc. 1993b. Results of the 1993 Dioxin Monitoring in Fish Tissue. EA Report No. 11370.06, prepared for Champion International Corporation, Canton, North Carolina. December. EA Engineering, Science, and Technology Inc. 1994. Results of the 1994 Dioxin Monitoring in Fish Tissue. EA Report No. 11370.07, prepared for Champion International Corporation, Canton, North Carolina. December. EA Engineering, Science, and Technology Inc. 1995. Results of the 1995 Dioxin Monitoring in Fish Tissue. EA Report No. 13043.01, prepared for Champion International Corporation, Canton, North Carolina. December. EA Engineering, Science, and Technology Inc. 1996. Results of the 1996 Dioxin Monitoring in Fish Tissue. EA Report No. 13176.01, prepared for Champion International Corporation, Canton, North Carolina. December. EA Engineering, Science, and Technology Inc. 1997. Results of the 1997 Dioxin Monitoring in Fish Tissue. EA Report No. 13353.01, prepared for Champion International Corporation, Canton, North Carolina. November. 25 EA Engineering, Science, and Technology Inc. 1998. Results of the 1998 Dioxin Monitoring in Fish Tissue. EA Report No. 13478.01, prepared for Champion International Corporation, Canton,North Carolina. December. EA Engineering, Science, and Technology Inc. 2000. Results of the 1999 Dioxin Monitoring in Fish Tissue. EA Report No. 13478.01, prepared for Champion International Corporation, Canton, North Carolina. January. EA Engineering, Science, and Technology Inc. 2001a. Study Plan for Pigeon River Dioxin Monitoring in Fish tissue. Prepared for Blue Ridge Paper Products Inc., Canton, North Carolina. November. EA Engineering, Science, and Technology Inc. 2001b. Results of the 2000 Dioxin Monitoring in Fish Tissue. EA Report No. 13745.01, prepared for Blue Ridge Paper Products Inc., Canton, North Carolina. December. EA Engineering, Science, and Technology Inc. 2001c. Results of the 2001 Dioxin Monitoring in Fish Tissue. EA Report No. 13900.01, prepared for Blue Ridge Paper Products Inc., Canton, North Carolina. December. EA Engineering, Science, and Technology Inc. 2003. Results of the 2002 Dioxin Monitoring in Fish Tissue. EA Report No. 13900.02, prepared for Blue Ridge Paper Products Inc., Canton, North Carolina. December. EA Engineering, Science, and Technology Inc. 2004. Results of the 2003 Dioxin Monitoring in Fish Tissue. EA Report No. 13900.03, prepared for Blue Ridge Paper Products Inc., Canton, North Carolina. January. Food and Drug Administration. 1981. FDA advises Great Lakes States to monitor dioxin- contaminated fish. FDA Talk Paper dated 28 August, in Food Drug Cosmetic Law Reports, paragraph 41, 321. Commerce Clearing House, Inc. 8 September. Food and Drug Administration. 1983. Statement by Stanford A. Miller, Director, Bureau of Foods, FDA before the Subcommittee on Natural Resources, Agriculture Research and Environment,U.S. House of Representatives. 30 June. Henry,T.B., and J.L. Wilson. 2006. Results of 2005 dioxin monitoring in fish tissue. Prepared for Blue Ridge Paper Products, Inc., Canton Mill, Canton, North Carolina. February 2006. Henry, T.B., and J.L. Wilson. 2007. Results of 2006 dioxin monitoring in fish tissue. Prepared for Blue Ridge Paper Products, Inc., Canton Mill, Canton, North Carolina. January 2007. Henry, T.B., and J. L. Wilson. 2008. Results of 2007 dioxin monitoring in fish tissue. Prepared for Blue Ridge Paper Products, Inc., Canton Mill, Canton, North Carolina. April 2008. 26 North Carolina Department of Environment, Health, and Natural Resources. 1991. Fish Tissue Dioxin levels in North Carolina: 1990 update. Division of Environmental Management, Water Quality Section. U.S. Environmental Protection Agency (U.S. EPA). 1994. Analytical procedures and Quality Assurance for Multimedia Analysis of Polychlorinated Dibenzo-para-dioxins and Polychlorinated Dibenzofurans by High-Resolution Gas Chromatography/High-Resolution Mass Spectrometry(Method 8290). U.S. Environmental Protection Agency (U.S. EPA). 1989. Interim Procedures for Estimating Risk Associated with Exposures to Mixtures of Chlorinated Dibenzo-p-dioxins and Dibenzofurans (CDDs and CDFs) and 1989 Update Report No. EPA/625/3-89/016, U.S. EPA, Risk Assessment Forum,Washington, D.C. Versar, Inc. 1984. Sampling Guidance Manual for the National Dioxin Study. U.S. Environmental Protection Agency. EPA Contract 68-01-6160. Work Order Number 8.7. Office of Water Regulations and Standards, Monitoring and Data Support Division, Washington, D.C. Final Draft. July. Wilson, J.L. 2006. Study plan revision: Dioxin monitoring in fish tissue, Waterville Lake. Prepared for Blue Ridge Paper Products, Inc. Canton Mill, Canton, North Carolina. March 2006. World Health Organization (WHO). 1997. Exposure and Human Health Reassessment of 2,3,7,8-Tetrachlorodibenzo-p-dioxin (TCDD) and Related Compounds: Part II: Health Assessment of 2,3,7,8-Tetrachlorodibenzo-p-dioxin(TCDD) and Related Compounds. 27 @I muman Mom How T1 20011 E+ "APPENDICES" Blue Ridge Paper Products Inc dba Evergreen Packaging Canton, NC APPENDIX A: CHAIN OF CUSTODY FORM APPENDIX B: TESTAMERICA WEST SACRAMENTO ANALYTICAL REPORT APPENDIX C: BLUE RIDGE PAPER CANTON MILL FISH FILLET TISSUE ANALYSIS RESULTS 1990-2004 APPENDIX D: 2006 REVISIONS TO DIOXIN MONITORING PLAN 28 APPENDIX A CHAIN OF CUSTODY FORM 29 a Chain of Temperature on Receipt Custody Record Drinking Water? Yes❑ No❑ THE LEADER IN ENVIRONMENTAL TESTING Ta-4124(1007) Orient Pm/ed Manager Date Chalnof Custody Number L r `lsonf 073914 A dress Telephaanee Number gma CodejTax�N/Wnber Lab Numbsr e r (N - l� - �! Page of e Ciry Sttse ➢p Cade Site Contact Lob Contact Analysis(Attach list it more space is needed) c Project Name and Location(Srete) CaakdWaybill Number 1r� i L — '�'S �C"1 p £ _ Special)nstructfons/ ConlracWumhase OrdeNoacre Iva. 1 Containers& S 0 Conditions of Receipt Matrix Preservatives Sample I.D.No.and Description Date Time $ o o ax c (Containers foreach sampte maybe combined on one line) , F 3 t &6 - •' s -6-0 1010 _ X x x �eM DS;to cs i�rz�s " " - 55— -rig l L K 1C X 1� m oSr�P 3 11F{s W 'L SZ-S-PAX 600 K k X a it o D - .i 55-5--08 Ix XX X a�1�e 3 t12. fD O lk Me s: iN6 O ?C 1C w ' 0 Possible Hazard IdenbBcadon Semple Disposal (A fee may be assessed if samplas are retained X(lon-Hazard ❑ Flammahte ❑Skin bdtanl ❑Potean B ❑ Unknovm ❑Retam To C6'oal ❑ Olsposel By Lab ❑Archhre For —Months longerthan 1 month) { TumAreund Rate Required OC Requirements(specIty) ❑24 Hours ❑4qioum ❑ 7Days ❑ 14 Days ❑21 Days ❑ Other 1.Relinqu he Dato Time L Race Ne y Date ! Time 08 a 0 96 8./�. 2.Relinqu a e DBISP Tune 2.Rnivad DalA Time oi Dl 9.Relinqu' a i ;—POf- Data Tame a Recervetl ay D e Time 9/13 08 Piq H � /r GIj KH N d� ''7GK a 4A4rLl •r fJ o wl j ck PZ0 YY• DISTRIBUTION.- W E-Relumedlo Clientivlfh Repoa: CANARY-Slays with the Semple:PINK-Field bpy APPENDIX B TESTAMERICA WEST SACRAMENTO ANALYTICAL REPORT 30 estAmerica THE LEADER IN ENVIRONMENTAL TESTING i -- - August 28, 2008 TestAmerica Project Number: G8H140369 PO/Contract: 7605001 Blue Ridge Paper Products Inc 175 Main Street P.O. Box 4000 Canton, NC 28716 Dear Mr. Pryately, This report contains the analytical results for the samples received under chain of custody by TestAmerica on August 14, 2008. These samples are associated with your Waterville Lake— Fish Tissue project. The test results in this report meet all NELAC requirements for parameters that accreditation is required or available. Any exceptions to NELAC requirements are noted in the case narrative. The case narrative is an integral part of this report. If you have any questions, please feel free to call me at(916) 374-4402. Sincerely, / J� kk�iYMl1r>U Jill Kellmann Project Manager 880 Riverside Parkway West Sacramento,CA 95605 tel 916.373.5600 fax 916.372.1059 www.testamericainc.com G8H146369 TestAmerica West Sacramento(916)373-5600 1 of 541 Table of Contents TestAmerreca West Sacramento Project Number G8H140369 Case Narrative Quality Assurance Program Sample Description Information Chain of Custody Documentation BIOLOGIC, 8290, Percent Lipids Samples: 1, 2, 3, 4, 5 Sample Data Sheets BIOLOGIC, 8290, Dioxins/Furans Samples: 1, 2, 3, 4, 5 Sample Data Sheets Method Blank Reports Laboratory QC Reports GSH140369 TestAmenca West Sacramento(916)373-5600 2 of 541 Case Narrative TestAmerica West Sacramento Project Number GBH140369 BIOLOGIC, 8290, Dioxins/Furans Sample(s): 2, 4, 5 The samples required a confirmation analysis for 2,3,7,8-TCDF on August 26, 2008. There were no other anomalies associated with this project. GBH140369 TestAmerica West Sacramento(916)373-6600 3of 541 1N ACCOH .r TestAmerica THE LEADER IN ENVIRONMENTAL TESTING < a TestAmerica Laboratories West Sacramento Certifications/Accreditations Alaska UST-055 New York* 11666 ©i oe n ;:i� . Arkansas 04-067-0 Penns Ivania 68-1272 �011J;9 9122. , ':' . ' ",`��SnuffiPC arohna'G ,+;i`., F8a0,1`40.02$.aspit;"- Colorado NA Texas TX 270 2004A 7�' � Florida* E87570 Virginia 00178 1 , Hawaii NA West Vir imia 9930C 334 ev,� a#✓rlaa-3`3�'�v'x::vit.'ae u2,u,;5.��`a3-.>F,.4�z-�EX1-..+,., J. . �d� < 1� Fs�.rma204679 rtu �a Louisiana* 01944 NFESC NA Nevada CA44 USDA Foreign Plant 37 82605 IR =a Nevrlers *x a C1I005 1t1 USDiC�E6ret .Sol: . S NA *NELAP accredited. A more detailed parameter list is available upon request.Updated 9121107 QC Parameter Definitions QC Batch:The QC batch consists of a set of up to 20 field samples that behave similarly(i.e.,same matrix) and are processed using the same procedures,reagents,and standards at the same time. Method Blank: An analytical control consisting of all reagents,which may include internal standards and surrogates,and is carried through the entire analytical procedure. The method blank is used to define the level of laboratory background contamination. Laboratory Control Sample and Laboratory Control Sample Duplicate(LCS/LCSD): An aliquot of blank matrix spiked with known amounts of representative target analytes. The LCS(and LCSD as required)is carried through the entire analytical process and is used to monitor the accuracy of the analytical process independent of potential matrix effects. If an LCSD is performed,it may also be used to evaluate the precision of the process. Duplicate Sample(Di):Different aliquots of the same sample are analyzed to evaluate the precision of an analysis. Surrogates: Organic compounds not expected to be detected in field samples,which behave similarly to target analytes. These are added to every sample within a batch at a known concentration to determine the efficiency of the sample preparation and analytical process. Matrix Spike and Matrix Spike Duplicate(MS/MSD): An MS is an aliquot of a matrix fortified with known quantities of specific compounds and subjected to an entire analytical procedure in order to indicate the appropriateness of the method for a particular matrix. The percent recovery for the respective compound(s)is then calculated. The MSD is a second aliquot of the same matrix as the matrix spike,also spiked,in order to determine the precision of the method. Isotope Dilution: For isotope dilution methods,isotopically labeled analogs(internal standards)of the native target analytes are spiked into the sample at time of extraction. These internal standards are used for quantitation,and monitor and correct for matrix effects. Since matrix effects on method performance can be judged by the recovery of these analogs,there is little added benefit of performing MS/MSD for these methods. MS/MSD are only performed for client or QAPP requirements. Control Limits: The reported control limits are either based on laboratory historical data,method requirements,or project data quality objectives. The control limits represent the estimated uncertainly of the test results. GSH140369 TestAmerica West Sacramento(916)373-5600 4 of 541 cQclusea a TestAme�ca Nonconformance Memo THE LEADER IN EIVIRONUENTAL TESTING NCM#: 07-0082424 NCM Initiated By: virginia grandfleld Classification: Observation Date Opened: 08/27/2008 Status: CLOSED Date Closed: 08/27/2008 Production Area: Dioxin Data Review Tests: 8290 Lot 1i'a(Sample#'s): G81-1140369(2,4,5), QC Batches: 8235310, Nonconformance: Dioxin observation Subcategory: DB-225 and Confirmation Name Date Description virginia grandfleid 08/27%2008 The following samples required Confirmation(CON)and/or Dilution(D). Lot# GSH140369 Sample In)Timeln)Date Filename Reason 2 17:52 8/26/2008 25AU088D2 CON 4 18:29 8/26/2008 25AU088D2 CON 5 19:05 8/26/2008 25AU08SD2 CON • o Name Date Corrective Action Virginia grandfield 08/27%2008 Client Notification Qqmmary Client Protect Manager Notified Response How Notified Note Response Response Note • . . Verified By Due Date Status Notes This section not yet completed by OA. Approva Date Approved Approved By Position Date Printed: 8/27/2008 Page 1 of 1 68H140369 TestAmeriea West Sacramento(916)373-5600 5 of 541 Samp9e Summary TestA merica West Sacramento Project Number GSH140369 WO# Sample# Client Sample ID Samplina Date Received Date KT631 1 SITE 4A CHANNEL CAT R-FILLET(5) 8/51200310:10 AM 811412008 09:15 AM KT632 2 SITE 4A COMMON CARP R-FILLET(3)8/51200812:30 PM 8/14/2008 09:15 AM KT633 3 SITE 49 CHANNEL CAT R-FILLET(5) 8/512008 04:00 PM 811412008 09:15 AM KT634 4 SITE 49 COMMON CARP R-FILLET(3)8/512008 04:40 PM 811412008 09:15 AM K1`635 5 SITE 48 COMMON CARP WS 8/512003 05:50 PM 8114/2008 09:15 AM Notes(s): • The analytical results of the samples listed above are presented on the follovring pages. All calculations are performed before rounding to avoid round-off errors in calculated results. Results noted as'ND'were not detected at or above the stated limit This report must not be reproduced,except in full,without the written approval of the laboratory. Results for the following parameters are never reported on a dry weight basis:color,corrosivity,density,fiashpolnl, ignitability,layers,odor,paint filler test,pH,porosity,pressure,reactivity,redox potential,specific gravity,spot tests, solids,solubility,temperature,vismsfty,and weight. GBH140369 TestAmerlca West Sacramento(916)373-5600 6 of 541 g Chain of Temperature on Receipt an Custody Record Drinking WateR Yes[] No❑ THE LEADER IN ENVIRONMENTAL TESTING Tru�mza(1cm) Ckent Pmiect Manager Date Chatnol Custody Number L r 7 9 A dress Telephone Number rea Code if N bar tab Number r 'A— y$- t n kI m I I Pago--L— of Clry Fstate Zfp Coda Site Contact I Lab Contact Analysis(AUach list if mom space is needed) Project Name and Lccat/on(state) /V CarrivaWaybill Number i L — "S 1 '1 5 0 a Special Instructions/ ContrectIPurchese omerrctuote No. Lu Containers& 0 Conditions of Receipt Matrix a' Preservatives 'J Sample I.D.No.and Description Dare (Contalmus foreachsample mayboeombinedon onoline) 34A Q6,14MO 8dk - •' s -6-68 1 X I I I YX' CeM �siFe �5f�'l!{ r! ,t - , - -0g 12 r, St 5S^5-U`d 600 X I I X Xi a5 iLPls) A4ta XIt 0 S: W a -U 0 K i w V w m � o 0 i Passible Hazard identification Sample Disposal (A fes may be assessed if samples are retained 'KNon-Hazard ❑ Flammable ❑Skin trdmnt ❑ Poison B ❑ Unknown ❑ Retum To Cllant ❑ Oispcsal ey Lab ❑Amh1vo For Months fangarfh m I month) Tam Around Time Required UU Requirements fSpe*f ) ❑24 Hours ❑4a ours ❑ 7 Days ❑ 14 Days ❑21 Days ❑ Omer 1.Relinqu )a Date Time 1.Rocofve y Dete / Trme 0$ o f7 J 0 0 B.- . ARalinquis Oa! Tune 2.R lve y Datb Tinto a Da Trme 3.Received By Da a Time V13 o f p ro `t Gomrgents N Nip / W l�P <� a Lm" o� I3 o rfAli j lac a + DISTRIBUTION: W TE-Retumed to Clientwlth Report; ANARY-Stays with me Sample; PINK-Fien 'py LIST Tes u me ca LOT RECEIPT men TestAmerica Westt Sacramento THE LEADER IN ENVIRONMENTAL TESTING CLIENT 0 \ rPM T!►�L/ LOG# Z LOT#(QUANTIMS ID) C7 Io QUOTE#� / R� 1 LOCATION Initials Date DATE RECEIVED TIME RECEIVED. DELIVERED BY Z'�FEDEX ❑CA OVERNIGHT ❑ CLIENT ❑AIRBORNE ❑'GOLDENSTATE ❑ DIAL ❑ UPS ❑BAX GLOBAL ❑GO-GETTERS ❑TAL COURIER ❑VALLEY LOGISTICS ❑MORGAN HILL COURIER ❑OTHER CUSTODY SEAL STATUS�TACT ❑BROKEN ❑ NIA CUSTODY SEAL#(S) Za `� SHIPPPING CONTAINERS) ❑TAL CLIENT ❑6A TEMPERTURE RECORD(IN"C) IR 4❑ 5❑ ❑ OTHER COC#(S) :7 :5 q ly TEMPERATURE BLANK Observed: Corrected: SAMPLE TEMPERATURE_-t-r— m �{2 yD Observed: Average: Corrected Average:-:�X% COLLECTOR'S NAME: ❑Verified from COC KNol on COC pH MEASURED ❑YES ❑ANOMALY PINIA , LABELEDBY.......................................................................................... LABELSCHECKED BY......................................... .. ............................. PEER REVIEW NA SHORT HOLD TEST NOTIFICATION SAMPLE RECEIVING WETCHEM 6N/A VOA-ENCORESZ-NIA ❑METALS NOTIFIED OF FILTERIPRESERVE VIA VERBAL&EMAIL NIA ,reCOMPLETE SHIPMENT RECEIVED IN GOOD CONDITION WITH ❑NIA APPROPRIATE TEMPERATURES,CONTAINERS, PRESERVATIVES ❑CLOUSEAU ❑ TEMPERATURE EXCEEDED(2°C-6°C)r 1/A �P�❑WET ICE ❑ BLUE CE ❑GEL PACK ❑ NO COOLING AGENTS USED ❑ PM NOTIFIED Notes: '1 Acceptable temperature range for State of Wisconsin samples Is<4°C. LEAVE NO SPACES BLANK. USE"NIX IF NOT APPLICABLE. QA-185 5105 EM. Page 1 GBH140359 TestAmerica West Sacramento(916)373-5600 8 of 641 TestAmerica West Sacramento Bottle Lot Inventory Test emedca Lot THE LEADER IN EWVIFCINAICNTAL TESTING ID' 1 1 2 1 3 1 4 5 6 1 7 1 8 9 10 1 11 12 13 14 15 1 16 17 18 19 120 VOA' VOAh` AGB AGBs 250AGB 250AGBs ri I I 250AGBn 500AGB _AGJ 500AGJ 250AGJ 125AGJ _CGJ 500CGJ 250CGJ 125CGJ Pi PJn 500PJ 500PJn 500PJna 500PJznlna 250PJ 250PJn 250PJna 250PJznlna Acelate Tube _"CT Encore Folder/filter PUF Petri/Filter XAD Trap Ziploc 1 2 1 3 1 4 1 5 6 7 8 9 10 11 121 131 14 15 M18 h=hydrochloric acid s=sulfuric acid na=sodium hydroxide n =nitric acid zn=zinc acetate Number of VOAs with air bubbles present/total number of VOA's QA-185 5105 EIA Page 3 LEAVE NO SPACES BLANK USE'NA"IF NOT APPLICABLE. G8H140369 TestAmerIca West Sacramento(916)373-5600 9 of 641 DIM ® L®G I C , 8290 , Dioxins/Furans G6H14D369 TestAmerica West Sacramento(916)373-560D 10 of 641 Blue Ridge Paper Products Inc , Client Sample ID: SITE 4A CHt11UM CAT R-FTLET(5) Trace Level Organic Compounds Lot-Sample #.._: GSH140369-001 Work Order #...: RT6311AC Matri.X.........: BIOLOGIC Date Sampled...: 08/05/08 Date Received..: 08/14/08 Prep Date......: 08/22/08 Analysis Date..: 08/26/08 Prep Batch #..-: 8235310 Dilution Factor: 1 DETECTION PARAMETER RESULT LIMIT UNITS METHOD 2,3,7,8-TCDD ND 0.29 pg/g SW846 8290 Total TCDD ND 0.29 pg/g SW846 8290 . 1,2,3,7,8-PeCDD ND 0.42 pg/g SW846 8290 Total PeCDD ND 0.69 pg/g SW846 8290 1,2,3,4,7,8-HXCDD ND 0.28 pg/g SW846 8290 1,2,3,6,7,8-HXCDD ND 1.7 pg/g SW846 8290 1,2,3,7,8,9-HXCDD ND 0.58 pg/g SW846 8290 Total HXCDD 3.8 pg/g SW846 8290 1,2,3,4,6,7,8-HpCDD 96 pg/g SW846 8290 Total HpCDD 3.40 pg/g SW846 8290 OCDD 510 Pg/g SW846 8290 2,3,7,8-TCDF ND 0.12 pg/g SW846 8290 Total TCDF ND 0.89 pg/g SW846 8290 1,2,3,7,8-PeCDF ND 0.063 pg/g SW846 8290 2,3,4,7,8-PeCDF ND 0.34 pg/g SW846 8290 Total PeCDF ND 0.78 pg/g SW846 8290 1,2,3,4,7,8-HXCDF ND 0.20 pg/g SWB46 8290 1,2,3,6,7,8-HXCDF ND 0.076 pg/g SW846 8290 2,3,4,6,7,8-HXCDF ND 0.091 pg/g SW846 8290 1,2,3,7,8,9-HXCDF ND 0.070 pg/g SW846 8290 Total HXCDF ND 0.99 pg/g SW846 8290 1,2,3,4,6,7,8-HpCDF ND 0.75 pg/g SW846 8290 1,2,3,4,7,8,9-HPCDF ND 0.33 pg/g SWO46 8290 Total HpCDF ND 1.4 pg/g SW846 8290 OCDF ND 4.4 Pg/g SW846 8290 PERCENT RECOVERY INTERNAL STANDARDS RECOVERY LIMITS 13C-2,3,7,8-TCDD 73 (40 - 135) 13C-1,2,3,7,8-PeCDD 63 (40 - 135) 13C-1,2,3,6,7,8-HXCDD 82 (40 - 135) 13C-1,2,3,4,6,7,8-HPCDD BO (40 - 135) 13C-OCDD 84 (40 - 135) 13C-2,3,7,8-TCDF 76 (40 - 135) 13C-1,2,3,7,8-PeCDF 66 (40 - 135) 13C-1,2,3,4,7,8-HXCDF 84 (40 - 135) 13C-1,2,3,4,6,7,8-HPCDF 86 (40 - 135) GBH140369 TestAmeriea West Sacramento(916)373.5600 11 of 541 Blue Ridge Piper Products Inc Client Sample ID: SITE 4A COMKON CARP R-FIVXE'(3) Trace Level Organic Compounds Lot-Sample 9...: G89140369-002 Work Order $-..: KT6321AC Matrix........... BIOLOGIC Date Sampled_-_: 08/05/08 Date ReCeiVO(I..: 08/14/08 Prep Date......: 08/22/08 Analysis Date..: 08/26/08 Prep Batch 0...: 9235310 Dilution Factor: i DETECTION PARAMETER RESULT LIMIT UNITS METHOD 2,3,7,E-TCDD 1.2 pg/g =846 8290 Total TCDD 1.2 pg/g SN846 8290 1,2,3,7,8-PeCDD ND 0.95 pg/g SW846 8290 Total PeCDD ND 3.6 pg/g SW846 8290 1,2,3,4,7,8-HXCDD ND 0.83 pg/g SW846 8290 1,2,3,6,7,8-HX0)D 2.9 J pg/g SW846 8290 1,2,3,7,8,9-HXCDD ND 0.55 pg/g SW846 8290 Total HXCUD 2.9 pg/g SW846 8290 1,2,3,4,6,7,E-HpMD 10 pg/g SW846 8290 Total HpCDD 10 pg/g SW846 8290 OCDD 39 pg/g SWB46 8290 2,3,7,8-TCDF 2.2 CON pg/g SW846 8290 Total TCDF 2.8 pg/g SW846 8290 1,2,3,7,8-PeCDF ND 0.96 pg/g SW846 8290 2,3,4,7,8-PeCDF ND 1.2 pg/g SW846 8290 Total PeCDF ND 6.0 pg/g SW846 8290 1,2,3,4,7,8-HXCDF ND 1.8 pg/g SW846 8290 1,2,3,6,7,8-HXCDF ND 0.49 pg/g SW846 8290 2,3,4,6,7,8-HXCDF ND 0.32 pg/g SW846 9290 1,2,3,7,8,9-HXCDF ND 0.085 pg/g SW846 8290 Total HXCDF ND 6.4 pg/g SW846 8290 1,2,3,4,6,7,8-HpCDF ND 0.95 pg/g SW846 8290 1,2,3,4,7,8,9-HpCDF ND 0.27 pg/g SW846 8290 Total HpCDF ND 1.5 pg/g SW846 8290 OCDF ND 0.16 pg/g SW846 8290 PERCENT RECOVERY INTERNAL STANDARDS RECOVERY LIMITS 13C-2,3,7,87TCDD 85 (40 - 135) 13C-1,2,3,7,8-PeCDD 80 (40 - 135) 13C-1,2,3,6,7,8-HXCDD 90 (40 - 135) 13C-1,2,3,4,6,7,8-HpCDD 92 (40 - 135) 13C-OCDD 93 (40 - 135) 13C-2,3,7,8-TCDF 89 (40 - 135) 13C-1,2,3,7,8-PeCDF 78 (40 - 135) 13C-1,2,3,4,7,8-HXCDF 92 (40 - 135) 13C-1,2,3,4,6,7,8-HpCDF 97 (40 - 135) MOTH(S): 1 Estimated rerun,Result is less than the reporting limit. CON Confirmation analysis. 0 GSK140369 TestAmerica West Sacramento(916)373-5600 12 of 541 Blue Ridge Paper Products Inc Client Sample 3D: SITE 4B MURM CAT R-FILLHT(5) Trace Level Organic Compounds Lot-Sample #...: GSH140369-003 Work Order #...: KT6331AC Matrix..........: BIOLOGIC Date Sampled...: 08/05/08 Date Received..: 08/14/08 Prep Date......: 08/22/08 Analysis Date. .: 08/26/08 Prep Batch #...: 8235310 Dilution Factor: 1 DETECTION PARAMETER RESUVr LIMIT UNITS METHOD 2,3,7,8-TCDD ND 0.34 pg/g SW846 8290 Total TCDD ND 0.34 pg/g SW846 8290 1,2,3,7,8-PeCDD ND 0.32 pg/g SW846 8290 Total PeCDD ND 0.84 pg/g SW846 8290 1,2,3,4,7,8-HxCDD ND 0.17 pg/g SW846 8290 1,2,3,6,7,8-HXCDD ND 0.74 pg/g SW846 8290 1,2,3,7,8,9-HxCDD ND 0.18 pg/g SW846 8290 Total HxCDD ND 0.74 pg/g SW846 0290 112,3,4,6,7,8-HPCDD ND 1.5 pq/g SW846 8290 Total HpCDD ND 1.5 pg/g SW846 8290 OCDD 5.1 J pg/9 SW846 8290 2,3,7,8-TCDF NO 0.12 pg/g SW846 8290 Total TCDF ND 2.7 pg/g SW846 8290 1,2,3,7,8-PeCDF ND 0.075 pg/g SW846 8290 2,3,4,7,8-PeCDF ND 0.29 pg/g SW846 8290 Total PeCDF ND 2.0 pg/g SW846 B290 1,2,3,4,7,8-HxCDF ND 0.36 pg/g SVIS46 8290 1,2,3,6,7,8-HXCDF ND 0.45 pg/g SW846 8290 2,3,4,6,7,8-HxCDF ND 0.14 pg/g SW846 8290 1,2,3,7,8,9-HxCDF ND 0.10 pq/g SW846 8290 Total HxCDF ND 2.3 pg/g SW846 8290 1,2,3,4,6,7,8-HPCDF ND 0.44 pg/g SW846 8290 1,2,3,4,7,8,9-HpCDF ND 0.75 pg/g SW846 8290 Total HPCDF ND 1.0 pg/g SW846 8290 OCDF ND 0.32 pq/g SW846 8290 PERCENT RECOVERY INTERNAL STANDARDS RECOVERY LIMITS 13C-2,3,7,8-TCDD 83 (40 - 135) 13C-1,2,3,7,8-PeCDD 72 (40 - 135) 13C-1,2,3,6,7,8-HXCDD 86 (40 - 135) 13C-1,2,3,4,6,7,8-HeCDD 90 (40 - 135) 13C-OCDD 93 (40 - 135) 13C-2,3,7,8-TCDF 88 (40 - 135) 13C-1,2,3,7,8-PeCDF 75 (40 - 135) 13C-1,2,3,4,7,8-HxCDF 90 (40 - 135) 13C-1,2,3,4,6,7,8-BPCDF 95 (40 - 135) NOTE(S) . r - 1 FSdvuted result.Reran is I—dun the reponing Kraft. GSH140359 TestAmerlce West Sacramento(916)373-5600 13 of 541 Blue Ridge Paper Products Inc Client Sample ID: SITS 4B COxMEN CARP R-F3LLET(3) Trace Level Organic compounds Lot-Sample #...: GSH140369-004 Work Order #---: KT6341AC Hatrix....... ... BIOLOGIC Date Sampled...: 08/05/08 Date Received..: 08/14/08 Prep Date......: 08/22/08 Analysis Date.. : 08/26/08 Prep Batch #---: 8235310 Dilution Factor: 1 DETECTION PARAMETER RESULT LIMIT UNITS METHOD 2,3,7,8-TCDD ND 0.36 pg/g SW846 8290 Total TCDD ND 0.36 pg/g SW846 8290 1,2,3,7,8-PeCDD ND 0.49 pg/g SW846 8290 Total PeCDD ND 1.9 pg/g SW846 8290 1,2,3,4,7,8-HXCDD ND 0.35 pg/g S14846 8290 1,2,3,6,7,8-HXCDD ND 1.2 pg/g SW846 8290 1,2,3,7,8.,9-HXCDD ND 0.25 pg/g SW846 8290 Total HxCDD ND 1.2 pg/g SW846 8290 1,2,3,4,6,7,8-HpCDD 7.8 pg/g SW846 8290 Total HpCDD 11 Pg/g SW846 8290 OCDD 31 pq/g SW846 8290 2,3,7,8-TCDF 0.84 T,CON pg/g SW846 8290 Total TCDF 0.84 pg/g SW846 8290 1,2,3,7,8-PeCDF ND 0.28 pg/g SW846 8290 2,3,4,7,8-PeCDF ND 0.41 pg/g SW846 8290 0 2.4 pg/g SW846 829 Total PeCDF ND - 1,2,3,4,7,8-HxCDF ND 0.63 pg/g SW846 8290 1,2,3,6,7,8-HXCDF ND 0.22 pg/g SW846 8290 2,3,4,6,7,8-HpCDF ND 0.12 pg/g SW846 8290 1,2,3,7,8,9-HXCDF ND 0.045 pg/g SW846 8290 Total HXCDF ND 3.0 pg/g SWB46 8290 1,2,3,4,6,7,E-HpCDF ND 0.39 pg/g SW846 8290 1,2,3,4,7,8,9-HpCDF ND 0.19 pg/g SW846 8290 Total HpCDF ND 0.76 pg/g SW846 8290 OCDF ND 0.45 pg/g SW846 8290 PERCENT RECOVERY INTERNAL STANDARDS RECOVERY LIMITS 13C-2,3,7,8-TCDD 82 (40 - 135) 13C-1,2,3,7,8-PeCDD 70 (40 - 135) 13C-1,2,3,6,7,8-HXCDD 87 (40 - 135) 13C-1,2,3,4,6,7,8-HPCDD 88 (40 - 135) 13C-OCDD 92 (40 - 135) 13C-2,3,7,8-TCDF 84 (40 - 135) 13C-1,2,3,7,8-PeCDF 73 (40 - 135) 13C-1,2,3,4,7,8-HpCDF 91 (40 - 135) 13C-1,2,3,4,6,7,8-HpCDF 94 (40 - 136) NOTE(S) - J Fs lmawd rauII.R mlt is tas t mt tte reponino limit. CON Confimtatian analysis. GSH140369 TestAmeriaa West Sacramento(916)373-5600 14 of 541 Blue Ridge Paper Products Inc Client Sample 3D: S= 433 C0MMU CWRP WE Trace Level Organic Compounds Lot-Sample #...: GSH140369-005 Work Order #...: KT6351AC Matrix.........: BIOLOGIC Date Sampled...: 08/05/08 Date Received..: 08/14/08 Prep Date......: 08/22/08 Analysis Date..: 08/26/08 Prep Batch #...: 8235310 Dilution Factor: 1 DETECTION PARAMETER RESULT LIMIT UNITS METHOD 2,3,7,8-TCDD 0.78 J pg/g SW846 8290 Total TCDD 0.79 pg/g SW646 8290 1,2,3,7,8-PeCDD ND 1.1 pg/g SW846 8290 Total PeCDD ND 4.8 pg/g SW846 8290 1,2,3,4,7,8-HXCDD ND 1.0 pg/g SW846 8290 1,2,3,6,7,8-HXCDD 3.8 J pg/g S9846 8290 1,2,3,7,8,9-HxCDD ND 0.60 pg/g SW846 8290 Total HXCDD 3.8 pg/g SW846 8290 1,2,3,4,6,7,8-HpCDD 11 pg/g SW846 8290 Total HpCDD it Pg/g SW846 8290 OCDD 24 pg/g SW846 8290 2,3,7,8-TCDF 2.7 CON pg/g SW846 0290 Total TCDF 4.1 pg/g SW846 8290 1,2,3,7,8-1?eCDF ND 1.1 pg/g SW846 8290 2,3,4,7,8-PeCDF ND 1.3 pg/g SW846 8290 Total PeCDF ND 22 Pg/g SW846 8290 1,2,3,4,7,8-HXCDF ND 1.1 pg/g SW846 8290 1,2,3,6,7,8-HxCDF ND 0.78 pg/g SW846 8290 2,3,4,6,7,8-HXCDF ND 0.39 pg/g SW846 8290 1,2,3,7,8,9-HXCDF ND 0.085 pg/g SW846 8290 Total HxCDF ND 22 pg/g SW846 8290 1,2,3,4,6,7,8-HpCDF ND 1.4 pg/g SW846 8290 1,2,3,4,7,8,9-HpCDF ND 0.50 pg/g SW846 8290 Total HPCDF ND 4.0 pg/g SW846 8290 OCDF ND 0.20 pg/g SW846 8290 PERCENT RECOVERY INTERNAL STANDARDS RECOVERY LIMITS 13C-2,3,7,8-TCDD 84 (40 - 135) 13C-1,2,3,7,8-PeCDD 80 (40 - 135) 13C-1,2,3,6,7,8-HxCDD 91 (40 - 135) 13C-1,2,3,4,6,7,8-HPCDD 92 (40 - 135) 13C-OCDD 92 (40 - 135) 13C-2,3,7,8-TCDF 87 (40 - 135) 13C-1,2,3,7,8-PeCDF 78 (40 - 135) 13C-1,2,3,4,7,8-HxCDF 91 (40 - 135) 13C-1,2,3,4,6,7,8-HpCDF 98 (40 - 135) NOTE(S) : 7 EsmaW result Result is IM than ate repoaing limit. CON Confirmation analysis. G8H740369 TestAmerica West Sacramento(916)373-5600 16 of 641 QC BATA ASSOMAn®N SUNMARY i GOH140369 Sample Preparation and Analysis Control Numbers ANALYTICAL LEACH PREP SAMPLE# MATRIX METHOD BATCH # BATCH # MS RUN# 001 BIOLOGIC SW846 8290 8235310 BIOLOGIC SW846 8290 8235311 002 BIOLOGIC SW846 8290 8235310 BIOLOGIC SW846 9290 8235311 003 BIOLOGIC SWB46 8290 9235310 BIOLOGIC SW846 8290 8235311 004 BIOLOGIC SW846 8290 8235310 BIOLOGIC SW846 8290 8235311 005 BIOLOGIC SW846 8290 8235310 BIOLOGIC SW846 8290 8235311 GBH140369 TestAmerica Wosl Saemmento(916)373-5600 160541 F . b1ETHOD BLANH REPORT Trace Level Organic CempoundS Client Lot 4...: G8H140369 Work order 9 -: XVMEElAA t7atrix.........: BIOLOGIC NB Lot-Sample $: GSH220000-310 Prep Date......: 08/22/08 Analysis Date..: 08/26/08 Prep Batch #F--.: 8235310 Dilution Factor: 1 DETECTION PARAMETER RESULT LIMIT UNITS METHOD 2,3,7,8-TCDD ND 0.050 pg/g SW846 8290 Total TCDD ND 0.050 pg/g SW846 8290 1,2,3,7,8-PeCDD ND 0.078 pg/g SW846 8290 Total PeCDD ND 0.078 pg/g SW846 8290 1,2,3,4,7,8-HXCDD ND 0.10 pg/g SW846 8290 1,2,3,6,7,8-HXCDD ND 0.081 Pg/g SWB46 a290 1,2,3,7,8,9-HXCDD ND 0.081 pg/g SW846 8290 Total HxCDD ND 0.10 pg/g SW846 8290 1,2,3,4,6,7,8-HPCDD ND 0.13 pg/g SW846 8290 Total HpCDD ND 0.13 pg/g SW846 8290 OCDD ND 0.47 pg/g SW846 8290 2,3,7,8-TCDF ND 0.030 pg/g SW846 8290 Total TCDF ND 0.030 Pg/g SW846 8290 1,2,3,7,8-PeCDF ND 0.042 pg/g SW846 8290 2,3,4,7,8-PeCDF ND 0.041 pg/g SW846 8290 Total PeCDF ND 0.044 pg/g SW846 8290 , 1,2,3,4,7,8-HXCDF ND 0.055 Pg/g SW846 8290 1,2,3,6,7,8-HXCDF ND 0.046 pg/g SW846 8290 2,3,4,6,7,8-HXCDF ND 0.053 pg/g SW846 8290 1,2,3,7,8,9-HXCDF ND 0.063 Pg/4 SW846 8290 Total HXCDF ND 0.063 pg/g SW846 8290 1,2,3,4,6,7,8-HpCDF ND 0.097 pg/g SW846 8290 1,2,3,4,7,8,9-HPCDF ND 0.12 pg/g SW846 8290 Total HpCDF ND 0.12 pg/g SW846 8290 OCDF ND 0.11 Pg/g SW846 8290 PERCENT RECOVERY INTERNAL STANDARDS RECOVERY LIMITS 13C-2,3,7,8-TCDD 82 (40 - 135) 13C-1,2,3,7,8-PeCDD 73 (40 - 135) 13C-1,2,3,6,7,8-HXCDD 86 (40 - 135) 13C-1,2,3,4,6,7,8-HPCDD 91 (40 - 135) 13C-OCDD 94 (40 - 135) 13C-2,3,7,8-TCDF BS (40 - 135) 13C-1,2,3,7,8-PeCDF 74 (40 - 135) 13C-1,2,3,4,7,8-HXCDF .89 (40 - 135) 13C-1,2,3,4,6,7,8-HPCDF 96 (40 - 135) NOTH(S) : r Calculations are performed below munding to avoid mundaffwon In oiwiorcd read s GSH140359 TestAmeriea West Saommento(916)373-5600 17 of 541 LABORATORY CONTROL SAMPLE EMEATION REPORT Trace Level Organic Compounds Client Lot #...: GSH140369 [Sorb: Order ()---: KWEEIAC Matrix.........: BIOLOGIC LCS Lot-Sample$; GSH220000-310 Prep Date......: 08/22/08 Analysis Date..: 08/26/08 Prep Batch $...: 8235310 Dilution Factor: 1 PERCENT RECOVERY PARAMETER RECOVERY LIMITS METHOD 2,3,7,8-TCDD 105 (50 - 150) SW846 8290 1,2,3,7,8-PeCDD 100 (50 - ISO) SW846 8290 1,2,3,4,7,8-HaCDD 105 (50 - 150) SW846 8290 1,2,3,6,7,8-HxCDD 103 (so - 150) S9846 8290 1,2,3,7,8,9-HECDD 105 (50 - ISO) SW846 8290 1,2,3,4,6,7,8-HPCDD 105 (so - 150) SW846 829D OCDD 106 (50 - 150) SW846 8290 2,3,7,8-TCDF 100 (so - 250) SW846 9290 1,2,3,7,8-PeCDF 103 (50 - 150) SW846 8290 2,3,4,7,8-PeCDF 99 (50 - ISO) SW846 8290 1,2,3,4,7,8-HxCDF 100 (so - ISO) SW846 8290 _ 1,2,3,6,7,8-HaCDF 99 (so - 1501 SW846 8290 2,3,4,6,7,8-HxCDF 105 (so - 150) SN046 8290 1,2,3,7,8,9-HRCDF 109 (50 - 150) SW846 8290 1,2,3,4,6,7,8-HPCDF 108 (so - 150) SW846 8290 1,2,3,4,7,8,9-HPCDF 108 . (50 - 150) SW846 8290 OCDP 110 (50 - 150) SW846 8290 PERCENT RECOVERY INTERNAL STANDARD RECOVERY LIMITS 13C-2,3,7,8-TCDD 87 (40 - 135) 13C-1,2,3,7,8-PeCDD 76 (40 - 135) 13C-1,2,3,6,7,8-HxCDD 91 (40 - 135) 13C-1,2,3,4,6,7,8-HpCDD 99 (40 - 135) 13C-OCDD 105 (40 - 135) 13C-2,3,7,8-TCDF 91 (40 - 135) 13C-1,2,3,7,8-PeCDF 79 (40 - 135) 13C-1,2,3,4,7,8-HXCDF 99 (40 - 135) 13C-1,2,3,4,6,7,8-HpLDF 103 (40 - 135) NOTE(S) . Calwlations are performed before rounding to avoid roond�ff errors in calculated result[. Bold print denotes control paramettts GBH140369 TestAmerica West Sacramento(916)373-5600 18 of 641 i I LABORATORY CONTROL SAIMLB DATA REPORT Trace Level Organic Compounds Client Lot $___: GBH140369 Work Order 8...: KVMEE1AC matrix BIOLOGIC LCS Lot-Sample$: GSH220000-310 Prep Date......: 08/22/08 Analysis Date..: 08/26/08 Prep Batch #...: 8235310 Dilution Factor: 1 SPIKE MEASURED PERCENT PARAMETER AMOUNT AMOUNT UNITS RECOVERY METHOD 2,3,7,8-TCDD 20.0 21-0 pg/g 105 SW846 8290 1,2,3,7,8-PeCDD 100 100 pg/g 100 SW846 8290 1,2,3,4,7,8-Hx(9D 100 105 pg/9 105 SW846 8290 1,2,3,6,7,8-Hx= 100 103 p9/9 103 SH846 8290 1,2,3,7,8,9-HXMD 100 105 P9/9 105 S9846 8290 1,2,3,4,6,7,8-HpCDD 100 105 pg/g 105 SW846 8290 OCDD 200 212 pg/g 106 SW646 0290 2,3,7,8-TCDF 20.0 20.0 pg/g 100 SW846 8290 1,2,3,7,8-PeCDF 100 103 pg/g 103 S9846 8290 2,3,4,7,E-PeCDF 100 99.3 pg/g 99 SW846 8290 1,2,3,4,7,8-HRCDF 100 100 pg/g 100 S0846 8290 1,2,3,6,7,8-HXCDF 100 98.E pg/g 99 S0846 8290 2,3,4,6,7,8-HaCDF 100 105 pg/g 105 SN846 8290 1,2,3,7,8,9-HBCDF 100 109 pg/g 109 SW846 8290 1,2,3,4,6,7,8-9pCDF 100 108 pg/g 108 SW846 8290 1,2,3,4,7,8,9-HPCDF 100 108 pg/g 208 SW846 8290 - OCDF 200 219 PS/9 110 SW846 8290 PERCENT RECOVERY INTERNAL STANDARD RECOVERY LIMITS 13C-2,3,7,8-TCDD 87 (40 - 135) 13C-1,2,3,7,8-PeCDD 76 (40 - 135) 13C-1,2,3,6,7,8-HXCDD 91 (40 - 135) 13C-1,2,3,4,6,7,8-HPCDD 99 (40 - 135) 13C-OCDD 105 (40 - 135) 13C-2,3,7,8-TCDF 91 (40 - 135) 13C-1,2,3,7,8-PeCDF 79 (40 - 135) 13C-1,2,3,4,7,8-HXCDF 99 (40 - 135) 13C-1,2,3,4,6,7,8-HPCDF 103 (40 - 135) NOTES) : Calcotations arc perforrnod before rounding to avoid roundott errors in calculated results Bold print devotes MMMI patam:ters GSH140369 7estAmerles West Seerernento(916)373-5600 19 of 541 BIOLOGIC5 82905 Percent Lipids GSH140369 TestAmerica West Sacramento(916)373-5699 20 of 541 r Blue Ridge Paper Products Inc Client Sample ID: SIM 4A CBANNIM CAT R-VXLLE v(5) Trace Level Organic Compounds Lot-Sample #___: GSH140369-001 1fork Order $... : KT6311AA Matrix.........: BIOLOGIC Date Sampled...: 08/05/08 Date Received..: 08/14/08 Prep Date......: 08/22/O8 Analysis Date..: 08/26/OB Prep Batch 0...: 8235311 Dilution Factor: 1 DETECTION PARAMETER RESULT LIMIT UNITS METHOD Percent Lipids 3_7 t SN846 8290 GBH140369 TestAmerlca West Sacramento(916)373-6600 21 of 641 Blue Ridge Paper Products Inc Client Sample ID: SITE 4A COMM CARP R-FILLRT(3) Trace Level organic Compounds Lot-Sample $...: G8H140369-002 Work Order (#...: KT632M Matrix.........: BIOLOGIC Date Sampled...: 08/05/08 Date Received.-: 08/14/08 Prep Date......: 08/22/08 Analysis Date..: 08/26/08 Prep Batch R...: 8235311 Dilution Factor: 1 DETECTION PARAMETER RESULT LIMIT UNITS METHOD Percent Lipids 14 W SW846 0290 GOH140369 TestAmeriea West Sacramento(916)373-6600 22 of 541 Blue Ridge Paper Products the Client Sample ID: SITE 4B CHANNEL CAT R-T'TTMET(5) Trace Level OrgaMC Compounds Lot-Sample #...: G8H140369-003 Work Order #...: KT6331AA Matrix.......--: BIOLOGIC Date Sampled...: 08/05/08 Date Received..: 08/14/OB Prep Date......: 08/22/08 Analysis Date..: 08/26/08 Prep Batch 0...: 8235311 Dilution Factor: 1 DETECTION PARAMETER RESULT LIMIT 'UNITS METHOD Percent Lipids 3.9 $ SW846 8290 e GBH140369 TestAmerica West Sacramento(916)373-5600 23 of 541 Blue Ridge Paper Products Inc Client Sample ID: SITE 4B COMMM CARP R-FILLS '(3) Trace Level Organic Compounds Lot-Sample #...: M140369-004 Work Order #...: KT634MA Mtrix..... ....: BIOLOGIC Date Sampled...: 08/05/08 Date Received..: 08/14/08 Prep Date......: 08/22/08 Analysis Date..: 08/26/08 Prep Batch #...: 8235311 Dilution Factor: 1 DETECTION PARAMETER RESULT LIMIT UNITS METHOD Percent Lipids 4.5 SWB46 8290 GSH140369 TestAmerica West Sacramento(016)373-6600 24 of 541 Blue Ridge Paper Products Inc Client Sample ID: SITE 411 COMM CARP FA; Trace Level Organic compounds Lot-Sample (#...: GSH140369-005. Work Order 5...: KT6351AA matrix. ........e BIOLOGIC Date Sampled...: 08/05/08 Date Received..: 08/14/08 Prep Date......: 08/22/08 Analysis Date. .: 08/26/08 Prep Batch #_.- 8235311 Dilution Factor: 1 DETECTION PARAMETER RESULT LIMIT UNITS METHOD Percent Lipids 13 SUB46 8290 GBH140369 TestAmerlca West Sacramento(916)373-5600 25 of 541 rr'• APPENDIX C BLUE RIDGE PAPER CANTON MILL FISH FILLET TISSUE ANALYSIS RESULTS, 1990-2004 r I 31 5r1 Blue Ridge Paper Canton Mill Fish Fillet Tissue Analysis Results, 1990-20040). 1990 Results(°) 1991 ResuttP) Number of Length Number of Length Station species Fish Range(mm) 2,3,7,8-TCDD- Station Species Fish Range(ma) 2,3,7,8-TCDDtct 1 Rock bass 5 151-197 ND(0.15) 1 Rock bass 10 151-190 ND(0.40) RM 64.5 Rock bass 5 153-213 ND(0.15) RM 64.5 Redbreast sunfish 10 106-178 ND(0-33) Black redhorse 2 380-383 ND(0.20) Black redhorse 5 358471 ND(0.35) 2 Redbreast sunfish 5 185496 1.4 2 Redbreast sunfish 8 154-189 0.87 RM 59.0 Redbreast sunfish 5 148-201 3.4 RM 59.0 Redbreast sunfish 8 154-202 0.93 Common carp 1 517 19.7 Common carp 10 491-570 9.7 3 Redbreast sunfish 5 188-203 0.79 3 Redbreast sunfish 10 176-209 ND(0.89) RM 52.3 Redbreast sunfish 5 191-199 2.6 RM 52.3 Bluegill 6 164-197 ND(0.83) Common carp 2 489-555 4.2 Common carp 10 408463 2.4 i 4A Bluegill 5 178-192 ND(12) 4A Lmgemouthbass 7 313468 3.0 RM 41.5 Bluegill 5 153-174 ND(0.63) RM 41.5 Black crappie 10 173 216 ND(0.63) Common carp 1 574 27 Common carp 10 502-688 23 4B Bluegill 5 183-196 0.76 4B Bluegill 5 196-212 ND(0.34) RM 39.0 Largemouth bass 2 279400 ND(1.8) RM 99.0 Bluegill 5 190-208 ND(0.62) i Common carp 4 551-639 66 Common carp 10 532-605 40 5 Redbreast sunfish 10 143-223 0.98 RM 16.5 Spotted bass 2 266-368 ND(035) Common carp 2 511-539 1.7 Total Fish Filleted 57 138 I 1 I I 1992 Resultst°h 1993 Resultst°) Number of Length Number of Length Station Species Fish Range(mm) 2,3,7,8-TCDDt`h Station Species Fish Range(mar) 2,3,7,8-TCDDt°t ' 1 Rack bass 10 147-M ND(0.085) I Rock bass 10 185-208 ND(0.10) RM 64.5 Redbreast sunfish 10 147-182 ND(0.075 RM 64.5 Redbreast sunfish 5 148-203 ND(0.12) , Black redhorse 6 365-441 1.4 Black redhorse 10 365-410 ND(0.80) 2 Redbreast sunfish 10 180-220 0.72 2 Redbreast sunfish 10 169.206 ND(0.27) RM 59.0 Redbreast sunfish 30 178.220 ND(0.38) RM 59.0 Redbreast sunfish 10 140-191 ND(0.15) Common carp 10 486.581 9.3 Common carp 10 462-620 3.1 3 Redbreast sunfish 10 175-200 ND(0.34) 3 Redbreast sunfish 10 155-210 ND(0.27) RM 52.3 Redbreast sunfish 10 183-200 ND(0.29) RM 52.3 Redbreast sunfish 7 180-213 ND(0.36) Common carp 10 439-600 4 Common cup 10 440-576 3.4 4A Black crappie 10 153.232 ND(0.094) 4A Black crappie 10 178-201 ND(0.15) RM 41.5 Black crappie 10 177-221 ND(0.10) RM 41.5 Black crappie 10 182-204 ND(0.089) Common cup to 492.622 29 Common carp to 525-61 1 19 4B Blucgill 10 182.212 ND(0.23) 4B Largemouth bass 10 190-310 ND(0.12) RM 39.0 Largemouth bass 5 215-332 ND(0.19) RM 39.0 Bluegill 10 185-210 ND(0.20) Common carp 10 558-640 5I Common carp 10 530.644 28 5 Redbreast sunfish 10 175-245 ND(0.38) 5 Redbreast sunfish 6 180-231 ND(0.17) RM 19.0 Spotted bass 2 256-355 ND(0.30) RM 19.0 Smallmouth bass 9 212-281 ND(0.13) Smallmauth buffalo 5 428-510 0.61 Smatlmouth buffalo 5 450.550 ND .41 Total Fish Filleted 158 162 1994 Resultst°t 1995 Results(c) Number of Length Number of Length Station Species Fish Range(mm) 2,3,7,8-TCDDt) Station Species Fish Range(maxi) 2,3,7,8-TCDD(°) 1 Rock bass 6 156-185 ND(0.083) 1 Rock bass 10 162 205 ND(0.10) RM 64.5 Redbreast sunfish 30 ISS-197 ND(0.I0) RM 64.5 Rock bass 10 150-220 ND(0.26) Black redhorse 3 367-435 ND(0.096) Black redhorm 7 375-464 ND(0.21) 2 Redbreast sunfish 10 176-206 ND(0.073) 2 Redbreast sunfish 10 152-194 ND(0.20) RM 59.0 Redbreast sunfish 10 160-210 ND(0.092) RM 59.0 Redbreast sunfish 10 161-188 ND(0.16) Common carp 10 490-590 0.99 Comon carp 10 435-664 1.7 3 Redbreast sunfish 10 148.196 ND(0.15) 3 Redbreast sunfish 10 170-206 ND(0.18) RM 52.3 Redbreast sunfish 10 158-210 ND(0.074) RM 52.3 Redbreast sunfish 10 154-202 ND(0.20) Common carp 10 456.565 0.74 Common carp 10 391-571 1.2 4A Black crappie 10 203-231 ND(0.085) 4A Largemouth bass 5 281-439 2.0 RM 41.5 Bluegin 10 185-205 ND(0.084) RM 41.5 Bluegill 10 167-199 ND(0.26) Common carp 10 465-591 3.4 Common carp 10 520-615 5.8 4B Black crappie 10 200215 ND(0.084) 4B Largemouth bass 9 248.391 0.69 RM 39.0 Black crappie 10 195-220 ND(0,062) RM 39.0 Bluegill 8 158-216 ND(0,34) Common carp 10 520-635 6.6 Common carp 4 532-626 11.0 5 Redbreast sunfish 6 129289 ND(0.075) 5 Smallmouth bass 9 280-423 ND(0.11) RM 19.0 Smallmouth bass 9 234-442 ND(0.11) RM 19.0 Redbreast sunfish 7 163-192 ND(0.15) Smallmouth buffalo 9 440-520 ND 0.089 Black redborse 7 440481 ND 0.45) Total Fish Filleted 163 156 1996 Rmultsot 1997 Results( Number of Length Number of Length ' Salon Species Fish Range(me) 2,3,7,8-TCDDt`t Station Species Fish Range(mm) 2,3,7,8-TCDDot . 1 Redbreast sunfish 5 154-185 ND(0.13) 1 Redbreast sunfish 5 144-161 ND(0.11) RM 64.5 Rock bass 5 16D-208 ND(0.085) RM 9.5 Rock has 5 162-194 ND(0.23) Black redhorse 5 401-440 ND(0.089) Black redhorse 4 291-424 ND(022) 2 Redbreast sunfish 5 179-187 ND(0.10) 2 Redbreast sunfish 5 183-200 ND(0,26) RM 59.0 Redbreast sunfish 5 193-191 ND(0.12) RM 59.0 Redbreast sunfish 5 160-18I ND(0.12) Common carp 5 543-580 1.5 Common carp 5 506-615 1.4 3 Redbreast sunfish 5 184.190 ND(0.13) 3 Redbreast sunfish 5 197-202 ND(0.18) RM 52.3 Redbreast sunfish 5 165.185 ND(0.13) RM 52.3 Redbreast sunfish 5 164-195 ND(0.18) Common carp 5 516-630 0.87 Common carp 5 450-505 ND(0.33) 4A Back crappie 5 216-233 ND(0.15) 4A Back crapppie 5 215-231 ND(0.27) RM 41.5 Black crappie 5 215-229 ND(0.18) RM 41.5 Back crappie 5 220-230 ND(0.10) Common carp 5 562.632 42 Common carp 5 570.655 2.3 Channel catfish 5 419-482 2.0 4B Black crappie 5 223-258 ND(0.11) 4B Black crappie 5 226-241 ND(0.17) RM 39.0 Largemouth bass 5 278-310 ND(0.13) RM 39.0 Largemouth bass 5 270-360 ND(0.21) Common carp 5 470.623 4.0 Common carp 5 605.690 11.0 Fathead catfish 5 430540 0.62 5 Rock bass 4 169-186 ND(0.077) 5 Rock bass 5 143-214 ND(0.15) RM 19.0 Smallmouth bass 5 315-454 ND(0.12) RM 19.0 SmArtouth bass 5 278-367 ND(0.27) SmalLmuth buffalo 5 451-555 ND 0.12) Smallmouth buffalo 5 406-525 ND 0.22 Total Fish Filleted 89 Total Fah Filleted 99 1998 Results" 1999 Results(b) Number of Length Number of Length Station Species Fish Range(mm) 2,3,7,8-TCDDt°t Station Species Fish Range(MM) 2,3,7,8-TCDDt°t 1 Redbreast sunfish 5 145-176 ND(0.19) 1 Redbreast sunfish 5 141-177 ND(0.21) RM 64.5 Rock bass 5 158-179 ND(0.29) RM 64.5 Rock bass 5 164-180 ND(0.37) Black redhorse 5 340-396 ND(0.18) Black redhorse 5 352-427 ND(0.33) 2 Redbreast sunfish 5 164-177 ND(0.20) 2 Redbreast sunfish 5 167-190 ND(0,37) RM 59.0 Redbreast sunfish 5 166-193 ND(0.28) RM 59.0 Redbreast sunfish 5 158-179 ND(0.29) Common carp 5 551.661 1.3 Common carp 5 544-615 ND(0,27) 3 Redbreast sunfish 5 168-193 ND(0.34) 3 Redbreast sunfish 5 169-189 ND(0.36) RM 52.3 Redbreast sunfish 5 167-200 ND(0.22) RM 52.3 Redbreast sunfish 5 162-176 ND(0.37) Common arp 5 449.550 ND(0.38) Common carp 5 500-591 0.57 4A Black crappie 5 220-240 ND(0.49) 4A Black crappie 5 220-268 ND(0,19) RM 41.5 Largemouth bass 5 227-330 ND(0.15) RM 4I.5 Black crappie 5 219 244 ND(0.08) Common carp 5 585fi21 1.6 Common carp 5 574-645 D.58 Channel catfish 5 416-458 ND(0.28) Channel catfish 5 425482 0.83 4B Black crappie 5 233-252 ND(0.15) 4B Black crappie 5 233-244 ND(0.27) RM 39.0 Largemouth bass 5 259-330 ND(0.17) RM 99.0 Largemoeth bass 5 276-305 ND(0.32) Common carp 5 563-696 9.1 Common carp 5 621-680 4.7 Hathad catfish 5 414-523 ND(0.20) Flathead catfish 5 372,513 ND(0.46) 5 Rock bass 4 155-190 ND(0.11) 5 Rock bass 5 170-203 ND(0.29) RM MO Smallmouth bass 5 295-365 ND(0.21) RM 19.0 Smallmouth bass 5 297-430 ND(0.19) Smallmouth buffalo 5 464-537 ND(0.31) Smallmouth buffalo 5 476.565 ND 0.31) Total Fish Filleted 99 Total Fish Filleted 100 2000 Results(b) 2001 Resultst4 Number of Length Number of Length Station Species Fish Range(man) 2,3,7,8-TCDDt t Station Species Fish Range(mm) 2,3.7,3-TCDDt`t I Redbreast sunfish 5 137-148 ND(0.48) 1 Black redhorse 5 312407 ND(0.25) RM 64.5 Rock bass 5 162-186 ND(0.45) RM 64.5 Black redhorse 5 357-396 ND(0.38) ' 2 Redbreast sunfish 5 169-176 ND(0.31) 2 Common carp 5 456.555 ND(0.27) RM 59.0 Redbreast sunfish 5 164-181 ND(0.43) RM 59.0 Common carp 5 505-582 ND(0.42) 3 Redbreast sunfish 5 169-181 ND(0.43) 3 Common carp 5 504-615 ND(0.35) RM 52.3 Redbreast sunfish 5 186-199 ND(0.32) RM 52.3 Common cup 5 514-569 ND(0.53) 4A Black crappie 5 212 2L1 ND(0.29) 4A Channel catfish 5 476-612 1.2 RM 41.5 Black crappie 5 220.24I ND(0.24) RM 41.5 Common carp 5 528-668 1.3 Conlmon carp 4 559-604 1.1 Channel catfish 5 435487 ND(0.70) 4B Black crappie 5 213-231 ND(0.41) 4B Flathead catfish 5 405-463 ND(0.29) RM 39.0 Black crappie 5 220.230 ND(0.37) RM 39.0 Common carp 5 654-723 5.6 Common carp 4 593-712 4.4 Flathead catfish 5 407450 ND(0.42) 5 Rock bass 5 171-198 ND(0.45) 5 Black redhorse 5 437497 ND(0.26) RM 19.0 Smallmouth bass 5 209-238 ND(0.31) RM 19.0 Black redhorse 5 427476 ND .3 Total Fish Filleted 98 Total Fish Filleted 40 r • 2002 Resultst'4 2003 Resultsrot Number of Length Number of Length Station species Fish Range(mar) 2,3,7,8-TCDDtg Station Species Fish Range(mm) 2,3,7,8-TCDDt°t 1 Black redhorse 5 372-431 ND(0.14) 1 Black redhorse 5 343-420 ND(0.20) RM 64.5 .RM 64.5 2 Common carp 5 517-548 ND(0.28) 2 Common carp 5 512-584 ND(0.18) RM 59.0 RM 59.0 3 Common carp 5 575-632 ND(0.22) 3 Common carp 5 545-605 ND(0.31). RM 52.3 RM 52.3 4A Common carp 5 523-649 2.2 4A Common carp 5 655-717 3.4 RM 41.5 Channel catfish 5 425.475 ND(0.31) RM 41.5 Flathead catfish 5 521-575 ND(DL=0.35) . 4B Common carp 5 647.670 6.6 4B Common carp 5 602-745 12.0 RM 39.0 Flathead catfish 5 418.505 14D(0.22) RM 39.0 Flathead catfish 5 511.533 ND(DL-0.20) 5 Black redhorse 5 430.489 ND(0.14) 5 Black rcdhorse 5 445-524 ND(DL=0.19) RM 19.0 RM 19.0 i Total Fish Filleted 40 Total Fish Meted 40 2004 Resultsw Number of Length Station Species Fish Range(rmn) 2,3,7,8-TCDD(`) - 1 Black redhorse 5 352440 ND(0.11) RM 64.5 2 Common carp 5 545-668 ND(0.19) RM 59.0 Channel catfish 5 369453 ND(0.17) 3 Common carp 5 587-609 ND(0.27) RM 52.3 4A Common carp 5 598-655 1.7 RM 41.5 Flathead catfish 5 508-565 ND(0.30) 4B Common carp 5 570-W 1.6 RM 39.0 Channel catfish 5 485.542 ND(0.31) 5 Black redhorse 5 420480 ND(0.13) RM 19.0 Total Fish Filleted 40 ' (a) Survey conducted by EA Engineering,Science,and Technology. Analyses conducted by ENSECO laboratories 1990-1994,Quamerra Laboratories 1995-1999,Severn Trent Laboratories in 2 2003. (h) Survey conducted in August. (c) Survey conducted in August and September. (d) Survey conducted in September. (e) Units=ppt(parts per trillion)or p819(picogram per gram) ND =Non-delectable at the detection limit in parentheses. i i 7 I APPENDIX D 2006 REVISIONS TO DIOXIN MONITORING PLAN 32 Michael F.Easley,Governor pP W ATFq William G.Ross Jr.,Secretary \pa pG North Carolina Department of Environment and Natural Resources Alan W.Klimek,P.E.Director CII 7 Division of Water Quality Coleco H.Sullins,Deputy Director CE � 'd uality June 6, 2006 JUN Me Mr. Paul S. Dickens Manager,Environmental Affairs BLUE RIDGE PAPER PRODUCTS I Blue Ridge Paper Products BUS OEPARTPAEUi P.O. Box 4000 Canton,North Carolina 28716 Subject: Revisions to Dioxin Monitoring Plan Blue Ridge Paper Products NPDES No.NC0000272 Dear Mr. Dickens: The Water Quality Section has reviewed your request for modifications to the subject study plan originally approved by the Division of Water Quality in February 1990. The 2001 dioxin fish tissue monitoring plan is approved with the following changes: o Elimination of main stem river sampling stations -beginning in 2006 fish tissue samples will be collected only from Waterville Lake. o Collect a least one whole body bottom feeder sample from Waterville Lake(stations 4A or 4B)to monitor ecological impacts of dioxin contamination in bottom species. o Continue with the collection of bottom feeder fillet samples in Waterville Lake as approved in the 1990 study plan. After reviewing your request to eliminate whole body dioxin analyses from Waterville Lake, our staff recommends that this analysis be continued. Although the Waterville Lake data submitted in your 2005 report shows low levels of dioxin, data submitted by Progress Energy in 2005 showed a mean dioxin TEQ value of 6.7 pg/g for common carp. The value was above the 4.0 pg/g TEQ value used by NCDHHS to post fish advisories for dioxin. As this time the dioxin advisory for Waterville Lake remains in effect, and in our view,warrants continued monitoring. If you have any further questions or comments please feel free to contact Mark Hale at 919/733- 6946. ncsr iy, immie verton , ironmental Sciences Section cc: Roger Edwards-ARO Dr.Luanne Williams—NCDHHS Susan Wilson -DWQ Permits John Crutchfield—Progress Energy W. a��El�`rZ N.C.Division of Water Quality 1617 Mail Service Center Raleigh,North Carolina 27699-1617 (919)733-7015 Customer Service 1-877-623.6748 BLUE RIDGE copy PAPER PRODUCTS INC. Certified Mail Return Receipt Requested 7099 3220 0007 0371 6235 30 March 2006 Mr. Mark Hale Environmental Biologist Environmental Services Section Division of Water Quality North Carolina Department of Environment and Natural Resources 1621 Mail Service Center Raleigh,North Carolina 27699-1621 Subject: Study Plan Revision Dioxin Monitoring in Fish Tissue—Waterville Lake March 2006 NPDES No. NC0000272 Blue Ridge Paper Products Inc. Canton Mill Dear Mr. Hale— The subject study plan revision is enclosed for Division of Water Quality(DWQ)review and approval. Background The Blue Ridge Paper Products Inc.mill in Canton, North Carolina has completed biological monitoring for dioxin in fish in the Pigeon River for the past 16 years. This annual biological monitoring is a requirement of the Canton Mill's NPDES permit. The permit requires that we follow a study plan approved by the DWQ for this work. Dioxin in fish sample collection and reporting for 2002 through 2005 was conducted under the December 2001 Study Plan for Pigeon River Dioxin Monitoring in Fish Tissue prepared by EA Engineering, Science and Technology. EA Engineering completed the dioxin in fish sampling and reporting for years 2002 thru 2004. In 2005,Blue Ridge Paper contracted with the University of Tennessee, Knoxville(UTK)Department of Forestry,Wildlife and Fisheries for the dioxin in fish tissue work. UTK followed the 2001 Study Plan for the 2005 dioxin in fish sampling and report. The 2005 report was submitted to the DWQ on 20 Feb 2006. 175 Main Street a PO Box 4000 Canton, North Carolina 28716 o 828-646-2000 Raising Your Expectations Mark Hale, NC DENR DWQ,ESS- 3/30/06, Page 2 Biological Monitoring Review The first annual dioxin fish tissue sampling study of the Pigeon River was in 1990. At that time, public health fish consumption advisories related to dioxin were in place for the Pigeon River downstream of the Canton Mill for both North Carolina and Tennessee reaches of the river. Dioxin fish tissue concentrations determined from annual sampling declined sharply following completion of the Canton Mill modernization in 1993. Dioxin fish tissue sample concentrations in bottom feeding species at main stem river sample locations became non-detect in 2000 and have remained below analytical detection levels since that time. Dioxin fish tissue sample concentrations in sport fish species from all sampling locations in the Pigeon River became non- detect in the mid-1990s. Based on annual fish tissue sampling, the State of North Carolina lifted the dioxin in fish advisory for the Pigeon River upstream of Waterville Lake in August 2001. The State of Tennessee lifted the dioxin in fish advisory for the Tennessee portion of the Pigeon River in January 2003. The only fish advisory remaining is for carp in Waterville Lake. Dioxin levels in carp collected from Waterville Lake since 2000 continue to be at or near analytical detection levels and are below the North Carolina Department of Health and Human Services (NC DHHS) dioxin toxicity equivalent(TEQ)fish advisory action level of 4 parts per trillion(ppt). The NC DHHS has indicated that two consecutive years of TCDD TEQ levels in carp of 3 ppt or less would provide basis for lifting the public health advisory for consumption of carp from. Waterville Lake(e-mail correspondence from Dr. Luanne Williams, DHHS to Blue Ridge Paper dated 9,Mar 2006). The TCDD TEQs for carp fillet composite samples from Stations 4A&4B in Waterville Lake for the last two years are as follows: Year Station 4A Station 4B 2004 2.5 ppt 2.2 ppt 2005 2.1 ppt 3.6 ppt Study Plan Revision Blue Ridge Paper proposes the following changes to the 2001 biological monitoring Study Plan: o elimination of main stem river sampling stations --fish tissue samples beginning in 2006 will be collected only from Waterville Lake Blue Ridge Paper Products Inc 175 Main Street o PO Box 4000 Canton, North Carolina 28716 o 828-646-2000 Raising Your Expectations Mark Hale, NC DENR DWQ,ESS- 3130/06, Page 3 © elimination of whole body fish composite samples from the lake-- only composite fillet samples of target bottom feeding fish species will be collected for laboratory analysis of dioxin. The 2006 study plan revision is enclosed for your review and approval. A copy of the 2001 study plan is also enclosed for your reference. Summary The 2006 dioxin in fish sampling work is planned for the mid-summer period of August and early September. We request DWQ approval of the 2006 study plan revision no later than the end of May 2006. Please contact us if you have questions. Paul S. Dickens J. Glenn Rogers Manager,Environmental Affairs Water Compliance Coordinator 828-646-6141 828-646-2874 dickep@blueridgepaper.com rover¢@blueridyepaaper.com Enclosures: Study Plan Revision Dioxin Monitoring in Fish Tissue— Waterville Lake March 2006 Prepared by University of Tennessee for Blue Ridge Paper Products Study Plan for Pigeon River Dioxin Monitoring in Fish Tissue December 2001 Prepared by EA Engineering for Blue Ridge Paper Products cc(w/enclosures): Bryn Tracy- NC DENR DWQ,ESS Susan Wilson—NC DENR DWQ,Permits Sergei Cherinkov—NC DENR DWQ, Permits Roger Edwards—NC DENR DWQ,ARO Keith Haynes - NC DENR DWQ, ARO Dr. Louanne Williams—NC DHHS Larry Wilson—UTK Billy Clarke—Roberts & Stevens John Crutchfield—Progress Energy Blue Ridge Paper Products Inc 175 Main Street o PO Box 4000 Canton, North Carolina 28716 o 828-646-2000 Raising Your Expectations c o py BLUE rUDGE PAPER PRODUCTS INC. STUDY PLAN REVISION DIOXIN MONITORING IN FISH TISSUE Watervifle Lake Prepared for: Blue Ridge Paper Products, Inc. Canton Mill Canton,North Carolina NPDES No.NC 0000272 Prepared by: J.1Larry Wilson,Ph.D. Departments of Forestry,Wildlife and Fisheries University of Tennessee I£noxville,Tennessee March 2006 Study Plan—2006 Dioxin Monitoring in Fish Tissue,Waterville Lake University of Tennessee for Blue Ridge Paper Products Inc.Canton Mill Page I INTRODUCTION The Blue Ridge Paper Products Inc. Canton Mill conducts annual biological monitoring of dioxin in fish in the Pigeon River under conditions of the NPDES permit for the mill. This monitoring for years 2002 thru 2005 was in accordance with the December 2001 Study Plan for Pigeon River Dioxin Monitoring-in Fish Tissue prepared by EA Engineering, Science and Technology(EA 2001a). This document details changes for dioxin in fish monitoring beginning in 2006. The 2001 study plan is incorporated by reference. The specific changes to the 2001 study plan include: o elimination of main stem river sampling stations --fish tissue samples in 2006 will be collected only from Waterville Lake o elimination of whole body fish composite samples from the lake-- only composite fillet samples of target bottom feeding fish species will be collected for laboratory analysis of dioxin. The 2006 dioxin in fish tissue sampling from Waterville Lake will be conducted by personnel from the University of Tennessee, Knoxville(UTK),Department of Forestry, Wildlife and Fisheries. SAMPLE LOCATIONS The schedule for fish tissue collection will be consistent with prior years targeting dry weather periods in late August and early September. UTK will collect and prepare fish tissue samples from two locations in Waterville Lake on the Pigeon River(PRM 39.0-41.5). In previous studies,the fish collection sites in Waterville Lake have been designated 4A(PRM 41.5) and 4B (PRM 39.0). Site 4A is located approximately 21.8 RM downstream from the Canton Mill outfall, near the Messer Branch-Pigeon River confluence. Site 4B is in the vicinity of the Wilkins Creek-Pigeon River confluence, approximately 24.3 RM downstream from the Canton Mill outfall. Fish sampling will be conducted in the vicinity of each location described above; however, the distance or effort at each station will depend on how difficult it is to collect target fish species at that location. In 2005, common carp in the lower portion of the Waterville Lake were extremely difficult to collect. FISH COLLECTION TECHNIQUES AND TARGET SPECIES The goal of the 2006 fish collection effort is one composite bottom feeder fillet sample at each Waterville Lake sampling station 4A and 4B. Each composite consists of 3 to 5 similarly sized (shortest specimen within 75% of the length of the longest) adult individuals of the target species. Common carp (Cyprinus caipio) and channel catfish(Ictalurus punctatus) are the targeted bottom feeder species at sites 4A and 4B. Every reasonable effort will be made to collect the desired size, species, and number of fish. However, the outcome of sampling effort Study Plan—2006 Dioxin Monitoring in Fish Tissue,Waterville Lake University of Tennessee for Blue Ridge Paper Products Inc.Canton Mill Page 2 each year is dependent on physical river conditions and the natural diversity and abundance of target fishes at each location. The field investigators will be equipped with an array of collecting gear, which will enable sampling of all habitats regardless of river conditions. The US EPA recommends active methods of fish collection in the Sampling Guidance Manual (Versar 1984), such as electrofishing, trawling, angling, or seining. These are preferred over passive methods (e.g., gill nets,trap nets, trot lines)because samples are collected from more defineable areas (Versar 1984). Electro- fishing may be used at both locations (4A and 4B); gill nets may also be used in areas where water depth will limit the electro-fishing gear. A boat electrofishing unit(pulsed direct current, Smith Root Type VIA electro-fisher powered by a 240-volt, 5000-Watt generator) will be provided. Electro-fishing techniques will follow those described in the National Dioxin Study (Versar 1984). All gill nets will be pulled and examined on a regular basis to reduce specimen stress or mortality, and specimens submitted for analysis will be selected for good health and condition. Fish collection techniques and level of effort(time) expended at both locations (4A and 413)will be recorded. Total study effort for the 4A/413 collections in 2005 took 460 gill-net hours and approximately six hours of electro-fishing over a four-day period to obtain the necessary specimens. Channel catfish were easily caught, but common carp were extremely difficult to collect,particularly in the lower portion of the lake(413). In summary, fish tissue samples will be collected as follows: o bottom-feeder composite—one composite bottom feeder fillet sample at each location 4A and 413 o catfish composite—one composite catfish fillet sample at each location 4A and 413 SAMPLE PREPARATION All fish tissue samples will be prepared in accordance with U.S. EPA Region IV recommendations (Cummingham 1990 as described in EA 2001a). To prevent cross- contamination between sampling stations, all sampling equipment likely to come into contact with the fish will be rinsed extensively with site water between stations. Specimens collected at each location will be sorted by size and species, and target species identified. UTI,will obtain a 3 to 5-fish composite sample at each location(4A and 4B) which meet the species/size objectives discussed earlier. All specimens retained will be immediately placed on ice for later processing. All fish submitted for tissue analysis will be measured to the nearest millimeter(TL) and weighed to the nearest gram(wet weight). Following collection of channel catfish and common carp, each specimen will be prepared for shipment and analysis. Samples will consist of epaxial muscle tissue and skin from one side of the fish. Fillet samples will be prepared by removing scales (or removing the skin from Study Plan—2006 Dioxin Monitoring in Fish Tissue,Waterville Lake University of Tennessee for Blue Ridge Paper Products Inc.Canton Mill Page 3 catfishes) and then malting an incision behind the opercula (on both sides of the fish) from the base of the spine (behind the skull) to just below the pectoral fin. Care will be taken to cut through the epaxial muscle without puncturing the rib cage or gut lining. A second incision will be made along the length of the spine to the caudal fin on both sides of the fish. The muscle will be cut away from the rib cage to obtain a fillet. Fillet knives will be solvent rinsed(hexane and acetone) between fish from different locations. Each composite sample will be wrapped in aluminum foil (dull side toward sample),labeled, and placed on dry ice. One side fillets will be sent to Severn Trent Laboratory for analysis; the opposite side fillets will be retained by Blue Ridge Paper as back-up fillets. All individual specimens (fillets) composing a single composite sample will placed together in a water-tight plastic bag labeled with the station name, sample number, and the number of samples in that composite. All labels will contain following information: sample identification number, sample location and station identification, sampling team initials,date of collection, species name, and sample type (i.e.,fillet). A chain-of-custody form will be filled out for each cooler of samples submitted for analysis, and each form will include composite specific information and instructions. All samples will be frozen solid prior to shipment to the analytical laboratory. The frozen samples will be packed on dry ice and shipped via overnight delivery to Severn Trent Laboratory (STL)—Sacramento for analysis. The back-up fillets will be retained in a freezer at the Canton Mill until laboratory analytical results for the composite fillet samples are received and verified; the back-up fillet samples will then be destroyed. SAMPLE ANALYSIS The composite fillet fish tissue samples received by STL will be analyzed for dioxin(2,3,7,8- TCDD), furan(2,3,7,8-TCDF) and related isomers using EPA Method 8290 (US EPA 1994). Percent lipids will also be determined for each composite sample. STL will provide laboratory analytical reports including QA/QC summaries and completed chain-of-custody forms documenting receipt by the lab. REPORTING Results of 2006 dioxin in fish tissue sampling from Waterville Lake will be submitted to the NC DENR within 180 days of the completion of field work as required by the Blue Ridge Paper NPDES permit. The fish tissue sampling and analytical report will follow the general format of prior year reports. Dioxin toxicity equivalent(TEQ) levels will be calculated for all 17 chlorodibenzo dioxin and furan(CDD/F) isomers included in EPA Method 8290. The TEQ of each detectable isomer will be calculated based on the toxicity equivalent factor(TEF)for the isomer provided by the World Health Organization(WHO 1997). The measured concentration of each CDD/F isomer will be multiplied by its appropriate TEF to obtain a concentration of the isomer equivalent to the toxicity of 2,3,7,8-TCDD, the most toxic of the CDD/F isomers. Non- detectable concentrations will be treated as zero values for TEQ calculation. As requested by the Study Plan—2006 Dioxin Monitoring in Fish Tissue,Waterville Lake University of Tennessee for Blue Ridge Paper Products Inc.Canton Mill Page 4 NC DHHS (Williams 2006), the TEQ results for the last two years will be presented in a columnar, side-by-side format to allow easy comparison against health advisory action levels. References EA Engineering,Science,and Technology Inc. 1990. Study Plan for the Monitoring of Dioxin in Fish Tissue. EA Report No. 11370.01,prepared for Champion International Corporation, Canton, North Carolina. EA Engineering,Science,and Technology Inc. 1991. Results of the 1990 Dioxin Monitoring in Fish Tissue. EA Report No. 11370.02,prepared for Champion International Corporation,Canton,North Carolina. EA Engineering,Science,and Technology Inc. 1992. Results of the 1991 Dioxin Monitoring in Fish Tissue. EA Report No. 11370.03,prepared for Champion International Corporation, Canton,North Carolina. EA Engineering,Science,and Technology Inc. 1993a. Results of the 1992 Dioxin Monitoring in Fish Tissue. EA Report No. 11370.05,prepared for Champion International Corporation,Canton,North Carolina. April. EA Engineering,Science,and Technology Inc. 1993b. Results of the 1993 Dioxin Monitoring in Fish Tissue. EA Report No. 11370.06,prepared for Champion International Corporation,Canton, North Carolina. December. EA Engineering,Science,and Technology Inc. 1994. Results of the 1994 Dioxin Monitoring in Fish Tissue. EA Report No. 11370.07,prepared for Champion International Corporation,Canton,North Carolina. December. EA Engineering,Science,and Technology Inc. 1995. Results of the 1995 Dioxin Monitoring in Fish Tissue. EA Report No. 13043.01,prepared for Champion International Corporation,Canton,North Carolina. December. EA Engineering,Science,and Technology Inc. 1996. Results of the 1996 Dioxin Monitoring in Fish Tissue. EA Report No. 13176.01,prepared for Champion International Corporation,Canton,North Carolina. December. EA Engineering,Science,and Technology Inc. 1997. Results of the 1997 Dioxin Monitoring in Fish Tissue. EA Report No. 13353.01,prepared for Champion International Corporation,Canton,North Carolina. November. EA Engineering,Science,and Technology Inc. 1998. Results of the 1998 Dioxin Monitoring in Fish Tissue. EA Report No. 13478.01,prepared for Champion International Corporation, Canton,North Carolina. December. EA Engineering,Science,and Technology Inc. 2000. Results of the 1999 Dioxin Monitoring in Fish Tissue. EA Report No. 13478.01,prepared for Champion International Corporation,Canton,North Carolina. January. EA Engineering,Science,and Technology Inc. 2001a. Study Plan for Pigeon River Dioxin Monitoring in Fish tissue. Prepared for Blue Ridge Paper Products,Canton,North Carolina. November. Study Plan—2006 Dioxin Monitoring in Fish Tissue,Waterville Lake University of Tennessee for Blue Ridge Paper Products Inc.Canton Mill Page 5 EA Engineering,Science,and Technology Inc. 2001b. Results of die 2000 Dioxin Monitoring in Fish Tissue. EA Report No. 13745.01,prepared for Blue Ridge Paper Products, Canton,North Carolina. December. EA Engineering,Science,and Technology Inc. 2001c. Results of the 2001 Dioxin Monitoring in Fish Tissue. EA Report No. 13900.01,prepared for Blue Ridge Paper Products,Canton,North Carolina. December. EA Engineering,Science,and Technology Inc. 2003. Results of the 2002 Dioxin Monitoring in Fish Tissue. EA Report No. 13900.02,prepared for Blue Ridge Paper Products,Canton,North Carolina. December. EA Engineering,Science,and Technology Inc. 2004. Results of the 2003 Dioxin Monitoring in Fish Tissue. EA Report No. 13900.03,prepared for Blue Ridge Paper Products,Canton,North Carolina. January. Henry,A.G.and J.L.Wilson. 2006. Results of 2005 Dioxin Monitoring in Fish Tissue. Center for Environmental Biotechnology and Department of Forestry,Wildlife and Fisheries, University of Tennessee,Knoxville,Tennessee. U.S.Environmental Protection Agency(US EPA). 1994. Analytical Procedures and Quality Assurance for Multimedia Analysis of Polychlorinated Dibenzo-para-dioxins and Polychlorinated Dibenzofurans by High Resolution Gas Chromotography/High Resolution Mass Spectrometry(Method 8290). Versar,Inc. 1984. Sampling Guidance Manual for the National Dioxin Study. U.S.Environmental Protection Agency. EPA Contract 68-01-6160. Work Order Number 8.7. Office of Water Regulations and Standards,Monitoring and Data Support Division,Washington,D.C.Final Draft July. Williams, L. 2006. E-mail correspondence from North Carolina Department of Health and Human Services to Blue Ridge Paper Products concerning review of 2005 Dioxin Monitoring in Fish Report, March 9. World Health Organization(WHO). 1997. Exposure and Human Health Reassessment of 2,3,7,8- Tetrachimodibenzo-p-dio2cin(I'CDD) and Related Compounds: Part II Health Assessment of 2,3,7,8-Tetr2dilorodibenzo-P-dioxin(TCDD and Related Compounds. COCKY EA Project 13900.01 STUDY PLAN FOR MGEON MVER DNOM N Gild®MT®RM IN MSH MSSUE Prepared for: Blue Ridge Paper Products Canton, NC Prepared by. EA Engineering, Science, and Technology 444 Lake Cook Road, Suite 18 Deerfield, IL 60015 December2001 TABLE OF CONTENTS Page I..........Introduction .................................................................................... 1-1 2. Station Locations .............................................................................. 2-1 3. Fish Collection Techniques and Target Species .......................................... 3-1 4. Sample Preparation ........................................................................... 4-1 5. Analysis of Fish Tissue Samples ............................................................ 5-1 6. Quality Assurance ............................................................................. 6-1 7. Project Schedule ............................................................................... 7-1 8. Monitoring Report ............................................................................. 8-1 9. References ...................................................................................... 9-1 i 1. INTRODUCTION This study plan details the materials and methods that will be used to annually assess the levels of dioxins and fur•ans in fish tissues from the Pigeon River downstream of the discharge from the Blue Ridge papermill in Canton,North Carolina. This study plan was developed in response to requirements in the mill's current NPDES permit(Permit No. NC0000272). Changes to original permit conditions as detailed in letters from North Carolina Division of Water Quality(NCDWQ)and North Carolina Department of Health and Human Services (NCDHHS)dated 22 August 2001 and 31 August 2001,respectively have been incorporated into this study plan. Section 2 of this study plan provides information regarding the locations of the sampling stations. Section 3 details the techniques that will be used to collect fish at each station and the target species. Section 4 describes the procedures that will be used to prepare the collected fishes for tissue analysis, Section 5 specifies the analytical technique that will be used to determine the concentrations of the different dioxin and furan isomers in each tissue sample. The Quality Assurance plan is presented in Section 6,and the project schedule, monitoring report, and references are found in Sections 7, 8, and 9,respectively. 1 2. STATION LOCATIONS Six stations have been established for the collection of fishes (Figure 2-1 and Table 2-1). Station 1,the background site, is located at Pigeon River Mile(RM)64.5 adjacent to the Canton Recreational Park, approximately 1.2 RM upstream from the Canton Mill outfall. Except at very high flows,the Canton Mill dam blocks the movement of fishes thereby preventing the interaction of control and monitoring station fishes. Station 2 is located at RM 59.0, upstream from Clyde,NC and approximately 4.3 RM downstream from the Canton Mill outfall. Station 3 is located at RM 52.3 just upstream of the old Rt. 209 bridge, approximately 11.0 RM downstream from the Canton Mill outfall. Stations 4A and 4B are located in Waterville Lake at RM 41.5 and 39.0,respectively. Station 4A is located approximately 21.8 RM downstream from the Canton Mill outfall,near the Messer Branch-Pigeon River confluence. Station 4B is in the vicinity of the Wilkins Creek-Pigeon River confluence, approximately 24.3 RM downstream from the Canton Mill outfall. Stations 4A and 4B correspond to the upper and lower ends,respectively, of Waterville Lake. Station 5 is at RM 19 near Bluffton,TN,44.3 miles downstream of the mill outfall. Fish sampling will be conducted in the immediate vicinity of each location described above,however,the sample reach may be extended somewhat, if necessary,to facilitate collection of the required number of fish. 2 1-40 Station 5 RM 19.0 5 Bluffton TN-- ,Hartford,TN .� TENNESSEE N ••—�� NORTH CAROLINA kx Cte its m \9 Hydro Plant rig (26.0) I` Gc r\F 0 % \ f 5G• j� ep Walters Dam— B Station 4B Station 4A RM 39.0 RM 41.5 4 Waterville Lake Final Creek New Hepco Bridge FLOW Jonathan Creek Old Rt.209 3 Station 3 Station 2 Mill 63.3 l RM 52.3 RM 50.0 RM 3.3 WaynesvilleSTP— 2 fI Canton NC Outfall d RM 50A F`Gtee Clyde Station 1 1 RM 64.5 (Control) Figure 2-1. Fish tissue sampling station locations on the Pigeon River. TABLE2-1 PIGEON RIVERSAMPLING STATIONS Station River Station Location and Numb Mile Distance from Ontfail Site DescrintioNFiabitat Tvae Fish Community 1 645 Pigeon Riverupstream from Canton, Characterized by riffle,run,and pool habitats. Maximum Relative abundance dominated by minnows and darters. River ' NC,adjacent to Canton Recreational depth approximately 6 ft. Substrate primarily cobble and chub,greenfin darter and rock bass are dominant. Northern hog Park(1.2 RM upstream from Canton boulders interspersed with gravel and sand. sucker,black redhorse,mirror shiner,redbreast sunfish,central Mill outfalO, stoneroller,greenside darter,and mottled sculpm arc common. 2 59.0 Pigeon River upstream from Clyde,NC Characterized by riffle,ran,and pool habitats with canopy Relative abundance dominated by redbreast sunfish,central (4.3 RM downstream from the Canton cover. Maximum depth approximately 5 ft. Substrate stoneroller,and northern hog sucker. Mill outfall). primarily cobble/gravellsaud with some boulders and bedrock. 3 52.3 Pigeon River in the vicinity of the Rt Characterized by riffle,ran,and pool habitats with some Redbreast sunfish,northern hog sucker,and common carp arc 209 bridge(11.0 RM downstream canopy cover. Maximum depth approximately 5 ft. dominant. Central stoneraller is common. from the Canton Mill outfall) Substrate primarily bedrock and boulders with some cobble and sand/gravelffines deposited in pool areas. 4A 41.5 Upper Waterville Lake(21.8 RM Characterized by deep-water lentic habitat,bedrock, Relative abundance dominated by blackcmppie. Bluegill, downstream from the Canton Mill and soft bottom sediments. Maximum depth sampled Flathead catfish,channel catfish,largemouth bass,and common outfalp approximately 14 ft. carp are common. 4B 39.0 lower Waterville Lake(243 RM Characterized by deep-water lcmic habitat,bedrock, Relative abundance of catch dominated by black crappic. downstream from the Canton Mill and softbotmm sediments. Maximum depth sampled Bluegill,channel catfish,flathead catfish,and carp ire common. outfal0 approximately 40 ft. Very steep banks with little cover. 5 19.0 Pigeon River near Bluffton,TN,just Characterized by deep pools and runs with some shallow Central stoneraller and northern hog sucker arc dominant. upstream of 140(443 RM downstream riffles. Maximum depth approximately 6 to 8 ft. Substrate Smalimouth bass,whitetail shiner,telescope shiner,greehside, from the Canton Mill outfall) primarily bedrock,boulder,and cobble. drier,and banded sculpin are common. Except for smalimouth bass and rock bass,centrmchids are uncommoon. 3. FISH COLLECTION TECHNIQUES AND TARGET SPECIES A listing of the Pigeon River fish collection techniques is provided below: Station Number River Mile Sampling Technique 1 64.5 Electrofishing 2 59.0 Electrofishing 3 52.3 Electrofishing 4A 41.5 Gill nets 4B 39.0 Gill nets 5 19.0 Electrofishing Except in Waterville Lake,the principal sampling gear will be electrofishing. Depending on depth,either a pram or boat electrofisher will be used. Gillnetting is the most effective technique for the collection of bottom-feeder species from the Waterville Lake monitoring stations. Gill nets will be checked at least once a day,usually within 12 hours of being deployed. Other appropriate sampling techniques may be used if necessary. Field notes will be recorded at each sampling station including the type of sampling gear,level of effort(time),flow and clarity conditions,and selected physiochemical data(e.g., dissolved oxygen, water temperature, and conductivity [electrofishing locations only])using accepted proceedures and equipment. All fishes submitted for tissue analysis will be measured(total length),weighed(wet weight),examined for anomalies, and recorded on a standard Fisheries Data Sheet(Figure 3-1). The goal of the fish collection effort is to collect one composite bottom feeder fillet sample at each of the six sampling stations. Each composite will consist of 3 to 5 similarly sized (shortest specimen within 75%of the length of the longest) adult individuals of the target species. Common carp will be the target species at Stations 2,3,4A,and 4B,with northern hog sucker and black redhorse as alternative species in the riverine portion of the river below the mill(i.e., Stations 2 and 3). Common carp are absent at Stations I.and 5. At these stations,black redhorse will be the target bottom feeder, with northern hog sucker and smallmouth buffalo being alternative species. Alternative representative bottom feeder species may be collected in the rare event that these target species are not collected. In Waterville Lake, one additional fillet composite sample using either channel catfish or flathead catfish will be collected at Stations 4A and 4B. Catfish are rare in the river between the mill and Waterville Lake. However,in the event that three or more catfish of a similar size are encountered at either Stations 2 or 3, a catfish fillet composite will be prepared for either or both of these stations. In addition to the fillet composites, a whole body composite consisting of 3-5 similarly sized common carp will be collected at either Station 4A or 4B in Waterville Lake. 5 Table 3-1 Fish Collection Techniques Station Number Station Location Sampling Technique 1 Pigeon River Mile 64.5 Electrofishing 2 Pigeon River Mile 59.0 Electrofishing 3 Pigeon River Mile 52.3 Electrofishing 4A Pigeon River Mile 41.5 Gill nets 4B Pigeon River Mile 39.0 Gill nets 5 Pigeon River Mile 19.0 Electrofishing In summary,fish will be collected as follows: o Bottom feeder fillet composite—one sample at all six stations o Catfish fillet composite—one sample at Stations 4A and at 4B c Common carp whole body composite—one sample from either Station 4A or 4B 0 Catfish fillet composite—one sample at Stations 2 and at 3,if specimens are encountered 7 4. SAMPLE PREPARATION t Fillet samples will consist of the epaxial muscle tissue from one side of the fish. The fillet from the other side will be retained as a backup until laboratory results are obtained, Bottom feeder whole-body samples will consist of the entire fish. Specimens collected will be rinsed in site water, stunned with a sharp blow to the head and placed on wet ice until processing.Each fish selected for analysis will be weighed and measured. Fillet samples will be prepared by removing-all scales (or removing skin from catfishes) and subsequently making an incision behind the opercula(on both sides of the fish)from the base of the spine(behind the skull)to just below the pectoral fin. Care will be taken to not puncture the gut lining. A second incision will be made along the length of the spine to the caudal fin on both sides of the fish. The epaxial muscle will then be gently cut away from the rib cage to obtain a fillet. In this fashion, all flesh and skin(except catfishes) will be obtained fiom head to tail. The fillets from specimens comprising a particular composite will be combined, then the sample will be wrapped in aluminum foil (dull side toward sample),placed in a water-tight plastic bag,labeled (see Section 6), and placed on wet ice. Within 24 hours of processing, the samples will be frozen, 8 f 5. ANALYSIS OF FISH TISSUE SAMPLES Samples will be analyzed for dioxin using EPA Method 8290 (U.S. EPA 1994). Percent lipids will also be determined for each sample. The laboratory will measure the concentration of 17 isomers of chlorodibenzo dioxins and furans (CDD/F). The toxic equivalent(TEQ) of each detectable isomer will be calculated based on toxicity equivalent factors (TEF)provided by the World Health Organization(WHO 1997). The measured concentration of each CDD/F isomer will be multiplied by its appropriate TEF to obtain a concentration of that isomer equivalent to the toxicity of 2,3,7,8-TCDD,the most toxic of the many CDD/F isomers. As per the directive of NCDHHS,non-detectable concentrations will be treated as zero values for TEQ calculations. 9 r 6. QUALITY ASSURANCE The following procedures will be followed to prevent contamination of samples collected at different stations or between composites collected at the same station. Dip nets,fish scalers, and holding containers will be rinsed with site water prior to use at each station. All fish will be rinsed in site water to remove any debris (e.g., sediment)prior to procming. During processing, the measuring board will be wrapped with clear plastic wrap and this wrap will be changed among stations. Fillet knives will be solvent rinsed (hexane and acetone)between fish from different stations. Each composite sample will be wrapped in aluminum foil (dull side toward sample),labeled, and placed on dry ice within 24 hours of processing. All fillets or whole bodies composing a single composite sample will be foil-wrapped,then placed in a water-tight plastic bag labeled with the station name, sample number, and the species in that composite. All labels will contain the following information: o Sample identification number, o Station identification, o Sampling team initials, o Date of sample collection, o Species name, o Sample type(i.e.,fillet or whole body) o A unique composite number Chain-of-Custody(COC)sheets will be completed following sample preparation and compositing. The composite identification number and corresponding number and type of fish comprising that composite sample will be recorded on the COC. Copies of all COCs will be retained. Following completion of sampling,samples will be shipped on dry ice to the analytical laboratory via an overnight courier. Upon receipt,the laboratory will compare the contents with that noted on the COC sheets and will note the condition of the samples. 10 7. PROJECT SCHEDULE To be consistent with past collections, all samples will be collected in August or September. A final report will be provided to NCDEQ within 180 days of sampling. 11 T� 8. MONETORING REPORT Each annual monitoring report will include the sampling methods and procedures employed, a description of the sampling locations, descriptions of each fish collected (e.g.,species,length and weight), as well as the results of the chemical analysis (reported as individual TCDD/F isomers and 2,3,7,8-TCDD Toxic Equivalent Values). Also included in appropriate appendices will be.field notes,copies of all chain-of-custody sheets, and any pertinent memorandum or communication record forms. 12 9. REFERENCES U.S. Environmental Protection Agency(U.S.EPA) 1994. Analytical Procedures and Quality Assurance for Multimedia Analysis of Polychlorinated Dibenzo-para-dioxins and Polychlorinated Dibenzofurans by High-Resolution Gas Chromatography/High- Resolution Mass Spectrometry(Method 8290). World Health Organization(WHO). 1997. Exposure and Human Health Reassessment of 2,3,7,8-Tetrachlorodibenzo-p-dioxin(TCDD) and Related Compounds: Part II Health Assessment of 2,3,7,8-Tetrachlorodibenzo-p-dioxin(TCDD) and Related Compounds. r 13