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HomeMy WebLinkAboutNC0000272_2009 Dioxin Monitoring Fish Tissue_20100111 29)0 0 �JJJ Olex-11 "j] M-moandlom in I no F 1 s he T II �J is t 1e Blue Ridge Paper Products Inc dba Evergreen Packaging Canton , NC Roger Edwards, NC DWQ ARO 1/6/2010 Page 2 Distribution with enclosure: NC Division of Water Quality(two copies) Certified Mail Central Files 1617 Mail Service Center Raleigh,NC 27699-1617 John Cruchfield Progress Energy. 410 South Wilmington Street PEB 7 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 6ih 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 Evergreen Packaging—Canton Mill 175 Main Street • PO Box 4000 Canton, North Carolina 28716 • 828-646-2000 RESULTS OF 2009 DIOXIN MONITORING IN FISH TISSUE Prepared for: Blue Ridge Paper Products Inc., dba Evergreen Packaging Canton Mill Canton, North Carolina Prepared by: i 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 December 2009 i '� TABLE OF CONTENTS Page List of Tables . . . . . . . . . . . . . . . . . ii List of Figures. . . . . . . . . . . . . . . . . iii 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 . . . . . . . . . . . . . 13 . 6. ANALYTICAL RESULTS . . . . . . . . . . . . . 15 7. REFERENCES . . . . . . . . . . . . . . . 27 8. APPENDICES 30 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 2009 . . . . . . . . . . . . . . . . . 9 6-1 Summary of Pigeon River fish tissue analysis results—2009 . . . . 17 6-2 Toxicity equivalence factors for CDD/F isomers. . . . . . . . 18 6-3 Summary of CDD/F isomer analyses, toxicity equivalent factors, and toxicity equivalent values for the 2009 Pigeon River fish tissue composites . . . . . . . . . . . . . 20 6-4 Blue Ridge Paper Canton Mill fish fillet tissue analysis results 2005—2009 . . . . . . . . . . . . . . . . . 22 ii - LIST OF FIGURES Number Title Page ES-1 TCDD concentrations in carp fillets collected from the Pigeon River, 1990-2009. . . . . . . . . . . . . . . . . . v ES-2 TCDD concentrations in catfish fillets collected from the Pigeon River, 1997-2009. . . . . . . . . . . . . . . . . . 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-la Lengths of fish collected from Waterville Lake for tissue analysis, 2004-2009 . . . . . . . . . . . . . . . . . 11 4-lb Weights of fish collected from Waterville Lake for tissue analysis, 2004-2009 . . . . . . . . . . . . . . . . . 12 6-1 TCDD concentrations in carp fillets collected from the Pigeon River, 1990-2009 (Stations 4A and 4B) . . . . . . . . . . . 25 6-2 TCDD concentrations in catfish fillets collected from the Pigeon River, r 1997-2009 (Stations 4A and 4B) . . . . . . . . . . . . 26 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 2009 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 2009 fish tissue sampling report using the revised protocol of 2006. Bottom feeding species (channel catfish and common carp) were collected in August 2009 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 2,3,7,87TCDD 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 (1.1 ppt) in fillet composites collected at Station 4A, and at Station 4B was estimated at 0.93 ppt (level below reporting limit). In the common carp whole body composite collected at Station 4B, the concentration of 2,3,7,8-TCDD was estimated at 0.68 ppt (level below reporting limit). The concentration of 2,3,7,8-TCDF was estimated at 0.52 ppt in common carp fillets at Station 4A, and 2.9 ppt was measured in common carp fillets at Station 4B. The mean weights of common carp collected from Stations 4A and 4B (4.335 kg, Station 4A; 4.848 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 other previous years (2008, 4.727, Station 4A, 4.067, Station 4B; 2006, 4.505 kg, Station 4A, 5.637 kg, Station 4B; 2005, 3.857 kg - Station 4A, 4.695 kg- Station 4B; 2004, 3.750 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 2009 were 11-17%. 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. This sampling year (2009) completes this additional two year request for 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, 1990-2009 (Stations 4A and 4B). 70 - 1 60 \ \ 50 \ Station 4A \ \ -t-Station 46 40 V \ - m \ c i 30 a \ 0 \ p 20 U \ H \ 10 0 - 19901991 1992 1993 1994 1996 1996 1997 19981999 2000 2001 2002 2003 2004 2005 2006 2007 2008 2009 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- 2009 (Stations 4A and 413). 2.50 2.00 _ --♦- Station 4A w- Station 4B c 01 .50 N r 1.00 m Lf. � b b p a ' f ■ b p � ■ U ■ b �\ a 11- 0.50 -- •- - i b a 0.00 1997 1998 1999 2000 2001 2002 2003 2004 2005 2006 2007 2008 2009 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 46, 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 2009 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 2009 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 2009 fish tissue study is number 20 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, 2008, and 2009)). 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., 2009). 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 2009 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, 2007, and 2008 (Henry and Wilson 2007, 2008, and 2009), 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 2009 was approximately at full pool and was similar to water levels in 2006. Stations 4A and 4B sample areas covered approximately the same surface area as water levels in 2004-2006. 2 Table 2-1. Pigeon 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) steep banks with little cover. 3 Figure 2-1. Fish tissues were collected from two sites (4A and 4B) for dioxin analyses 1 in 2009. More precise geographical locations of each site are presented in Figure 2-2. BN�)pM1n,iN HalloW.1N xcar erouire BRtlge (�'g) TOWSSEE N C neeeCroe /,••••,�re k ^••_• NORTH` .�..�• CAROI➢1A ' Rse) i L O"'� �/ NOTE:River mRes of nulnsWm mmpltng lecatl¢n or m(060)-1 T Nbu6ry mouth sh0vm in parentk¢sea. 2 �Bypa0setl 3 xe0ck AFah¢nae.n .Sampling SM.l �e w9W¢D. ltbl¢MPOLNm cearwcrne 4B Q k G H op (N1.11 4A 1426j+ Cmak N 101 oem W WHepcu Datlge RNwsid (40 Wpm e.g. (MJ) (4£1) ADo ul ebco �RCW 1 1 ae0k F . (W-11 � (40.0) B0lew eyag (A.1) T(61e 0�F Fug .Baaeo Ism g0ee0CI R6 fi. (+10) Flb0 u (6S0) Wryn 1`A.01WWTp me 000a1 Lemon,NC WOynavgb C11V4NC (CG.gI (54A) 4 Grassy Klwb i Illy' op U.WNNMDmn � WAT C.g Ria � k IR � N \ 286 � yN-a n MsxbnNl ASrry�n fr.�.r��;a 354s - p eri°°1347 17347 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 (Ictalums puuctatus) were the targeted species at sites 4A and 4B. In addition to fillet samples, one whole body common carp was collected from Station 4A. 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 4A 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 2009 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. r � 6 --1 4. FISH COLLECTION TECHNIQUES AND LEVEL OF EFFORT Sampling was conducted during 3-4 August 2009. 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 2009, the mean total length of carp was 672 mm and fish ranged from 620-698 mm. In 2008, the mean total length for carp was 663 mm and fish ranged from 630-686 mm. Previously, fish collections were conducted by EA Engineering, Science, and Technology (see References), and the mean for carp total length was 618 mm 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). f ' 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 0.8 h electrofishing and 78.9 h gill netting. 7 4 Table 4-1. Fish collection techniques and level of effort. Station Sampling Sampling Number RM Dates Techniques Level of Effort Comments 4A 41.5 Mug 09 Gill nets 9.5 h An approximate 1.0 RM reach of river was sampled; sampling involved gill net sets just off shorelines and mid channel;the entire Boat 0.8 h area was electrofished. electrofishin 4B 39.0 4 Aug 09 Gill nets 69.4 h An approximate 1.4 RM reach was sampled; sampling involved gill nets at selected locations throughout the entire area. Nets were set off Boat 0.0 h the shoreline areas.Electrofishing was not utilized since sufficient electrofishing numbers of fish were collected in gill nets. 8 Table 4-2. Summary of fish composites collected at two stations in Waterville Lake, August 2009. Total Total Length whole body Date Station Species (HIM) (g) Sample type Composite 3 Aug 09 4A Channel catfish 493 1015 Fillet Ra (RM 41.5)Channel catfish 578 2200 Fillet R Channel catfish 520 1355 Fillet R MEAN 530 1523 4A Common carp 620 3380 Fillet R (RM 41.5)Common carp 653 3925 Fillet R Common carp 667 4190 Fillet R Common carp 698 5260 Fillet R Common carp 690 4920 Fillet R MEAN 666 4335 3 Aug 09 4A Common carp 697 4760 Whole body WBb (RM 41.5) 4 Aug 09 4B Channel catfish 469 910 Fillet R (RM 39.0)Channel catfish 574 1670 Fillet R Channel catfish 467 925 Fillet R Channel catfish 470 1130 Fillet R Channel catfish 535 1250 Fillet R MEAN 503 1177 4 Aug 09 4B Common carp 696 4800 Fillet R (RM 39.0)Common carp 647 4200 Fillet R Common carp 660 4460 Fillet R Common carp 675 5500 Fillet R Common carp 689 5280 Fillet R MEAN 673 4848 Ra right fillet composite WBb whole body composite 9 Target species were collected at both sampling stations in 2009. 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 three channel catfish and five common carp at Station 4A, and five channel catfish and five common carp at Station 4B. A single bottom feeder whole body common carp from Station 4A was submitted for analysis (Table 4-2). All 18 composites submitted for analysis in 2009 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-la-b 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 2009. The size of the carp taken for whole body tissue analysis from Station 4A in 2009 was similar to size of whole body fish collected in previous years. 10 CD Length (mm) A w O cn 0 L" 0 cn C 01 0 O O O O O O O O O 0 4A Cat 4A Carp 0 4B Cat V CD o 4B Carp CD Whole 0 4A Cat N Jw N 4A Carp EL $ 4B Cat (D 4B Carp CD r Whole C 4A Cat N 4A Carp y CD 0 Q� G 4B Cat { � rn 4B Carp Whole CD IP 4A Cat N 5 N 4A Carp y 0 0 4B Cat C N 4B CarpCD C CD Whole (D 4A Cat = 4ACarp -f .1 NCO 0 4B Cat 00 4B Carp Whole ■ mn 4A Cat N 4A Carp $ 4B Cat r- 4B Carp `ti Whole Max, Min and Mean of Weights taken from Fish Tissue Samples 2004-2009 9000 8000 7000 6000 5000 Cn 4000 0 3000 2000 1000 0 .. Q "r a a) "r Q — Q N Qf0 fa fa s N fa (a Qr.. Q a) N 0- M a°)c ° ca ° CU U to U ca to U as ° U ai U Ca ° Ca M Ca to ca U CO U m U L Q U U L Q U V L Q U m U L Q U U Q U m U L vQICTCp vQvm QVm d It CO Qvm Q9Tom 2004 2005 2006 2007 2008 2009 Figure 4-lb. Weights of fish collected from Waterville Lake for tissue analyses, years 2004-2009. 12 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 forth 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. 13 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 8/12/09 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. r 14 6. ANALYTICAL RESULTS The fish tissue samples were received in one shipment(8/12/09) at TestAmerica under chain-6f- 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 2001a). 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 2009 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 (1.1 ppt) in fillet composites collected at Station 4A, but was below detection level at Station 4B and estimated to be 0.93 ppt. In the common carp whole body composite collected at Station 4A, the concentration of 2,3;7,8-TCDD was estimated at 0.68 ppt. The concentration of 2,3,7,8-TCDF was below detection and estimated to be 0.52 ppt in common carp fillets at Station 4A, and was 2.9 ppt at Station 4B.The concentration of 2,3,7,8-TCDF in the common carp whole body sample collected at Station 4A was 1.6 ppt(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). hi cases where concentrations were below the level of detection, a value of 15 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. r , 16 Table 6-1. Summary of the Pigeon River fish tissue analysis results 2009. Station Percent Number Sample ID Composite/Sample Type 2,3,7,8-TCDD(°) 23,7,8-TCDF�a) Lipid 4A SITE 4A channel catfish 3 fillet samples 0.52b ND(DL=0.41) 9.5 SITE 4A common carp 5 fillet samples 1.1 0.52(b•`) 11.0 SrM 4A common carp 1 whole body sample 0.68ro' 1.6 6.8 4B SITE 4B channel catfish 5 fillet samples ND (DL=0.43) ND(DL=0.26) 7.0 SITE 4B common carp 5 fillet samples 0.93b 2.9 17.0 (a)Units=ppt(parts per trillion) or pg/g(picogram/gram) (b)Estimated results. Result is less than the reporting limit (c)Analyte was positively identified,but the quantitation is an estimate. (ND)Not detected, concentrations below the instrument detection limit(DL). 17 Table 6-2. Toxicity equivalence factors for CDD/F isomers. DIOXIN DIBENZOFURAN Isomer(a) TEF(b) 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-HxCDF 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-HpCDF 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. 18 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 0.058 ppt for channel catfish fillets collected'at Station 4B to 1.496 ppt for common carp collected from Station 4B. The values reported in years 2005-2008 for channel catfish are consistent with the results for 2009. Common carp TEQ results in 2007 were higher (Station 4A, 13.44 ppt; Station 4B, 5.35 ppt) than observed in previous years (2005-2006), and results for 2008 and 2009 (2009, Station 4A, 1.562; Station 4B, 1.496 ppt) are further evidence that the 2007 results were anomalous. The whole body sample for common carp collected at Station 4A had a TEQ result of 1.366 ppt. Table 6-4 illustrates 2,3,7,8 TCDD concentrations in common carp fillet samples collected in 2005, 2006, 2007, 2008, 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 (4.335 kg, Station 4A; 4.848 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 (2008, 4.727- Station 4A, 4.067 Station 4B; 2006, 4.505 kg - Station 4A, 5.637 kg - Station 4B; 2005, 3.857 kg - Station 4A, 4.695 kg- Station 4B; 2004, 3.750 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 2009 were 11.0-17%. 19 J Table 6-3. Summary of CDD/F isomer analyses, toxicity equivalent factors, and toxicity equivalent values for the 2009 Waterville Lake fish. STATION 4A Channel catfish fillet Common carp fillet Common car whole body TE CDD/F isomers TEF(°) Results(a) Q2 Results(a) TEC)" Results° TE c! Dibenzodioxin 2,3,7,8-TCDD 1.0 ND 0.52 1.1 1.1 0.68d 0.68 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 3.0d 0.300 3.5d 0.35 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 10 0.10 16 0.16 OCDD 0.0003 8.8d 0.003 27 0.008 54 0.016 Dibenzofuran 2,3,7,8-TCDF 0.1 ND 0.000 0.52 0.052 1.6 0.16 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 1,2,3,4,7,8-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 0.523 1.560 1.366 20 Table 6-3 (cont). Summary of CDD/F isomer analyses, toxicity equivalent factors, and toxicity equivalent values for the 2009 Waterville Lake fish. STATION 4B Channel catfish fillet Common carp fillet CDD/F isomers TEFI`I Results(a) TB ! > Results(') TEOcn� Dibenzodioxin 2,3,7,8-TCDD 1.0 ND 0.000 0.93d 0.93 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 2.5d 0.25 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 5.1 0.051 12 0.012 OCDD 0.0003 23 0.007 45 0.014 Dibenzofuran 2,3,7,8-TCDF 0.1 ND 0.000 2.9 0.29 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 0.058 1.496 (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. 21 Table 6-4. Blue Ridge Paper Canton Mill fish fillet tissue analysis results, 2005—2009 2005 Results(d) 2006 Results(e) Number Length Range Number Length Range Station Species of fish (mm) 2,3,7,8-TCDD('b) Station Species of fish (mm) 2,3,7,8-TCDD( ") I Black redhorse 5 359-384 ND(0.35) 4A Common carp 3 635-692 0.64(`) 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(`) RM 59.0 Channel catfish 3 443-460 ND(0.29) RM 39.0 Channel catfish 4 510-590 0.77(`) 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 0.76(`) 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 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 1 Table 6-4 (cont). Blue Ridge Paper Canton Mill fish fillet tissue analysis results, 2005—2009 2007 Results(d) 2008 Results(e) Number Length Range Number Length Range Station Species offish (min) 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 3 653-686 1.2 RM 41.5 Channel catfish 4 490-593 0.57�`) RM 41.5 Channel catfish 5 475-525 ND(0.29) 4B Common carp 5 672-728 ND(6.9) 4B Common carp 3 630-665 ND(0.36) RM 39.0 Channel catfish 5 505-670 0.67'`1 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 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 23 Table 6-4 (cont). Blue Ridge Paper Canton Mill fish fillet tissue analysis results, 2005 —2009 2009 Results(d) Number Length Range Station Species offish (mm) 2,3,7,8-TCDD(�b) 4A Common carp 5 620-698 1.1 RM 41.5 Channel catfish 3 493-578 0.52t`t 413 Common carp 5 647-696 0.93(`) RM 39.0 Channel catfish 5 467-574 ND(0.43) Total fish filleted= 18 (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 24 Figure 6-1. TCDD Concentrations in Carp Fillets Collected from the Pigeon River, 1990-2009 (Stations 4A and 4B). 70 t 60 \ 50 \ 0 Station 4A / \ —t-Station 4B O 40 \ `m \ a 30 1O \ a p 20 \ F \ 10 �. b Y � � 0 — 19901991 1992 1993 1994 1995 1996 1997 1998 1999 2000 20012002 2003 2004 2005 2006 2007 2008 2009 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. 25 Figure 6-2. TCDD Concentrations in Catfish Fillets Collected from the Pigeon River, 1997- 2009 (Stations 4A and 4B). 2.50 2.00 _ --�- Station 4A Station 4B c 0 1.50 CL a, • 1.00 m 0 .• a 0.50 a ■ b a 0.00 1997 1998 1999 2000 2001 2002 2003 2004 2005 2006 2007 2008 2009 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. 26 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 hie. 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 hie. 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. 27 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 hie., Canton, North Carolina. December. EA Engineering, Science, and Technology hie. 2001c. Results of the 2001 Dioxin Monitoring in Fish Tissue. EA Report No. 13900.01, prepared for Blue Ridge Paper Products hie., 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 hie., Canton, North Carolina. December. i 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, hie., Canton Mill, Canton, North Carolina. January 2006. Henry,T.B., and J.L. Wilson. 2006. Results of 2006 dioxin monitoring in fish tissue. Prepared for Blue Ridge Paper Products, Inc., Canton Mill, Canton, North Carolina. December 2006. 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. 28 Henry, T.B., and J. L. Wilson. 2008. Results of 2008 dioxin monitoring in fish tissue. Prepared for Blue Ridge Paper Products, Inc., Canton Mill, Canton, North Carolina. November 2008. 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 11: Health Assessment of 2,3,7,8-Tetrachlorodibenzo-p-dioxin(TCDD) and Related Compounds. 29 2 0 0 90 oj xM�on lour n I I no F Ish T I s ,ink fi 4 "APPENDICES" Blue Ridge Paper Products Inc dba Evergreen Packaging Canton , NC APPENDIX A CHAIN OF CUSTODY FORM 31 e Chai ➢ of Temperature on Receipt T esT^m e c ruS,f:dy Pecord r61.4124(1037) Drinking Water? Yes No Lid THE LEADER IN ENVIRONMENTAL TESTING _ --- t Clra Project Manager r� — rya�AA�.s1TJ- � 1l �j �„py,� f _ Yv, Lam// Darn Chain of C-711(r-%r% r, Address � � Telephone Nnm r(Area Code)/Far.Number Lab N tuber _ r�• _ 'V 1+1 V oty State Zp C000lt} Sire Conlacr Lab Contact na/ysls(Attach list i! Page' of G1 t!U 1 a Ye _ I ydj Z O 71 /' ���6 more space is needed) d fi Pr-c/orytN e�snd ifon( (ate) 0 meffwaybdl Number p Q ConlracbPurchase OidedQuote No. Containers& p Special instrUctions/ Matrix Prese ti I Conditions of Receipt _ t rvaves BCS ,� I � , 1 Sample 1.D.No.and Description' m Date Pine ! w (Contamers for each sample maybe combined on one line) Prt e -tt f't7�H4110 Cal •� fiS t_Lf I)�7l I I v+r- Ar 01vilf,s> P?.6k4-14K — �r l5Al _ t:;, N _ , CP ClN!ly}nn r rp (J a Possible HBZard/tlenfilcelion - � Sample Disposal — Non-Hawed ❑Flammable (A tee may be assessed if samp(ea are retained []Skin Irritant ❑ Porson 8 ❑ Unrcnown [j Nerum To Client Disposa!ByLab ❑Archive For Months longer than i month) TLmAmund Tlme Requin?d ----'pC Requirements(SpeuJy) ❑24Hou Hours ❑ 7Days .: ❑ 14Days ❑21Days ❑ other 1,Relfnq is y Date Tme 1.Rererved ey Date Time , RB/inquts B Da lime 2.Rec -J �y. .� �t�y `�y ' -U 3 3o A 2- i0 € 1 I rme tP H 3,Harinqui5heef By Date T'me 3.flecerved bate Time TComments N m DISTRIBUTION: WHITE-Returned to Ctrent wdh Report; CANARY-Stays with the Sample; PINK-Field Copy i APPENDIX B TESTAMERICA WEST SACRAMENTO ANALYTICAL REPORT _ 1 32 10 TestAmeneca AMU THE LEADER IN ENVIRONMENTAL TESTING - August 31, 2009 TestAmerica Project Number: G9H120259 PO/Contract: 10016001 Nick McCracken Blue Ridge Paper Products Inc PO Box 4000 Canton, NC 28716 Dear Mr. McCracken, This report contains the analytical results for the samples received under chain of custody by TestAmerica on August 12, 2009. These samples are associated with your 7605001S 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, Jill Kellmann Project Manager 880 Riverside Parkway West Sacramento, CA 95605 tel 916.373.5600 fax 916.372.1069 www.testamericaine.com GOH120259 TestAmerica West Sacramento(916)373-6600 1 of 518 r r Table of Contents TestAmerica West Sacramento Project Number G9H120259 Case Narrative Quality Assurance Program Sample Description Information Chain of Custody Documentation BIOLOGIC, 8290, Lipids, Percent (8290), Samples: 1, 2, 3, 4, 5 Sample Data Sheets Method Blank Report Laboratory QC Reports BIOLOGIC, 8290, Dioxins/Furans . Samples: 1, 2, 3, 4, 5 Sample Data Sheets G9H120259 TestAmerlca West Sacramento(916)373-5600 2 of 518 ( i Case Narrative TestAmerica !lest Sacramento Project Number C9HI2O259 BIOLOGIC, 8290, Dioxins/Furans Sample(s): 2, 4, 5 The above samples required a Confirmation (CON) analysis for 2,3,7,8-TCDF which occurred on August 29, 2009. Sample(s): 2 Analyte 2,3,7,8-TCDF in sample 2 has been qualified with a "Q" flag as the ion abundance ratios is outside of criteria. This analyte has been reported as an "estimated maximum possible concentration" (EMPC) because the quantitation is based on the theoretical ion abundance ratio for these analytes. Sample(s): 1, 2, 3, 4, 5 Several internal standard recoveries are lower than the method recommended criteria in the laboratory method blank associated with the samples. Generally, data quality is not considered affected if the internal standard signal-to-noise ratio is greater than 10:1, which is achieved for all internal standards in the sample. All detection limits are below the lower calibration limit and there is no adverse impact on data quality. There were no other anomalies associated with this project. G911120259 TestAmerica West Sacramento(916)373-5600 3 of 518 � r tN Al Test e�°Ica �tE 90,y c U � THE LEADER IN ENVIRONMENTAL TESTING a .. x TestAmerica Laboratories West Sacramento Certifications/Accreditations Alaska UST-055 New York* 11666 Arizona AZ0708 Ore one CA200065.= Arkansas 88-0691 Pe lvania 68-1272 "California* 01119CA South Carolina `arc'= 1 .- 8701'4, Colorado NA Texas T104704399-08-TX Connecticut = PH 691 Utab* UANI Florida* E87570 Virginia 00178 960 0 Was hm od. G12$1 h Hawaii NA West Vir ' is J9930C,334 IDinois'-_ 2'00060 �T ,Wisconsin,',` 998204686"- Kansas* E-10375 NFESC NA ',Lotiisiah0 30612 USAGE" ' NA Michi an 9947 USDA Foreign Plant 37-82605 "NavaBa;.': :CAd4-r p .fUSISAForet =Soiles *. `.P330=09-00036, New Jersey* CA005 US Fish&Wildlife LEI48388-0 GWho .. *NELAP accredited A more detailed parameter list is available upon mgwsL Updated 3/25/20091 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(DIJ):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 uncertainty of the test results. G9H720259 TestAmerica West Sacramento(916)373-5600 4 of 518 SAWLE SUMMARY G9H120259 SAMPLED SAMP WO # SAMPLE# CLIENT SAMPLE ID DATE TIME LH2XN 001 SITE 4A CHANNEL CAT(R) 08/03/09 14:00 LH2XX 002 SITE 4A COMMON CARP(R) FILLETS OB/03/09 15:11 LH2X5 003 SITE 4B CHANNEL CAT(R) FILLETS 08/04/09 10:17 LH2X9 004 SITE 4B COMMON CARP(R) FILLETS 08/04/09 10:54 LH2OJ 005 SITE 4A COMMON CARPWB (WHOLE BODY) 08/03/09 16:00 NOTE(S) - -The analytical results of the samples listed above am presented on she following pages. -All calculations are perfosmod before rounding to avoid roasdoff coons in calculated results. -Results owed as'NO'were nor detwed at or above the stated Grit. -7N$report mutt rot be reproduced,CIMI in full,without the wAlfen approval of the laboratory. -Results for the following pammccs are never reported on a dry weight basis:colon,corrosivity,density,flash;ohn,ignitabiGly,layers,odor, pains finer IU,pA.porosity pressure.reaction➢.redoX potential,Wdfe gravity.spot tests,solids.wlubiliry, erperature,visensity,and weight. G9H120259 TestAmerica West Sacramento(916)373-5600 5 of 518 N O'heain of Temperature on Receipt Te5 ' i�e�ECa Custody E eCord Drinking Water? Yes❑ Nou THE LEADER IN ENVIRONMENTAL TESTING TrLnza pow) , Pmlact Manager Date f Y N Chain of Custo_�dryfyNumber Address telephone Nunl r(Arrea CocfollFax Number 1� v � —n� m V l 1 n � Lab N mbar Page' r of f Cny sAte�le Zp Code Sire Contact Lab Contact nalysis ABach list if 1 GA- $ y, 'vr ' 'z�"��� more space is needed) h Prc/or51 Na osnd /(¢af.n(/gale) e CernenWaybirl Number �_"'� 314Q 1 C - Special oniracbPurchass OrderlQuota No. Containers N 0 p — MatrLr preservativesXOrj b �tConditions of Receipt .i Semple I.D.No_and Description' H (Containers for each sample may be combined on one line) Date TimB ¢ 4 i = Z g i -4 24- a '.It ct�&xd1e6ta C1� s �f3 11��1 I 3S1" 4 -eta d tr� g !Ig E' 10S9 _ CS, -6d m r dp9 coJr7 -; _ -•( • tro!+h"�^ � � J + C� �?�?J - (L-�f(�� I jl A Possible HTwardfdentirt—hon Sample Olsposal — -- -- — (A lee maybe assessed ifsamples am m!aincd Non-HazaM ❑ Flammable 0;Skm Irribril ❑ Prnson B ❑ Umm�own M Rerum To Client Disposal By Lab ❑ArGtive For Months longer than 1 month) Tum Amund Time Required - QC Requirements(Speedy) ❑24Hou C4V14ours ❑ 7Days .. ❑ 14 Days ❑21 Days ❑ Other__ - �.,• i.Rating 1s Dale Time I.Recervedeyr/'- --) _ �t Date Time 2 'ngms B f^ Ime a ZRacal By Dare.-r L�R" Tim f�Jv� 3.Rem dis ed V f�. \. b " Cf 9 BJ' I Date I Trme 3.Received I m O1 Comments N ®DISTRIBUTION: WHITE-Retumetl fo Cfrent lNm Report; CANARY-Stays with Me Sample; PINK-Field Copy { I LIST T st ric stA RECEIPT t Sacramento Tes4�smerica West SacramenQo THE LEADER IN ENVIRONMENTAL TES-ING CLIENT 7 _plo-ZL LOG# G LOT#(QUANI IMS ID)_ QUOTE#-,;),:W,6�_�LOCATION 7(O Initials Date DATE RECEIVED TIME RECEIVED -_— DELIVERED BY Q'FEDEX ❑ CA OVERNIGHT ❑ CLIENT ❑AIRBORNE ❑GOLDENSTATE ❑ DHI ❑ UPS. ❑ BAX GLOBAL ❑ CO-GETTERS ❑TAIL COURIER ❑VALLEY LOGISTICS ❑ MORGAN HILL COURIER ❑OT_H�EER CUSTODY SEAL STATUS �INTACT ❑ BROKEN ❑ N/A _ CUSTODY SEAL#(S) 1-qGI Z '7 ,�J,����1,�7 f SHIPPPING CONTAINERS ❑TAL T�CLIENT ❑ WA TEMPERTURE RECORD (IN°C) IR 4❑ 5,� ❑ OTHER-_ ___ CDC#(S) 7 -", 1(2 G ^MPERATURE BLANK Observed:�AA - Corrected_^ kMPLE TEMPERATURF�i Observed.=�t4 :.-�I . _::. � Average: r�t Z Corrected Average- 4t )"u 6GI' COLLECTOR'S NAME: ❑Verified from COC g'Not on CDC _ pH MEASURED ❑ YES ❑ ANOMALY .[J N/A LABELED BY............... ..... . .......... . ... .. ... .. ................ .. . LABELS CHECKED BY....... .... ................ . ........................ ... PEER REVIEW SHORT HOLD TEST NOTIFICATION SAMPLE RECEIVING _ WETCHEM E5N/A VOA-ENCORES[P-VIA _ ❑ METALS NOTIFIED OF FILTER/PRESERVE VIA VERBAL&EMAIL N/A COMPLETE SHIPMENT RECEIVED IN GOOD CONDITION WITH El N/A 9 APPROPRIATETEMPERATURES, CONTAINERS, PRESERVATIVES ❑ CLOUSEAU ❑TEMPERATURE EXCEEDED (2°C-6-C) Id/A _ C�,r�/ cp ❑ WET ICE ❑ BLUE ICE ❑ GEL PACK ❑ NO COOLING AGENTS USED ❑ PM NOTIFIED tes: •1 Acceptable temperature range for State of Wisconsin samples is<4°C. G9H120L*&VE NO SPACES BLANK. USE'NIX IF N%Mj1nneIQWmt Sacramento(916)373-5600 OA-1854109 RKE 7 of 518 TestAmerica West 5a .ament© Bode Lot Inventory .TEST C ID: eee�� TrF.eADFR IN$•PIIfCHMFNTP, TEaPNe ID: 1 2 3 4 5 617 8 9 10 11 12 13 14 15 16 17 1 18 1 19 20 VOA' IZZI VOAh' — - — AGB AGBs 250AGB 1 250AGBs 250AGBn 1 500AGB I AGJ 500AGJ 250AGJ i 125AGJ CGJ 500CGJ 250CGJ 125CGJ 500PJ 500PJn I 500PJna I 500PJzn/na 250PJ 250PJn 250PJna -t---� i 250PJzn/na I Acetate Tube TT Encore Folder/filter PUF 1 Petri/Filter _J XAD Trap Ziploc 1 2 3 1 4 5 6 7 8 9 1 10 11 1 12 13 14 15 16 1 17 18 19 20 j F -`---drochloric acid s= sulfuric acid na=sodium hydroxide n = nitric acid zn=zinc acetate I er of VOAs With air bubbles present/total number of VOA's QA-1854/09 RKE LEAVE NO SPACES BLANK USE"NA"IF NOT APPLICABLE GBH120259 TestAmerlea West Sacramento(916)373-5600 8 of 518 f � BIOLOGIC , 00 , Dioxins/Fur ns GgH120259 TestAmerica West Sacramento(916)373-5600 9 of 516 f � Blue Ridge Paper Products Inc . Client Sample ID: SITE 4A CHAN:dEL CAT(R) Trace Level Organic Compounds Lot-Sample #.__ : G9H120259-001 Work Order #...: LH2XNIAC Matrix....... ..: BIOLOGIC Date Sampled---: 08/03/09 Date Received..: 08/1:i/09 Prep Date...... : 08/19/09 Analysis Date..: 08/29/09 Prep Batch #---: 9230398 Dilution Factor: 0.96 DETECTION PARAMETER RESULT LIMP"_ UNITS METHOD 2,3,7,8-TCDD 0.52 J pg/g SW846 8290 Total TCDD 0-52 pg/g SW846 8290 1,2,3,7,8-PeCDD ND 0.70 pg/g SW846 8290 Total PeCDD ND 2.3 pg/g SW846 8290 1,2,3,4,7,8-HxCDD ND 0.35 pg/g SW846 8290 1,2,3,6,7,8-HxCDD ND 1.3 pg/g SW846 8290 1,2,3,7,8,9-llxCDD ND 0.32 pg/g SW846 8290 Total HxCDD ND 1.3 Pg/g SW846 8290 112,3,4,6,7,8-HpCDD ND 2.3 pg/g SW846 8290 Total HpCDD ND 2.3 pg/g SW846 8290 OCDD 8.8 J Pg/g SW846 8290 2,3,7,8-TCDF U]D 0.41 Pg/g SW846 8290 Total TCDF 2.9 pg/g SW846 0290 1,2,3,7,8-PeCDF ND 0.30 pg/g SW846 8290 2,3,4,7,8-PeCDF ND 0.70 pg/g SW846 8290 Total PeCDF ND 1.1 pg/g SW846 8290 1,2,3,4,7,8-HxCDF ND 0.44 pg/g SW846 8290 1,2,3,6,7,8-HxCDF ND 0.16 pg/g SW846 8290 2,3,4,6,7,8-HxCDF ND 0.12 pg/g SW846 8290 1,2,3,7,8,9-HXCDF ND 0.087 pg/g SW846 8290 Total HxCDF ND 1.2 Pg/g SW846 8290 1,2,3,4,6,7,8-HpCDF ND 0.19 pg/g SW846 8290 1,2,3,4,7,8,9-HeCDF ND 0.054 Pg/g SW846 8290 Total HpCDF NO 0.19 pg/g SW846 8290 OCDF AID 0.079 pg/g SW846 8290 PERCENT RECOVERY INTERNAL STANDARDS - RECOVERY LIMITS_ 13C-2,3,7,8-TCDD 90 (40 - 135) 13C-1,2,3,7,8-PeCDD 96 (41) - 135) 13C-1,2,3,G,7,8=HXCDD 86 (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 93 (40 - 3.35) 13C-1,2,3,7,8-PeCDF 92 (40 - 135) 13C-1,2,3,4,7,8-HKCDF 93 (40 - 135) 13C-1,2,3,4,6,7,8-HpCDF 90 (40 - 135) NOTE(S) : d Estimated resuh.Result is less than the reporting limit G9HU0259 TestAmerica West Sacramento(916)373-6600 10 of 518 � c Blue Ridge Paper Product:: Inc Client Sample 1D: SITE 4A COMMON CFh'RP(R) FILLETS Trace Level Organic Compounds Lot-Sample #-..: G9H120259-002 Work Order #...: LH2X7•:lAC Matrix.. ... ....: BIOLOGIC Date Sampled...: 08/03/09 Date Received..: 08/12/09 Prep Date.-.... : 08/19/09 Analysis Date..: 08/25/09 Prep Batch #...: 9230398 Dilution Factor: 0.95 DETECTION PARAMETER RESULT LIMI" UNITS METHOD 2,3,7,8-TCDD 1-1 Pg/g SW846 8290 Total TCDD 1.1 pg/g SW846 8290 1,2,3,7,8-PeCDD ND 0.92 pg/g SW846 8290 Total PeCDD 16 0.92 pg/g SW846 8290 1,2,3,4,7,8-HxCDD NO 0.90 pg/g SW846 8290 1,2,3,6,7,E-HxCDD 3-0 T Pg/g SW846 8290 1,2,3,7,8,9-HxCDD 111D 0.36 pg/g, SW846 8290 Total HxCDD 3-0 pg/g SW846 8290 1,2,3,4,6,7,8-HpCDD 10 Pg/g SW846 8290 Total HeCDD 3.0 Pg/g SW846 8290 OCDD 27 pg/g SW846 8290 2,3,7,B-TCDF 0.52 CON,,T,Q pg/g SW846 8290 Total TCDF 39 pg/g SW846 8290 1,2,3,7,8-PeCDF ND 0.92 pg/g SW846 8290 2,3,4,7,8-PeCDF NO 1.1 pg/g SW846 8290 Total PeCDF 13 pg/g SW846 8290 1,2,3,4,7,8-HpCDF NO 2.0 pg/g SW846 8290 1,2,3,6,7,E-HxCDF NO 0.35 pg/g SW846 8290 2,3,4,6,7,8-HXCDF NO 0.021 pg/g SW846 8290 1,2,3,7,8,9-HpCDF ND 0.16 pg/g SW846 8290 Total HpCDF 33 pg/g SW846 8290 1,2,3,4,6,7,8-HpCDF IdD 1.0 pg/g SW846 B290 1,2,3,4,7,8,9-HpCDF ND 0.17 pg/g SW846 8290 Total HpCDF NO 1.9 pg/g SW846 8290 OCDF NO 0.19 pg/g SW846 8290 PERCENT RECOVERY INTERNAL STANDARDS RECOVERY LIMITS _ 13C-2,3,7,8-TCDD 91 (40 - 135) 13C-1,2,3,7,8-PeCDD 94 (40 - 3.35) 13C-1,2,3,6,7,8-HXCDD 92 (40 - 135) 13C-1,2,3,4,6,7,8-HpCDD 102 (40 - 135) 13C-OCDD 97 (40 - 135) 13C-2,3,7,8-TCDF 90 (40 - 135) 13C-1,2,3,7,8-PeCDF 90 (40 - 135) 13C-1,2,3,4,7,8-HxCDF 101 (40 - 135) 13C-1,2,3,4,6,7,8-HpCDF 98 (40 - 135) NOTE(S) : J Esanmmd resWL Result is lms than am tepmting limit. CON Confnnadonanalysis. Q Fstimatmm xirn=pnssibletw =nzion aWC). G9H120259 TestAmerlca West Sacramento(916)373-5600 11 of 518 r Blue Ridge Paper Products Inc I, l Client Sample ID: SITE 4B CHANNEL CAT(R) FILLETS Trace Level Organic Compounds Lot-Sample #-..: G9P120259-003 Work Order #...: 1,112X';IAC Matrix- ...... .-: BIOLOGIC Date Sampled-.-: 08/04/09 Date Received..: 08/12/09 Prep Date..... .: 08/19/09 AnalYSiS Date_- ; OB/29/09 Prep Batch (). ..: 9230398 Dilution Factor: 0.96 DETECTION PARAMETER RESULT LIMP-'_-_. UNITS METHOD 2,3,7,8-TCDD ND 0.43 pg/g SW846 8290 Total TCDD ND 0.43 pg/g SW846 8290 1,2,3,7,8-PeCDD ND 0.69 pg/g SW846 8290 Total PeCDD ND 2.0 pg/g SW846 8290 1,2,3,4,7,8-HXCDD ND 0.37 pg/g SW846 8290 1,2,3,6,7,8-HXCDD ND 1.4 pg/g SW846 8290 1,2,3,7,8, 9-HXCDD ND 0.32 pg/g SW846 8290 Total HXCDD ND 1.4 pg/g SW846 8290 1,2,3,4,6,7,8-1FpCDD 5.1 pg/g SW846 8290 Total HpCDD 7-6 pg/g SW846 8290 OCDD 23 pg/g SW846 8290 2,3,7,8-TCDF DID 0.26 pg/g SW846 8290 Total TCDF 11 pg/g SWB46 8290 1,2,3,7,E-PeCDF ND 0.35 pg/g SW846 8290 2,3,4,7,8-PeCDF ND 0.34 pg/g SW846 8290 Total PeCDF 2.7 pg/g SW846 8290 1,2,3,4,7, E-HXCDF NO 0.64 pg/g SW846 8290 1,2,3,6,7,8-HXCDF ND 0.14 pq/g SW846 8290 2,3,4,6,7,8-HXCDF ND 0.087 pg/g SW846 8290 1,2,3,7,8,9-HXCDF NO 0.073 pg/g SW846 8290 Total HXCDF 2.7 PgAr SW846 8290 1,2,3,4,6,7,8-HpCDF NO 0.12 pg/g SW846 8290 1,2,3,4,7,8,9-HpCDF ND 0.052 pg/g SW846 8290 Total HpCDF NO 1.1 Pg/g SW846 8290 OCDF ND 0.34 pg/g SW846 8290 PERCENT RECOVERY INTERNAL STANDARDS RECOVERY LIMITS 13C-2,3,7,8-TCDD 95 (40 - 135) 13C-1,2,3,7,8-PeCDD 98 (40 135) 13C-1,2,3,6,7,8-HXCDD 91 (40 - 135) 13C-1,2,3,4,6,1,8-HXCDD 98 (40 - 135) 13C-OCDD 91 (40 - 135) 13C-2,3,7,8-TCDF 92 (40 - 135) 13C-1,2,3,7,8-PeCDF 93 (40 - 135) 13C-1,2,3,4,7,8-HXCDF 93 (40 - 135) 13C-1,2,3,4,6,7,8-HpCDF 96 (40 - 135) G9H120259 TestAmerlca West Sacmmeoto(916)373-5600 12 o1518 Blue Ridge Paper Productrs Inc Client Sample 3D: SITE 4B COMMON CARP(R) FTT•LETS Trace Level Organic Compounds Lot-Sample #___: 099120259-004 Work Order #.._: LH2X91AC Matrix......... BIOLOGIC Date Sampled.__: 08/04/09 Date Received..: 08/19/09 , Prep Date... ...: 08/19/09 Analysis Date_. : 08/29/09 Prep Batch #.. .: 9230398 Dilution Factor: 0.98 DETECTION PARAMETER RESULT LIMIT UNITS METHOD 2,3,7,8-TCDD 0.93 J pg/g SW846 8290 Total TCDD 0.93 pg/g SW846 8290 1,2,3,7,8-PeCDD ND 0.76 pg/g SW846 8290 Total PeCDD ND 6.5 pg/g SW846 8290 1,2,3,4,7,8-HxCDD ND 0.84 pg/g SW846 8290 1,2,3,6,7,8-HxCDD 2.5 J pg/g SW846 8290 1,2,3,7,8,9-HXCDD NO 0.59 pg/g SW846 8290 Total HxCDD 2.5 pg/g SW846 8290 1,2,3,4,6,7,8-HpCDD 12 pg/g SW846 8290 Total HpCDD 3.5 pg/g SW846 8290 OCDD 45 pg/g SW846 8290 2,3,7,8-TmF 2.9 CON Pg/g SW846 8290 Total TCDF 30 pg/g SW846 8290 1,2,3,7,8-PeCDF ND 1.0 pg/g SW846 8290 2,3,4,7,8-PeCDF NO 1.1 pg/g SW846 8290 Total PeCDF 3.4 pg/g SW846 8290 1,2,3,4,7,8-HxCDF ND' 2.4 pg/g SW846 8290 1,2,3,6,7,8-HXCDF NO 0.32 pg/g SW846 8290 2,3,4,6,7,8-HXCDF ND 0.27 pg/g SW846 8290 1,2,3,7,8,9-HxCDF NO 0.030 pg/g SW846 8290 Total HxCDF 18 pg/g SW846 8290 1,2,3,4,6,7,8-HpCDF ND 0,97 pg/g SW846 8290 1,2,3,4,7,8,9-HpCDF NO 0.043 pg/g SW846 8290 Total HpCDF 2.G pg/g SW846 8290 OCDF NO 0.17 pg/g SW846 8290 PFRCENT RECOV_RY INTERNAL STANDARDS RECOVERY LIMITS 13C-2,3,7,E-TCDD 92 (40 - 135) 13C-1,2,3,7,8-PeCDD 95 (40 - 135) 13C-1,2,3,6,7,8-HxCDD 90 (40 135) 13C-1,2,3,4,6,7, 8-I1pCDD 97 (40 - 135) 13C-0CDD 94 (40 - 135) 13C-2,3,7,8-TCDF 89 (40 - 135) 13C-1,2,3,7,8-PeCDF 92 (40 - 135) 13C-1,2,3,4,7,8-HxCDF 95 (40 - 135) 13C-1,2,3,4:,6,7,8-HpCDF 96 (40 - 11s) NOTE(S) • J Psiimated result.Result is Iess limn dte tcpaning limit. CON Cwsanadon analysis. G9H120259 TestAmerlea West Sacramento(916)373-5600 13 of 518 r ( Blue Ridge Paper Products Inc Client Sample ID: SITE 4A COMMON CARTtWB (WHOLE BODY) Trace Level Organic Cocdpuunds LOt-Sample #.. . : G9H120259-005 Work Order #... : LH2O1-1AC Matrix. . .. .....: BIOLOGIC Date Sampled. . .: 08/03/09 Date Received. .: 08/12/09 Prep Date.. . .. .: 08/19/09 Analysis Date. .: 08/211/09 Prep Batch #.... 9230398 Dilution Factor: 0.96 DETECTION PARAMETER RESULT LIMI^ UNITS METHOD 2,3,7,8-TCDD 0.68 J pg/g SW846 8290 Total TCDD 0.68 pg/g SW846 8290 1,2,3,7,8-PeCDD NO 0.94 pg/g SW846 8290 Total PeCDD ND 3.9 pq/g SW846 8290 1,2,3,4,7,8-HXCDD NO 0.99 pg/g SW846 8290 1,2,3,6,7,8-1xCDD 3.5 J pg/g SW846 8290 1,2,3,7,B,9-HxCDD ND 0.45 pg/g SW846 8290 Total HxCDD 6.4 pg/g SW846 8290 1,2,3,4,6,7,8-HpMD 16 pg/g SW846 8290 Total HpCDD. 23 pg/g SW846 8290 OCDD 54 Pg/g SW846 8290 2,3,7,8-TCDF 1.6 CON pg/g SW846 8290 Total TCDF 16 pg/g SW846 8290 1,2,3,7,8-PeCDF NO 0.76 pg/g SW846 8290 2,3,4,7,8-PeCDF NO 1.2 pg/g SW846 8290 Total PeCDF 3-6 pg/g SW846 8290 1,2,3,4,7,8-HxCDF NO 1.6 pg/g SW846 8290 1,2,3,6,7,8-HXCDF NO 0.52 pg/g SW846 8290 2,3,4,6,7,8-HxCDF NO 0.13 pg/g SW846 8290 1,2,3,7,8, 9-HxCDF NO 0.15 pg/g SW846 8290 Total HxCDF 8.3 pg/g SW846 8290 1,2,3,4,6,7,8-HpCDF NO 1.0 pg/g SW846 8290 1,2,3,4,7,8,9-HeCDF ND 0.11 pg/g SW846 8290 Total HpCDF NO 1.3 pg/g SW846 8290 OCDF NO 0.14 pg/g SW846 B290 PERCENT RECOVERY INTERNAL STANDARDS RECOVERY LIMITS 13C-2,3,7,3-TCDD 94 (40 - 135) 13C-1,2,3,7,8-PeCDD 98 (40 - 135) 13C-1,2,3,6,7,8=HxCDD 87 (40 - 135) 13C-1,2,3,4,6,7,8-HxCDD 91 (40 - 135) 13C-OCDD 87 (40 - 135) 13C-2,3,7,8-TCDF 92 (40 - 135) 13C-1,2,3,7,8-PeCDF 93 (40 - 135) 13C-1,2,3,4,7,8-HXCDF 92 (40 - 135) 13C-1,2,3,4,6,7,8-HpCDF 88 (40 - 135) NOTE(S) : f Fstimmed rrsalt.RMtt is Ins than the repaning IimiL - - -- CON Con[ittwtian analysis G9H120259 TestAmerica West Sacramento(916)373-5600 14 of 518 r , Q� DATA ASSOCUTIONSUAWARY G9H120259 Sample Preparation and Analysis Control Numbers ANALYTICAL LEACH PREP SAMPLE# MATRIX METHOD BATCH # BATCH # MS RUN# 001 BIOLOGIC -SW846 8290 9230398 BIOLOGIC SW846 8290 9230412 002 BIOLOGIC SW846 8290 9230398 BIOLOGIC SW846 8290 9230412 003 BIOLOGIC SW846 8290 9230398 BIOLOGIC SW846 8290 9230412 004 BIOLOGIC SW846 8290 9230398 BIOLOGIC SW846 8290 9230412 .005 BIOLOGIC SW846 8290 9230398 BIOLOGIC SW846 8290 9230412 GSH120259 TestAmerica West Sacramento(916)373-5600 15 of 518 METHOD BLANK REPORT Trace Level Organic Compounds Client Lot #...: G9H120259 Work Order #. .-: LJCPt+DAA Matrix. ... . . . . -: BIOLOGIC MB Lot-Sample #: G9H180000-398 Prep Date... . ..: 08/19/09 Analysis Date.-: 08/29/09 Prep Batch #... a 9230308 Dilution Factor: 1 DETECTION PARAMETER RESULT LIMIT UNITS METHOD 2,3,7,8-TCDD NO 0.039 pg/g SW846 8290 Total TCDD ND 0.039 pg/g SW846 B290 1,2,3,7,8-PeCDD ND 0.076 pg/g SW846 8290 Total PeCDD ND 0.076 pg/g SW846 8290 1,2,3,4,7,8-HxCDD ND 0.049 pg/g SW846 8290 1,2,3,6,7,8-HxCDD ND 0.040 pg/g SW846 8290 1,2,3,7,8,9-HxCDD ND 0.041 pg/g SW846 8290 Total HxCDD ND 0.049 pg/g SW846 8290 1,2,3,4,6,7,8-HpCDD ND 0.16 pg/g SW846 8290 Total HpCDD NO 0.17 pg/g SW846 8290 OCDD ND 1.8 pg/g SW846 8290 2,3,7,E-TCDF ND 0.18 pg/g SW846 8290 Total TCDF ND D.18 pg/g SW846 8290 1,2,3,7,8-PeCDF ND 0.20 pg/g SW846 8290 2,3,4,7,8-PeCDF ND 0.10 pg/g SW846 8290 Total PeCDF ND 0.20 pg/g SW846 8290 1,2,3,4,7,8-HXCDF ND 0.47 pg/g SW846 8290 1,2,3,6,7,8-HXCDF ND 0.094 pg/g SW846 8290 2,3,4,6,7,8-HxCDF ND 0.088 pg/g SW846 8290 1,2,3,7,8,9-HxCDF ND 0.13 pq/g SW846 8290 Total HxCDF ND 0.47 pg/g SW846 8290 1,2,3,4,6,7,8-HpCDF ND 0.32 pg/g SW846 8290 1,2,3,4,7,8,9-HeCDF ND 0.40 pg/g SW846 8290 Total HpCDF ND 0.40 pg/g SW846 8290 OCDF ND 0.32 pg/g SW846 8290 PERCENT RECOVERY INTERNAL STANDARDS RECOVERY LIMITS _ 13C-2,3,7,8-TCDD 39 * (40 - 135) 13C-1,2,3,7,8-PeCDD 37 * (40 - 135) 13C-1,2,3,6,7,87HxCDD 38 * (40 - 135) 13C-1,2,3,4,6,7,8-HpCDD 42 (40 - 135) 13C-OCDD 40 (40 - 135) 13C-2,3,7,8-TCDF 40 (40 - 135) 13C-1,2,3,7,8-PeCDF 38 * (40 - 135) 13C-1,2,3,4,7,8-Hx CDF 40 (40 - 135) 13C-1,2,3,4,6,7,8-HpCDF 42 (40 - 135) 1SOTE(S) : Calo la6cm;are performed before raunding to awid m=d­off errors in ralWamd revulm Surrogam mcovay is outside Stated eonaml loots. G9H120259 TeslAmerlea West Sacramento(916)373-5600 16 of 518 LABORATORY CONTROL SAMPLE EVALmTION REPORT Trace Level Organic Compounds Client Lot #...: G9H120259 Work Order #...: LSCPM.:AC Matrix. ..... . ..: BIOLOGIC LCS Lot-Sample#: G91f180000-398 Prep Date......: 08/19/09 Analysis Date..: 08/29,%09 Prep Batch #--- : 9230398 Dilution Factor: 1 PERCENT RECOVERY PARAMETER RECOVERY LIMITS METHOD 2,3,7,8-TCDD 3.00 (50 - 150) SW846 8290 1,2,3,7,8-PeCDD 100 (50 - 150) SW846 8290 1,2,3,4,7,8-HxCDD 108 (50 - 150) SW846 8290 1,2,3,6,7,E-HxMD 108 (50 - 150) SW846 8290 1,2,3,7,8,9-HxCDD 107 (50 - 150) SW846 8290 1,2,3,4,6,7,8-HpCDD 100 (50 - 150) SW846 8290 OCDD 103 (5o - 150) SW846 8290 2,3,7,8-TCDF 101 (50 - 150) SW846 8290 1,2,3,7,8-PeCDF lei (50 - 350) SW846 8290 2,3,4,7,8-PeCDF 100 (50 - 150) SW846 8290 1,2,3,4,7,8-HxCDF 101 (SO - 150) SW846 8290 1,2,3,6,7,8-HxCDF 100 (50 - 150) SW846 8290 2,3,4,6,7,8-HxCDF 101 (50 - 150) SW846 829D 1,2,3,7,8,9-HXCDF 106 (50 - 150) SW846 B29D 1,2,3,4,6,7,8-HpCDF 101 (50 - 150) SW846 8290 1,2,3,4,7,8,9-HpCOF 101 (50 - 350) SW846 8290 OCDF 102 (50 - 150) SW846 8290 PERCENT RECOVERY INTERNAL STANDARD RECOVERY LIMITS 13C-2,3,7,8-TCDD. 95 (40 = 135) 13C-1,2,3,7,8-PeCDD 97 (40 - 135) 13C-1,2,3,6,7,8-HxCDD 91 (40 - 135) 13C-1,2,3,4,6,7,8-HpCDD 100 (40 - 135) 13C-OCDD 93 (40 - 135) 13C-2,3,7,8-TCDF 93 (40 - 135) 13C-1,2,3,7,8-PeCDF 95 (40 - 135) 13C-3,2,3,4,7,8-HxCDF 96 (40 - 135) 13C-1,2,3,4,6,7,8-HpCDF 98 (40 - 135) NOTE(S) : Calculadow are performed before rounding to avid round-off mom in mlculaled resubs. Bold pant dwwm 0ontmf pamote m GSH120259 TestAmerlr West Sacramento(916)373-5600 17 of 518 1 LABORATORY CONTROL SAMPLE DATA REPORT Trace Level organic compounds Client Lot #...: G9H120259 Work Order #...: LJCPM'_AC Matrix------ ---- BIOLOGIC LCS Lot-Sample#: WR180000-398 Prep Date......: 08/19/09 Analysis Date..: 08/7.9.!D9 Prep Batch #...: 9230398 Dilution Factor: 1 SPIKE MEASURED PERCENT PARAMETER AMOUNT AMOUNT UNITS RECOVERY METHOD 2,3,7,8-TCDD 20.0 19.9 pg/g 100 SW846 8290 1,2,3,7,8-PeCDO 100 99.9 pg/g 100 SW846 8290 1,2,3,4,7,8-HxCDD 100 108 pg/g 108 SW846 8290 1,2,3,6,7,8-HxCDD 100 108 pg/g 108 S9846 8290 1,2,3,7,8,9-HxCDD 100 107 pg/g 107 SW846 8290 1,2,3,4,6,7,B-HpCDD 100 100 pg/g 100 SW846 8290 OCDD 200 206 pg/g 103 SW846 8290 2,3,7,8-TCDF 20.0 20.3 pg/g 101 SW846 8290 1,2,3,7,8-PeCDF 100 101 pg/g 101 SW846 0290 2,3,4,7,8-PeCDF 100 99.8 pg/g 100 SW846 8290 1,2,3,4,7,8-BxCDF 100 101 pg/g 101 SW846 8290 1,2,3,6,7,E-HxCDP 100 100 pg/g 1D0 SWB46 8290 2,3,4,6,7,8-HxCDF zoo 101 pg/g 101 SW846 8290 1,2,3,7,8,9-HxCDF 100 106 pg/g 106 S14846 8290 1,2,3,4,6,7,8-HpCDF 100 101 pg/g 101 SW846 8290 1,2,3,4,7,8,9-BpCDF 100 101 pg/g 101 SW846 0290 OCDF 200 203 pg/g 102 SW846 8290 PERCENT RECOVERY INTERNAL STANDARD RECOVERY LIMITS 13C-2,3,7,8-TCDD 95 (40 - 135) 13C-1,2,3,7,8-PeCDD 97 (40 - 135) 13C-1,2,3,6,7,8-HXCDD 91 (40 - 135) 13C-1,2,3,4,6,7,8-HpCDD 100 (40 - 135) 13C-OCDD 93 (40 - 135) 13C-2,3,7,8-TCDF 93 (40 - 135) 13C-1,2,3,7,8-PeCDF 95 (40 - 135) 13C-1,2,3,4,7,8-HXCDF 96 (40 - 135) 13C-1,2,3,4,6,7,8-HpCDF 98 (40 - 135) NOTE(S) : _ C11e,datlDn4 are performed before rouadinq ro avoid routs-off errors in calculated results. Hold prim da acs comml parameters G9H120259 TestAmerics West Sacramento(916)373-5600 18 of 518 BIOLOGIC , 00 , Percent Lipids GgH120259 YestAmerica West Sacramento(916)373-5600 19 of 51B Blue Ridge Paper Product:; Inc Client Sample ID: SITE 4A CHAWM CAT(R) Trace Level Organic Compounds Lot-Sample #---: G911120259-001 Work Order #...: LH2XV1_AA Matrix... ......: BIOLOGIC Date Sampled...: 08/03/09 Date Received.. : 08/12/09 Prep Date......: 08/19/09 Analysis Date..: 08/2F/09 Prep Batch #...: 9230412 Dilution Factor: 1 DETECTION PARAMETER RESULT LIMI"_ UNITS METHOD Percent Lipids 9.5 g SH846 8290 G9H120259 TestAmerlca West Sacramento(916)373-5600 20 of 518 Blue Ridge Paper Products Inc Client Sample ID: SITE 4A COMMON CARP(R) FILLETS Trace Level Organic Compounds Lot-Sample #._.: G9H120259-002 Work Order #...: LH2XXIAA Matrix.... .....: BIOLOGIC Date Sampled.._: 08/03/09 Date Received__: 08/12/09 Prep Date......: 08/19/09 Analysis Date..: 08/29/09 Prep Batch #_._: 9230412 Dilution Factor: 1 DETECTION PARAMETER RESULT LIMIT_ UNITS METHOD Percent Lipids 11 c SW846 8290 GSH120259 TestAmerica West Sacramento(916)373-5600 21 01518 I Blue Ridge Paper Products Inc Client Sample ID: SITE 433 CHANNEL. CXT(R.) FILLETS Trace Level Organic Compounds Lot-Sample #._.: G9H120259-003 Work Order #...: LH2X51AA Matrix. ... .....: BIOLOGIC Date Sampled...: 08/04/09 Date Received..: 08/15:/09 Prep Date.... ..: 08/19/09 ]analysis Date..: 08/25/09 Prep Batch #. ..: 9230412 Dilution Factor: 1 DETECTION PARAMETER RESULT LIM_I;' UNITS METHOD Percent Lipids 7.0 _ $ SW846 8290 G9H120259 TestAmerica West Sacramento(916)373-5600 22 of 518 I � Blue Ridge Paper Product:; Inc Client Sample ID: SITE 4B COMMON CARP(R) VME&&TS Trace Level Organic Comprwnds Lot-Sample #. ..: G9H120259-004 Work Order #...: LH2X91AA Matrix.........: BIOLOGIC Date Sampled._.: 08/04/09 Date Received. .: 08/1'l./09 Prep Date... . ..: 08/19/09 Analysis Date.. : 08/29/09 Prep Batch #... : 9230412 Dilution Factor: 1 DETECTION PARAMETER RESULT LIMIT UNITS METHOD Percent Lipids 17 g SW846 8290 GSH120259 TestAmerica West Sacramento(916)373-5600 23 o4 519 Blue Ridge Paper Productr: Inc Client .Sample ID: SITE 4A COMMON CARPWB (WHOLE BODY) Trace Level Organic Compounds Lot-Sample #... : G9H120259-005 Work Order #...: LH20jlAA Matrix. ........: BIOLOGIC Date Sampled...: 08/03/09 Date Received..: 08/12/09 Prep Date... . ..: 08/19/09 Analysis Date..: O8/2q/09 Prep Batch #..... 9230412 Dilution Factor: 1 DETECTION PARAMETER RESULT LIMPf UNITS METHOD Percent Lipids 6.8 $ SW846 8290 G911120259 TestAmerica West Sacramento(916)373.5600 24 of 518 t- APPENDIX C BLUE RIDGE PAPER CANTON MILL FISH FILLET TISSUE ANALYSIS RESULTS, 1990-2004 33 Blue Ridge Paper Canton Mill Fish Fillet Tissue Analysis Results, 1990-2000). 100 Resuasot 1991 Resulls°i) Number of Length Number of Length Station Species Fish Range(mm) 2,3,7,8-TCDDE-) Station species Fish Range(mm) 2,3,7.8-TCDDW I Rock bass 5 151-197 ND(0.15) 1 Rockbass 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 5 358.471 ND(0,35) 2 Redbreast sunfish 5 185-196 I.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 to 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 7-6 RM 52.3 Bluegill 6 164-197 ND(0.83) Common carp 2 489.555 4.2 Common carp 10 408463 2.4 4A Bluegill 5 178-192 ND(1.2) 4A Lagemoudh bass 7 313-468 3.0 RM 41.5 Bluegill 5 153-174 ND(0.63) RM 41.5 Black crappie 10 173.216 ND(0.63) Common emp 1 574 27 Common cup 10 502-688 23 - 4B Bluegill 5 183-196 0.76 4B Bluegill 5 186-212 ND(0.34) RM 39.0 Largemouth bass 2 279400 ND(1.8) RM 39.0 Bluegill 5 190.209 ND(0.62) Common carp 4 551-638 65 Common carp 10 532-605 40 5 Redbreast sunfish 10 143-223 0.98 RM 16.5 Spotted bass 2 266.368 ND(0.35) Commun carp 2 511-539 1.7 Total Fish Filleted 57 138 i i i Z91 85I Patai(!3 gs<3IRoJ, Tro)QN OSS-054 5 ogunq gtnougpmS 1910 QIS-8Zt, S olellnq gmouglmS (£l'0)QN IO ZTZ 6 sseq g)noug UIG 0'61 INN (OE'0)QN 59E-95Z Z sseq pauodS 0-61 m (LI'0)QN I99-081 9 gsgma lsmagpoN S (8E'0)QN Stz-SLT OT gsguns lmlgpzd S 87 969.OES OT dim nouvu03 IS M-855 OT dtm uourmo, (OZ'0)QN OIZ-S91 0t a!BanIH 0'6E INN (6E'0)QN ZEE-M S sseq tpnoma8n7 0'6E M (Zl'0)QN OT£-06T OI sseq tpno=9nj HY (EZ'O)QN ZIZ'LSI 01 g!ean!g at, 61 I19-SM 01 dtea uaunuoD GZ ZZ9161, OI d=uo=3 (680,0)QN >oZ--ZST OI a!ddei nmEl 5'I4INN COT-0)QN MLLT 01 o!dd=1oe1H 51tm (Sl'0)(IN TOZ-SLI OI atddua Nae!H tl4 (116010)QN ZE'Z-EST at a!ddm Xjmjg tl4 4'E 9LS-066 at dtm u=aD 4 00918£6 OT dim uouuuoZ) (9E'0)QN £It 08T L gs<.Nns lseaigpaN E'ZS P(a (6Z'O)QN OOZ-£SI OI gsynos 7seai4PaN E'ZS YIN (LZ'0)QN orz-m 01 gsgnns lsmagpaa E (w,o)QN OOZ-SLI 01 gsguns lmlgpoX £ I'£ OZ9196 Ol dim uo=oD E'6 ISS1984 OT dm uo=oo (ST'0)QN T61-OPI OT tlsg=)=Igpau 0'6S P(a (BE'0)QN OZZBLT OI gsguns umsgpaa 0'65 PM (LZ'0)QN 90Z-891 01 gsgum)smigpmd Z ZL'0 OZZ O81 01 gspm IsmlgPaa Z (08,0)UN OIY59£ 01 auogpal)plg VT 1#199E 9 aslogpm xae!g (ZT'0)(IN EOZ-SPI S gsguns ls=gpad S'h9 Wu 510-0)QN Z81Y41 01 gs9°ns tsmgpaa 5199 m (Oro)QN 80Z-S81 OI sseq Voa T (S80'0)QN 46T-L4I of sseq XooN I caQQDS-8 T'Z (unu)a8uug qS!d m!aadS nOPMS (oQQDTiT E'Z (mm)*Haag IMA sa!mdS uopmS g18uo-1 ;o jagmnN gftn Jo aagmnN wstl=U E66I tysljnmH Z66T 1994 Resultsol 1995 Results(e) Number of Lcogdr Number of Lung& Station Species Fish Range(mm) 2,3,7,8 TCDD01 Station Species Fish Range(mm) 2,3,7,8-TCDD(°) 1 Rock bass 6 156-185 ND(0.083) 1 Rock bass 10 162,205 ND(0.30) RM 64.5 Redbreast sunfish 10 155-197 ND(0.10) RM 64.5 Rock bass 10 150 220 ND(0.26) Black redhorse 3 367-435 ND(0.096) Black redhorse 7 375-464 ND(0.21) 2 Redbreast sunfish 30 176.206 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 10 161-185 ND(0.16) Common carp 10 490-590 0.99 Cocoon 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 30 158-210 ND(0.074) RM 52.3 Redbreast sunfish 10 154-202 ND(0.20) Common carp 10 456565 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 Bluegill 10 195.205 ND(0.084) RM 41.5 Biuegill 10 167-199 ND(0.26) Common carp 10 465-591 3.4 Common carp 10 520-615 5.8 4B Black cmppie I0 200215 ND(0.094) 0 Largemouth bass 9 248.391 0.68 RM 39.0 Black cmppre 10 195.220 ND(0.062) RM 39.0 BluegBl 8 158-216 ND(0.34) Common carp 10 520-635 6.6 Common cup 4 532-626 11.0 5 Redbreastsunfish 6 129.289 ND(0.075) 5 Smallmoudr bass 9 280-423 ND(0.11) RM 19.0 SmaRmouth bass 9 734 W ND(0.11) RM 19.0 Redbreast sunfish 7 163-192 ND(0.15) SmaWnouth buffalo 9 440.520 ND 0.089 Black redhorse 7 440-481 ND 10,451 Told Fish Filleted 163 155 I 1996 Resvltsol - 2997 Resultsal Number of Length Number of I. th Station Species Fish Rouge(tam) 2,3,7,8-TCDDk1 Station Species F(sh Rangc(tam) 2,3,7,6-TCDDt•t 1 Redbreast sunfish 5 154-185 ND(0.13) 1 Redbreast sunfish 5 144-161 ND(0.11) RM 64.5 Rack bass 5 160-209 ND(0.085) RM 64.5 Rock bass 5 162-M ND(0.23) Black redhorse 5 401-440 ND(0.089) Black redhorse 4 291-424 ND(0.22) - 2 Redbreast sunfish 5 179-187 ND(0.10) 2 Redbreat sunfish 5 183-200 ND(0.26) RM 59.0 Redbreast sunfish 5 183-191 ND(0.12) RM 59.0 Redbreast sunfish 5 160-181 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 5 187-202 ND(0.18) RM 52.3 Redbreast Sunfish 5 165•I85 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 Black crappie 5 216-233 ND(0.15) 4A Black crapppie 5 215.231 ND(0.27) RM 41.5 Black crappie 5 215-229 ND(0.18) RM 41.5 Black crappie 5 220-230 ND(0.30) Common carp 5 562.632 4.2 Common carp 5 570.655 2.3 Charnel catfish 5 418-482 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 catp 5 470-623 4.0 Common carp 5 605.690 11.0 Flathead catfish 5 430.540 0.62 5 Rock bass 4 169.186 ND(0.077) 5 Rock bass 5 143.214 ND(0.15) RM MO Smallmoudt bass 5 315454 ND(0.12) RM 19.0 3malrmou6t bass 5 278 367 ND(0,27) SmallmowhbuBalo 5 451-555 ND(0.12) Smallmouth buffalo 5 406-525 ND(0.22) Total Fish Filleted 89 Total Fish Filleted 99 j i ODI P2lail!3 gs!a MOM. 66 Pa7a@3 gsT31elo.L i£'D UN 595.9L? S opMnq ytnoulOewS (I£'0 QN LES-496 S OpDnq glnouglswS (61'0)ON OD-LO S sseq gmougpwS 0'61 M (TZ'0)(IN 59£-S64 S sseggmougj=S 0'6I Wit (6Z'0)CIN EOZ-OLI S sseq%ooll 5 (11,0)(IN 061-951 4 ssuq 31WE 5 (9Y'0)am EIS-ZL£ S IISMW pcagleld (OZ'0)(IN Us-plb S gs9leo PwgmLl L'b 089-TZ9 S dma uowwoZ) 1'6 MIX S dmo oowwon (Z£'0)am SOS-9LZ 5 sseq tpuu=21e 1 016E m (LT'0)QN GEC-65Z 5 sseq gtnowo8xj 016E m (LZ'0)(IN M-E£Z S aldd—spelg gq (91-0)QN M-E£'L S atdd=x0t[a at, Es'0 zw5Z4 5 gs91�IMMH J (8Z'O)QN 856'9T4 S gs9lea la=tD 85'0 S49-OLS S dleo uo=oJ 9.1 TZ9-585 S dm uauwo:) (80'0)GN OZ-6TZ S aldden)PelH 514 m (51'0)(IN OEL M S sseq glnowa8xwl ;'TV POI (21'0)QN 89Z-OZZ S OEM NMIE y4 (6ro)(IN Ot2-oZZ S alto%t10 V4 LS'O 169-005 S d=uouwoa On)(N OSS-6" S dma uoww03 (LE'0)(IN 9LT-Z91 S gs'3wls lsealgpag E'ZS PM (ZZ'0)(IN Ooz-L91 S gsyvn =igpad E'Z5 P111 On)(IN 68T-691 S qsg=v=gpoll £ (4E'0)aN 961.891 S gsgona Ise»gpad £ (LZ'D)QN 919-m 5 dleououwoo E9 199-15S S dwuouwo:) (6Z'0)(IN ELT-851 S gsgm lsealgpag 0'69 m (8Z'0)QN E61-991 S gspm lmlgm 0'69 M (L£'D)QN 061-L91 S gsgons lseugMll Z (ovo)QN LLI-*l S gsg=lseugpQ-d Z (EE'O)QN LZAZS£ S asiogpal>laelg (81'D)(IN 96E-o6E S astoiN 8oe1H (LE'0)QN 081-01 5 snq*ou S'99 m (6Z'O)QN 6LI-851 S sssq q=li 5'19 m (IZ'0)(IN L4I-14I S gs9uns lseasgPaU 1 (61'0)QN 9Li-SM S gs9m lseatgP11 I evQQJ.L-8'L'E'Z Ouw)o8deg Wd sawadg uoDetS wQ�Z-8'L'£'Z (aw)a8ueg gsld salxgq UOTIMS g11+va1 10 aagmnN g18u7L Jo nq=N �ys0usag 666i (oslllml18661: 2000 Resultsm 2001 Resultsf4 Number of Length Number of Length Station Species Fish Range(min) 2,3,7,8-TCDDt•1 Station Species Fish Range(o0N 23,7,8-TCDDt'1 I Redbreast sunfish 5 137-148 ND(0.48) 1 Black redborse 5 312407 ND(0.25) RM 645 Rock bass 5 162-186 ND(0.45) RM 64Z Black redhorse 5 35M96 ND(0.38) 2 Redbreast sunfish 5 169-176 ND(031) 2 Common carp 5 456-555 ND(0.27) RM 59.0 Redb=t smfish 5 164-181 ND(0.43) RM 59.0 Common carp 5 503-582 ND(0.42) 3 Redbreast sunfish 5 169.181 ND(OA3) 3 Common carp 5 SU-615 ND(0.35) RM 52.3 Redbreast sunfish 5 186-199 ND(0.32) RM 52.3 Common carp 5 514569 ND(0.53) 4A Buck crappie 5 212 2t1 ND(0.79) 4A Channel catfish 5 476.612 1.2 RM 41.5 Black crappie 5 220 241 ND(0.24) RM 41.5 Common carp 5 529-668 1.3 Common 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 405463 ND(0.29) RM 39.0 Black crappie 5 220.230 ND(0.37) RM 99.0 Common carp 5 654-723 5.6 Common carp 4 593 712 4A Flathead catfish 5 407.450 ND(0.42) 5 Rack bass 5 171-198 ND(0.45) 5 Black redhorse 5 437-497 ND(026) RM 19.0 Smallmomh bass 5 209.238 ND(0.31) RM 19.0 Black redhorse 5 427-476 ND 0,35) Total Fish Filleted 98 Total Fish Filleted 40 2002 Results" 2003 Resuttsm . Number of Length Number of Length Station Species Fish Range(Mm) 2,3,7,8 TCDIY') Station Species Nish Range(mm) 2,3,7,8-TCDDW I Black redhorse 5 372431 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(028) 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 cup 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 atFish 5 521-575 ND(DL=0.35) 4B Common carp 5 647.670 6.6 4B Common carp 5 6M-745 12.0 RM 39.0 Flathead catfish 5 418-SW ND(0,22) RM 39.0 Flathead catfish 5 511.533 ND(DL-0.20) 5 Black reamse 5 420489 ND(0.14) 5 Black redhorse 5 445-524 ND(DL=0.19) RM 19.0 RM 19.0 Total Fish Mated 40 Total Fish Filleted 40 1 200411esultstA Number of Length Station Species Fish Range(MM) 2,3,7,8-TCDD(`) I Black redhorse 5 352.440 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 5 570.66D 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 Fisch Filleted 40 (a) Survey conducted by EA Engineering,Science,and Technology. Analyses conducted by ENSECO Laboratories 1990-1994,Quanterra Laboratories 1995-1999,Severn Trent Laboratories in 2 2003. (b) Survey conducted in August. (c) Survey conducted in August and September. (d) Survey conducted in September. (e) Units=ppt(1»per edition)or p8i8(picogram per gram) ND=Non-detestable at the detection limit in parentheses. I APPENDIX D 2006 REVISIONS TO DIOXIN MONITORING PLAN 34 0�V�ArF9 Michael F.Easley,Governor William G.Ross Jr.,Secretary \0 QG North Carolina Department of Environment and Natural Resources Nan W.Klimek,P.E.Director ` - Division of Water Quality Coleen N.Sullins,Deputy Director ioM4 uality PIZ June 6,2006 JUN '� 2 im Mr. Paul S.Dickens Manager,Environmental Affairs CLUE RIDGE PAPER PRODUCTS ING Blue Ridge Paper Products OHS DEPARTMENT 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-begimiing 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. ince�ely,�`.s iEimrnie verton ronmental Sciences Section cc: Roger Edwards-ARO Dr.Luanne Williams—NCDHHS Susan Wilson -DWQ Permits John Crutchfield—Progress Energy 1 MICDENR N.C.Division of Water Quality 1617 Mail Service Center Raleigh,North Carolina 27699-1617 (919)733-7015 Customer Service 1-877-623-6748 COPY BLUE RIDGE PAPER PRODUCTS INC. Certified Mail Return Receipt Requested 7099 3220 0007 03716235 30 March 2006 Mr. Mark Hale Environmental Biologist Environmental Services Section Division of Water Quality Notch 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 Pi,2eon River'Dioxin Monitorine 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 o PC 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: a 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 c PO Box 4000 Canton, North Carolina 28716 a 828-646-2000 Raising Your Expectations Marl:Hale, NC DENR DWQ,ESS- 3/30/06, Page 3 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 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 dicicep@blueddeepaper.com rogera@blueridggpaner.com Enclosures: Study Plan Revision Dioxin Monitoring in Fish Tissue— Waterville.Lalce 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—UTIC Billy Clarke—Roberts &Stevens John Crutchfield—Progress Energy Blue Ridge Paper Products Inc 175 Main Street o PO Box 4000 Canton, North Carolina 28716 0 828-646-2000 Raising Your Expectations copy BLUE RIDGE PAPER PRODUCTS INC. STUDY PLAN REVISION DIOXIN MONITORING IN FISH TISSUE Wa ter vnllRe Lake Prepared for: Blue Ridge Paper Products,Inc. Canton Mill Canton,North Carolina NPDES No.NC 0000272 Prepared by: J.Larry Wilson,Ph.D. Departments of Forestry,Wildlife and Fisheries University of Tennessee I?moxville,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 thty 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: • 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 willl 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 carpio) and channel catfish(Ictalurtts 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 411);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 4B) will be,recorded. Total study effort for the 4A/4B 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 4B G catfish composite—one composite catfish fillet sample at each location 4A and 4B 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.UTK 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 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 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 Intetnational 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 Intemational 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. 13479.01,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. 20011. 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 Lalce University of Tennessee for Blue Ridge Paper Products Inc.Canton Mill Page 5 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,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 o f 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. Analydcal 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). V etsar,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, Match 9. World Health Organization(WHO). 1997. Exposure and Human Health Reassessment of 2,3,7,8- Tetradilorodibenzo-p-dioxin(TCDD)and Related Compounds: Part II Health Assessment of 2,3,7,8-Tetmchlorodibenzo-P-dioxin(TCDD and Related Compounds. COPY EA Project 13900.01 STUDY PLAN FOR PMEON MVER Prepared for.• Blue Ridge Paper Products Canton, NC Prepared by: EA Engineering, Science, and Technology 444 Lake Cook Road, Suite 18 Deerfield, IL 60015 Deeember=l 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 furaus 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 21.5 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 1-00 Station 5 RM 99.0 5 Bluffton TN-- (193 ,Hartford,TN .� TENNE_SSEE N NORTH CAROLINA g�9 Hydro Plant `v a. (26.U) 1 � 0 4fo4 ` � CenS _ Walters Dam— B Station4B Station4A ' RM 39.0 RM 49.5 4 Waterville Lake Fleas Creek New Hepco Bridge FLOW Jonathan Creek Old Rt.209 3 Station 3 Station 2 Mill Outfall RM 52.3 RM i 50.0 IM63.3 Waynesville STP--' 2 Canton,NC RM 50!4 aca _ e� � CI de Station 1 RM 64.5 (Control) Figure 2-9. Fish tissue sampling station locations.on the Pigeon River. TABLB2.1 PIGEON RPMR SAMPUNGSTAMONS Station River Station Location and Numb n Mile DistanM from Outf9l Aire Deecrintion Mabital Ipm Fish Cnmmh niN 1 64.5 Pigean Riverupstmam from Canton, Characterized by rife,ran,and pool habitats. Meximum Relative abundance dominated by minnows and dancrs. River NC,adjaccin to Canton Recreational depth approximately 6 ft. Substrate primarily cobble and chub,greman defter and rock bussam dominant. Northemhog Park(1.2 RM upstream fmm Canton boulders interspersed with gravel and sand, Mill mnfalp. sucker,black rcdhorse,mitmrshincr,redbceasl sunfish.eenmal stoneroller,greenside darter,and mottled sculpin arc common. 2 AD Pigeon River upstream fmm Clyde,NC Characterized by riffle,run,and pool habitats with canopy Relative abundance dominated by redbmst sunfish,central (4.3 RM downstream from the Canton rover.Muimum depth approximately5 ft. Substrate stoneroller,and northern hog sucker. Mill outfalp• primarily cobble/gmveVmnd with someboulders and bedrock. 3 52.3 Pigeon River in the vicinity of the Rt. Chnn cteriud by rife,ran,and pool habitats with some Redbreast sunfish,northern Ito.sucker,and common carp am 209 bridge(11.0 RM downstream cmopyeaver. Maximum depth nppwxinately5[L from the Canton Mill outfalp) Substrate priman7y bedrock and boulders with same dominant. Cmtml 5loncroller is common. cobble and sand/gravelffenes deposited in pool areas. 4A 41.5 UpperWatervite Lake(21.9 RM Characterized by deep-water lentelhabitat.bedrock, Relative abundance dominated by black cmppia Bluagill, downsteam from the Canton IvBll and softboltom sediments. Maximum depth sampled outfalp approximately 14 ft. fialbead catFslh.channel catfish,largemouth bass,and common carp arc common. 4B 39.0 Lower Waterville lake(243 RM Characterized by deep-water lamic habitat,bedrock, Relative abundance of catch dominated by black crappie. dowretneam from the Canton Mill and soft bottom sediments.Maximum depth sampled Bluagill,channel catfish,flathead catfish,and emp arc common. outfalp approximately 40 ft. VerysteepbankswiWdittlecover. 5 19.0 Pigeon Rivernear Bluffma,TN,just Characmrnad bydeep pools and mnswith someShzllow Cx tmistanemhlcrandnonhemilOgsuckernmdomiwnt. upstream of 140(443 RM downstream dies. Maximum depth approximately 6 to S A. Substrate Smaldmouth bass,whitetail shiner,telescope shiner.gmcmido from the Canton Mill outfalp primarily bedrock,boulder,and cobble, defter.and banded sculpin are common, fsxeept for smalhnouth bass and rock bass,xntmmbids am uneommoon. 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 Labe 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 1 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 Q Pigeon River Mile39.0 Gill nets 5 Pigeon River Mile 19.0 Electrofishing In summary,fish will be collected as follows: e Bottom feeder fillet composite—one sample at all six stations o Catfish fillet composite—one sample at Stations 4A and at 4B o Common carp whole body composite—one sample from either Station 4A of 4B o Catfish fillet composite—one sample at Stations 2 and at 3,if specimens are encountered 7 4. SAWL,E PRE,PARATLoN 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,stunted 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 malting an hncision 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 from head to tall. 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 1 5. ANALYSIS Or, )i ISH 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 I7 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 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 processing. 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?A 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_ c Sample identification number, o Station identification, o Sampling team initials, Date of sample collection, Species name, c Sample type(i.e.,fillet or whole body) 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. PROJE,CT 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 S. MONITORING 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 Dibenzofmans 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-dioxht(TCDD) and Related Compounds: Part 11 Health Assessment of 2,3,7,8-Tetrachlorodibenzo-p-dioxin(TCDD)and Related Compounds. 13