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HomeMy WebLinkAboutNC0000272_ReportEff.DischargeColorRed_19870301 EFFLUENT DISCHARGE COLOR REDUCTION PROJECT PIGEON RIVER .COLOR MODELING STUDY CHAMPION INTERNATIONAL CORPORATION CANTON MILL f _ CANTON, NORTH CAROLINA MARCH 1987 a TABLE OF CONTENTS Pa e EXECUTIVE SUMMARY . . . . . . . . . . . . . . . . . . . I INTRODUCTION . . . . . . . . . . . . . . . . . . . . . . 1 RIVER .GEOGRAPHY . . . . . . . . . . . . . . . . . . . . 1 SOURCES OF INFORMATION . . . . . . . . . . . . . . . . . 2 River Flow . . . . . . . . . . . . . . . . . . . . 2 River Flow Interpolation . . . . . . . . . . . . . 2 Color . . . . . . . . . . . . . . . . . . . . . . . 5 MODEL DEVELOPMENT . . . . . . . . . . . . . . . . . . . 5 Model Equation . . . . . . . . . . . . . . . . . . 5 Applying the Dilution Model at the State Line . . . 5 Applying the Dilution Model at HEPCO . . . . . . 6 Modifying the Dilution Model . . . . . . . . . . 6. Model Calibration . . . . . . . . . . . . . . . . . 7' . Final Model Results . . . . . . . . . . . . . . . . 7 t SUMMARY 'AND CONCLUSIONS . . . . . . . . . . . . . . . 7 APPENDIXES A - Calculations and Statistical Analysis of Data A-1 B - Raw Data . . . . . . . . . . . . . . . . . . . . B-1 EXECUTIVE SUMMARY A mathematical model was developed to project the impact of a 50% reduction in effluent color discharged from Champion International' s Canton, North Carolina Mill, on color concen- trations in the Pigeon River at the North Carolina-Tennessee border. The traditional dilution model approach was modified to account for a significant color loss across Walters Lake, just upstream of the intrastate border. This 'modified model yielded a mean error of estimate of 18 . 1% and was unbiased with regard to predicting color concentrations.. The results of this model are summarized below for the. current mill and the modernized mill with a 50% reduction in color. CONCENTRATION DISTRIBUTIONS Percent of Time Below a' Specific Concentration (North Carolina-Tennessee border) Color Concentration (nvm) Mill Confiauration 40 50 60 80 100 Current Mill 5% 12% 23% 47% 64%- Modernized Mill 40% 59% 73% 90% >95% t � I 30 AgTuToTA maasgsdn aqg uT aaATg uoa2Td aqy •aaATN psoag gouaag aqg ggTM aouanT3uoo sgT og mpaagsuMop uogup0 moa3 ATTszgusgsgnS saTapA aentg u0e2Td aqg 3o 4uaTppa2 Tpu0TgpnaTa aqy I uTspq gu9tppa2 g2Tg ATgusuTmopead aqg og anp uoTgpgTdTOead TPOOT Aq peoueni3uT AT2uoags sT pup ' (aegmegdag-ATnr) aemmns 2uTanp gs9mOT pup (TTady-Aasnupr) 2uTads ATapa/aaguTM agsT 2uTanp gs9g2Tg ATTsa9u92 sT M0T3 aeATg uoa2Td • (43 6£0 ' T uotgpnaTa ! 9 . 9 NZI) aassauuay 'gaodmaN ge (p2m 908) 210 09Z ' T Pup zTm 999 og pus (g3 9££ ' 3 uOTgpnaTa ! T • 93 PW) puTToaPD ggaON '00JaH gp (P2m 8£t) s3o 8L9 Pup zTm 09£ 0g (g3 ZL9 'Z uoTgsneTa ! T "v9 (PM) aTTW aaeTg) puTToaPD ggaON 'u04us0 asau (p2m 003 ) 930 OTC Pup zTm ££T gnogp moa3 espaaouT 'ATanTgOadsaa 'e2apgosTp upam pup eaap a2puTsaa •aassauuay uaagssa uT aaATg ppoag g0u9a3 aqg ggTM a0u9nT3u00 sgT og gsaMggaou ATTpa9u92 sm0l; pup' 'puiToapO ggaON 'dguno0 pooMAPH 3o suTpgunom aqg uT 99gsuT2Tao aaATg u092Td aqy Anawimm HaAIg •aapaoq egsgspaguT aqg gp su0tgsagua0u00 aoToo 3o segamTgse agpanoop daaA uT sggnsaa pup '9XPq saegTPM To aouan13uT aqg ao3 gunoo0p Og peT;Tpom sT gnq 1guanT33e TTTW u0gup0 aqg moa3 aoToo 3o uoTgnTTp uo AT92asT pessq sT Tapom sTgy aapaoq aassauuay-puTTOapD ggaON agg gp su0zgsagu90u00 a0T8O. aouanT3uT g0TgM saog0p3 agg 2uigTaosep ATTP0Tgpm97qgsm pad0T9n9p sT Tepom p sisATpup aqg 9gpgTTT0s3 oy • suoTgOes 2uTMOTTo3 aqg uT paMainaa \ sT aapaoq aassauuay-puTToasO ggaON aqg gp suOTgpaguaOuoo aoToo J uo sTanaT aoToo guenT33a uT uoTgonpea sTgg 3o gopdwT eqy •Arpog AagsnpuT agg uT sTTTm aoToo gsem0l eqg To auo dpe9aTe sT gI •v0Ta9my ggaON ui sTTTm aedpd pup dTnd g392x pagOsaTq TTp 30 a92apgDSTp aoToo gsaMoT aqg TTTW uogueo aqg a�[pm TTTM apngTu2pm sTgg To uoTgonpea y •TaeaT a2paeAp gueaano sgT moa3 %Og ATegpmTxoadds Aq aoToo guanT339 sgT 90np9a TTTM goTgM A2oTougoeg Toaguoo pup guamdTnbe Mau 2uTTTpgsuT TTTW uogus0 agg azTuaapom og sasodoad uoTdmpgO • suoTTp2 uOTTTTm 003 dTagpmTxoadde sT uogup0 apeu MoT3 aanTa a2paanp ATTpp aqy *Asp aad suOTTs2 uoTTTTm t, , ATagpmTxoadds gp aeATg uoa2Td aqg Og s92apgOSTp pup gusTd guam;eaag aagpmagsem Aappuooas PUP AaPMTad uaapom p g2n0agg sMOT3 guanT339 s ,TTTM egy • sgua2pea 2uTgosaTq eptxoTp auTaOTgO pus 'agtaoTgOodAq mnTOTsO 'apTxoapAiq mnTpos 'auTaoTgO 2UTSn se2pgs TpTguanbas uT pagOseTq sT dTnd aqy • ssaooad 2uT3l000 gXvaX aqg Aq auTd pup spooMpapg moa3 peonpoad sT sauTgoem aedpd xTs agg ao3 dTnd egonpbad aedpd 2uTgTaM PUP 2uTgutad aaggo pup 'aadpd aaTdoo 'aadpd adoTetiue 'Xoogs uogapo NTTM 2uTpnTOuT sgonpoad aadsd gXPax p9g0RQTq 3o Lisp aad sung 006T 3o dgTopdso p spq pup 906T uT uOTgsaedo us2eq 'uoTgpaodao0 TpuoTgsuaagul uOTdmsgO Aq pagpaado pup pauMo 'TTTW uogup0 aqy NOIS011Q02LLNI �✓ T 2 �^ Canton and for about 10 RM downstream is a relatively smooth- flowing stream (mean elevation gradient is - 9 ft/mi from RM 66 . 0 to RM 53 . 0 ) . Its gradient then increases (mean elevation gradient is - 19 ft/mi from RM 53. 0 to RM 42 . 0 ) before it enters Walters Lake, a Carolina Power and Light (CPL) hydroelectric impoundment (dam is at RM 37 . 8 ) . Pigeon River flow is diverted from Walters Lake through a 6-mile long tunnel to the CPL powerhouse near the North Carolina-Tennessee border at RM 26 . 0 . Except during high flow (dam spillage conditions ) , flow in the high gradient (- 55 ft/mi) original stream channel between the dam and the powerhouse consists of minor tributary inflow. The stream gradient, remains relatively high downstream to near Wilton Springs (mean elevational gradient is -24 ft/mi from RM 26 . 0 to RM 14. 3 ) before decreasing in the lower reach of the river (mean elevation gradient in - 10 ft/mi from RM 14. 3 to RM 4 . 2) . Peaking operations at the CPL powerhouse (0 discharge during no generation to ` 1 , 800 cfs ( 1163 mgd) discharge at full generation with three turbines operating) can result in substantial daily flow fluctuation in the Tennessee portion of the Pigeon River. The Canton Mill is the principal discharger to the Pigeon River in North Carolina. Primary wastewater treatment at the Mill was initiated in 1965; secondary treatment was brought on- . line in 1970 . Subsequent treatment plant improvements have included sludge dewatering and removal , and the addition of a third clarifier ( 1977) to secondary treatment. Other discharges to the Pigeon River in North Carolina include- municipal wastes from Canton (treated at the Champion facility) Clyde, and effluent from the Waynesville (municipal and industrial) treatment plant. Agriculture is common along some reaches of the Pigeon River and its tributaries. Figure 1 is a diagram of the Pigeon River between Canton, North Carolina and its confluence with the French Broad River near Newport, Tennessee. SOURCES OF INFORMATION River Flow Pigeon River flow data was obtained from the U. S. Geological Survey (USGS) for gauge stations at HEPCO, North Carolina (No . 03459500 ) , period of record 1928-1985; Cataloochee Creek, North Carolina (No. 03460000 ) , period of record 1935-1985 ; and Newport, Tennessee (No. 03461600 ) , period of record 1904-1981 . River Flow Interpolation Since the U. S. Geological Survey does not have a continuous gauging station at the North Carolina-Tennessee border, a flow r distribution was interpolated for the site. This interpolation was completed using flow frequency distributions from the HEPCO and Cataloochee Creek USGS stations in North Carolina and the Newport, Tennessee USGS station and associated drainage areas in Dem AM 41.0 AM 42.6 Cal CreekAM 40.0 hoe Wallers Lake Creek AM 42.5 AM 42.7 y Fine& Creek !-\ New Napeo Brldye _ FLOW -N- AM 48.2 Ferguson Bridge CnDlne JontlAan Cme4 CENh AM 52.3 RM 62.3 AM 62.9 AM 53.0 AM 59.2 AM 61.3 AM 62.4 AM 63.0 AM 53.5 AM 59.0 FlbFQVH AM 59.4 AM 63.1 R.M 57.7 0 AM 63.4 AM 64.1 Mill outlall Canlon,NC. glcAlend CreakkRM 60.0 RM\ Clyde AM 58.8 AM 64.7 AM 64.5 AM 65.9 __ :PIO11 Farm -•' Addition AM 61.5 Figure 1 w Diagram of the Pigeon River between Canton, North Carolina and Newport, Tennessee 4 r French Broad Riw Y , i%/// RM 7.4 RM 7.8 NewportTN. —N- AM 13.7 Cosby Creek a ®Willow springs ` • RM 19.3 1\ T Tennessee FLOW Hartford RM 24.9 North Carolina Fbyn(Plant - .RM 30.0 RM 26.0 RM 21.5 RM 22.0 . RM 33.2 Big Creek Walters Dee alters Lake Figure 1. (Cont.) l `J J 5 relation to the drainage area immediately above the North Carolina-Tennessee border. This information is tabulated in Table I of Appendix A. Color Waste treatment plant discharge and Pigeon River color data was obtained from the Canton Mill data record. Monthly average color values were used to minimize the influence of time-of-travel to the downstream sample locations. In the Tennessee section of the river, color data was obtained at the I-40 bridge sample location at RM 24. 7 (below the CPL powerhouse in Tennessee) . The I-40 bridge data set was edited to reflect only sampling periods when the powerhouse was discharging to remove bias as a result of samples collected during zero (0 ) discharge from the powerhouse (see the raw data set for this and other sampling sites in Appendix B) . MODEL DEVELOPMENT Model Equation The dilution model is based on an equation which accounts for color discharged from the Canton Mill wastewater treatment plant and background color of all dilution water entering the. Pigeon River above the North Carolina-Tennessee border. The model assumes color is conserved. Pigeon River flow data for the North Carolina-Tennessee border was interpolated due to the lack of a continuous USGS gauging station at the location ( see Flow Interpolation section of this report) . The equation format is : (WTPc * WTPf ) + ( (SLf - WTPf ) * De ) = SLc SLf where: WTPc = Waste Treatment Plant discharge color (ppm) WTPf = Waste Treatment Plant discharge flow (mgd) SLc = North Carolina-Tennessee border (State Line) color (ppm) SLf = North Carolina-Tennessee border (State Line) flow (mgd) Do = Color Concentration of all Dilution Streams ( 13 ppm) Applyine the Dilution Model at the State Line The dilution model was applied to predict color concen- trations at the North Carolina-Tennessee border and then evaluated to determine the accuracy of this prediction. Accuracy was evaluated using two criteria. The first criteria was determ- ination of the mean percent error of estimate. The result of this analysis shows that the dilution model has a mean error of estimate of 20 . 5%. The maximum error of estimate ( 90 percentile) 6 r1_'1 is 38 . 3%. The second analysis determined if the predicted data set was different from the actual data set. This would show if the model has a tendency to bias predictions high or low. The result shows that at a 99% confidence interval there is a significant difference and that the model tends to bias predicted values higher than actual values . Calculations for these analysis are included in Table II of Appendix A. Applying the Dilution Model at HEPCO Further analysis ''of the dilution model revealed that the model is accurate in estimating Pigeon River color concentrations at HEPCO, North Carolina ( just above Walters Lake) . Accuracy results for this application are a mean error of estimate of 14. 4% and the estimate is not biased (see Table III of Appendix A) . As shown previously, the dilution model estimate for the North Carolina-Tennessee border tends to bias high. Therefore, the dilution model needed to be modified to describe the change in color between HEPCO, North Carolina and the North Carolina- Tennessee border. Modifvina the Dilution Model From the above information it is apparent that dilution. of the Pigeon River between HEPCO, North Carolina and the, North ( Carolina-Tennessee border is not the only factor influencing color the concentration, leaving Walters Lake at the CPL powerhouse. To describe the change in concentration across the lake, a data set consisting of the ratio of HEPCO color and North Carolina- Tennessee border color (taken at the I-40 bridge sampling location) was developed. F = HEPCO color concentration I-40 color concentration Further analysis revealed that "F" values are inversely related to Pigeon River flow (measured at HEPCO) . An equation was developed through regression analysis (LOG-LOG) by correlating "F" values with river flow at HEPCO, North Carolina ( see Table IV of Appendix A) . The resulting equation yields a discrete "F value for any HEPCO flow: F = 10( -0. 224 * LOG ( HEf ) + . 781 ) Addition of this equation to the dilution model equation for the HEPCO, North Carolina location yields the final model equation: (WTPc * WTPE ) + ( (HEf - WTPE ) * De ) = SLc HEf * 10( -0. 224 * LOG ( HE f ) + 0. 781 ) i r� 7 where: WTPc = Waste Treatment Plant discharge color (ppm) WTPf = Waste Treatment Plant discharge flow (mgd) HEf = HEPCO, North Carolina flow (mgd) SLc = North Carolina-Tennessee border (State Line) color (ppm) Da = Color Concentration of all Dilution Streams ( 13 ppm) Model Calibration The accuracy of the modified model was evaluated with the same two criteria used for evaluating the dilution model applied to the North Carolina-Tennessee border. The result of the analysis shows that the final model is more accurate, having a mean error of estimate of 18 . 1% and a maximum error of estimate ( 90 percentile) of 35 . 2%. The analysis also shows that at a 99% confidence interval there is no a significant difference between the predicted data set and the actual data set (the model is not biased) . Calculations for these analysis are included in Table V of Appendix A. Final Model Results Figure 2 was generated by applying the final model to both the current long term average discharge color of 344 , 735 pounds/day and a 50% reduction of the average ( 172 , 368 l pounds/day) . The figure predicts the percent of time the color at the North Carolina-Tennessee border will be at or below a specific concentration. As illustrated, a 50% reduction of color in the Canton Mill effluent has a significant impact on the color at the North Carolina-Tennessee border. The model predicts that the modernized mill will achieve 100 ppm color or less at the North Carolina-Tennessee border greater than 95% of the time as opposed to 64% today. Additionally, a color concentration of 50 ppm or less will be achieved 59% of the time as opposed to only 12% of the time now. SUMMARY •AND CONCLUSIONS A dilution model approach was evaluated to determine the impact of a 50% reduction in color discharged from the Canton Mill on color concentrations at the North Carolina-Tennessee border. Because the dilution model predicted color concentrations at the border significantly higher than the actual concentrations , it was necessary to modify the model . After the modification, the model was more accurate and did not show any bias when predicting color concentrations at the North Carolina-Tennessee border. The mean error of estimate for the model is 18 . 1%. Based on this model, a 50% reduction of color from the Canton Mill will result in a major reduction of color at the North Carolina-Tennessee border, as summarized in following table. COLOR MODEL FOR STATE LINE 300 280 260 240 E 220 a a 200 Current Discharge 6 180 160 0 0 140 e 120 100 Projected Discharge 0 80 * 60 40 20 0 0 20 40 160 80 100 X Time Below Indicated Color Value Figure 2 0D 9 t CONCENTRATION DISTRIBUTIONS Percent of Time Below a Specific Concentration (North Carolina-Tennessee border) Color Concentration (pnm) Mill Confieuration 40 50 60 80 100 Current Mill 5% 12% 23% 47% 64% Modernized Mill 40% 59% 73% 90% >95% C . APPENDIX A CALCULATIONS AND STATISTICAL ANALYSIS OF DATA .:J l A-1 TABLE 2 Total HErCD Percent Catalcochee + rat. Creek N ! F'rewpgr�, '!s' 2hanne In .�,9 St:YatE. R.. ged4v4..1.+t7 KEPCO gw Creek Flow Flow F1ow per eq. M;.!,. DA Etzt="--= c 19 toF-,-,Cc_ad _________________ _________________ _________________ _________ ________ ____________________________________ Flew (Cfsl (ogd) (CFs) logd) (cfs) (ogd) (cfs) ;;gd) cfVM 2) (sgdtr:i-. Ms) (:g ) ------------ ------- ------- ------- ------- ------- ------- ------- ------- ------- ------- ------- ------- 45 175 113 29.2 19.9 204 13< 255 165 0.19U 0,i2$ 2�i+ i=? 90 211 136 35.0 22.6 24A 159 335 217 0.334 0,216 292 1"e8 65 243 157 39.9 25.8 283 193 402 26U 0,446 !.I8 344 :22 80 275 178 44.6 28.9 320 1-07 474 3U6 0.579 0,374 79 258 75 309 200 49.4 31,9 358 232 537 347 0.669 0.M 450 29i 70 345 223 54.6 35,3 400 258 607 392 0.777 0.502 506 321 65 382 247 60.2 38,9 442 286 685 443 0.9i0 0.558 557 366 60 421 272 66.3 42.3 407 315 768 496 1.052 1).630 631 LAS 55 463 299 77.0 47.2 536 346 851 550 i.i8i M'- 69'e 451 50 509 329 80.6 52.1 590 38, 925 598 1.2" 0,2:2 762 ,92 45 557 .360 9316 57.3 646 417 997 646 i.d25 0.356 144 534 4C 608 393 96.9 62.6 7•^,5 456 `.110 1-17 1.5i8 ME Si:) 35 667 431 107,0 69.2 174 500 1240 801 i:7"7 1,129 1013 i55 30 730 472 118.0 76.3 848 548 1390 899 2.03i 1.313 i196 728 25 807 522 132.0 85.3 939 607 1560 I)Oa" 2,3='8 ."1 1251 20 506 506 1.49.0 96.3 .05, 682 1710 i1t4 (' ! i5 i040 672 172,0 111,2 1212 763 2060 1331 78 2.954 L =7 J64 10 1254 808 206,0 133,1 1456 941 2440 1577 3.A 1-, 24 '26r 5 1700 1099 283.0 182.9 1983 1282 3010 1984 i,%W4 25 ; 1642 HEPCC, INC (FE1 Station = 350 eq. :4iles D,'dir�aga Area ,DA1 t,ataioochee Creek, NO (CC) Eta"crl = 49,2 Sq, ;}ilea Drainage Area Nawport, T11 (NE) Station = 666 Sq. Miles Drainage Araa North Carolina-Tennessee border (SL) = 536 Sq. Tiles Drainage Area Change in Flow per Sq. Mile Drainage Area: NEf-;HEf+CCf) NEda-tHEda+CCda) Esti•aated State Line Flow: SLGa f (Change in Flow Per Sq. Mile) + (HEf+CCf) r r r- 1-I O.! r'M Io `n « 1 ] N P] r cJ I.T o I I- I R'+ ! •C I .. I A t t'! C I C [.! .`lJ Y] C.1 r I 1`.. r!` ..rl I'.• r I• •CI Crl r rJ n r 1 U 1 4 1 r • I" !-1 C.I I 1 I f. I r.. I CV r :r •`y • I 1' CF W .n Y. r'1 U7 .v •-Y .f. .V C^ G 1.. _In `.I 11 V] w C'1 !.'} ..• 1 I CJ - ' r • N N I 1 r! I !r �! C 1 C'I ^' .l' `� •? 1" I 731 ,Y lu 1�1 •l'i 1 1 .a 1 C1 j 1 i ..•. V.y 1 1 r^i 2T; 1 1 1 1 1 1 1 I - 1 1 I 1 • 1 I C 1 47 U] `aT 4'J In Y al+ r� .. 41 I'-- O .f' '.� -• N O ['.+ [y d` r0 ._ =1 O f5 1 d x 1 u a m j 1 o C i ul .. r .-. o t.J .f• m '" ': °'] o w . r .-. .o m 1'a. .f• _• -o m m O .-, Iu 1 YS ri m wo- Mc: - _, oL] r-. m o- l_-T r,' ui � o n• _ wc•� N_ ram. t_] 1 in w r+J 1 i 1 H � H 1 i a ' _. E-1 a i o v n n• .J 3 +`. 1� w 4m7 PM� r0 nL'l ICI UN-'] C'J f o+fO..! POY]. 1P.•yS mI•n1' Nm�1 arU_]l MV.ry] rWy C NUlJ CQm'J 11, mP tto. C'w.4 rrn-• -mY rI.-.-. rh+i pVS er f`. 1•] hi CJ E 6. O• 1 _ � In ] cn V � 1 I m m In •r 4] IYJ CV ••� h `n ty V p O 4` U9 r4 N n- tr YS VJ m p. O r.J W !'] U'lFy P r� .l _ 1 r- U'] n w !'! r"l M P'.1 N hO y] M rn rV Cam' A w m Cn L7 N ;J C] CI ti] i ry wt' N ^ • U¢ -41�. li � 1 I 1 I I r:: M U` •• p- M y. U] CJ n P C' M CI` m hi hl r..T r- r� •O O 47 ry 1'] M M V. y] O• 1 1� m O O] cr. 1`. Vl p. r� •J] m U. O` [n !ti m rti.w -CI n. r'. 1 N Clr O 6 n' e-'• m P [l.. RI � Rli � ••• U O LS. 1 r_] 1 1 1 1 f� .n m CV r^J J] r` CY N .l. •rf ry -U -A m 1.1 m .0 y'a [n m W ^ .• •.. Cn fy O. C`l P 4o i .:} W. d' y- V' aY u} } Y W.f rt!' >' '.r V :l• W' aT W } K .Y. a}' q' 1 sa' i 1 1 1 1 M, y W fIi n] ni vi L] trl u_l V] In L'T u-] 4] In u4 4'J w .il w .n •O ,!'] 'S m CO m M rb CO m CIJ CA m I ^ CV M v uJ .•] ra pi O' r• ^ .N.. ^. N M ar U] .p r. pi P _ 1 1 I /. Y1 A-3 TABLE II (CONTINUED) (dl (Xd) 94solute 'ti•alue hr;thaoat;c Percent of Fercent Scat+=--;lc Difference Siffer?nce D'Ifference Near. -14.0 -2.42 20.47 Saz.P1a DeY;at1Cn 25.91 23.29 13.69 o. Data Faints 30 -A30 ------------------------------------ nean Percent Error of Estimate: 20.Sr. 4p r-uimat2 N4};i elm (90 Fercentiia) E--or of Cetiaate; 'a8.3X Stede<its "•" Test nes;jits 499 Percentile): 1(29, 0.01) _ 2.46 '?a: ud '.near, different?; t = d - ud - -14.03 - n = -2.97 equals 0. 31(14"0.5 25.911(30)^0.5 Fl; ud does not aqua! A. ?h?refere, ft?,ect 2m. The difference in means is a sianificant at a 97' ;:onfidence. 1 I 1 P CA �n 41 N r+ �] r� CJ ,O rT y P CA ` f.J rJ r+ h] •i+ C] .a ra v m 1 iJ]- o�• n]• :]:' n] t:li m Ln N as cum ]] G N cr"n m" m Gi w LG T m m m Ln ca' r:G'ai i �« ST to crl cn can Ln cn UI Ja .h .p. s. ;u .J„ }:, 1 1 1 1 I 1 "1 L;1 .1 rF,'• A 1 C i C4 Jn C,4 In CA .ia A Jy In 9 In Sa I 'GV• f Iry Tl _ N 4J y. cn CA 4J Cf- =! :h Jh Js Lll :N C n IT UI r a C I Yl .n F, Ca N 1-YJ ,-� ._ ,..- �. f9 'n Gn P ¢] ':/1 p] CT P N p.. . N F.] r [JI f.J n] [[l fJ" 'V � � 1➢ kJ 1 rv• 1 •p .C� T si w a! Cn -:] o :11 fa m P V m P Gt' y LL] V u] .n J) m o• •n —4 la ra Jn [r- C.n rJl F LJ CO CA rJ In 1-' o— V y V w F.J 41 N w u .P �O J ni h a ~ i m Je -u w N In P F.] cn cn Gn 1 i 1 r, i Fn � a 1•J N .ra ram. r N r.] 41 P J N N V F] CA •n coCfl P V !.] N •O -J V f.n Ln V O -O O• V r CA Cr In A CC P Ul a c po LI b 1 r •J I]• n) G w Lp P 4{ N y d !J N Ltl 1.. 0 O ,p N P V N CO fa 1 H I rn WWW r 1 1 ii � ij ti CA y 'S .,p P J •L> ,n N 411 Cn In R] .!� V.J Cn P -a CD .v UI N In P -Cl Ja ] ...J r-• G '� UI V, p In [D N •O 4{ .� 44 CJI O• -o '. W I H 1 1 I C3 I •v n n n I 'u - v •• 1�` . . FJ ram) N •-• In G N N r� r� r r r :.. :... ... n-i rF r.• r.., r+ 1,C7 F j .! C-n C4<-1 CA1A P w a.n Cj P V y p r —1 -G O F.l N O In a-- .A r P CAV "O 1.1 r-. N O N '!" -n N ti I:JI N 1 1 1 1 1 I I I • I 1 1 1 I 1 rl ...... y T t• - I 1 vi '1 4• IG I I•.) .... n. G.J :.:. n.J 41 CI 3. In ~J L I G] F l ..l �! IJ 'G! •" J] rJ C..1 I r ) Cl. � 1 I " P ~ �_.! la U� r-• p tr. t> •V CJ Ja �_ :., I_ � a+ ... n) 1 f.n :� N :A .+ 1 :�. �p In 'r. I •ta I,.) ;Jl Ln 'S) CI i.:) Cl.l ••l ,.1 Ln Y] r•a [1:1 CT Gll LY'l KJ -r 'h CT J V _r> .{a. ••. Cl] fID I A-5 TABLE III (CONTINUED) tt.501ute Value ;'.tf.ee3tiG a2r-ent Gf Percent Stat;StiG gif=erenCe difference Differeln Year, 7,27 8.24 14,4p .-aaia Deviatian iS,&3 17,22 M 14 Ac. Tata Foi: t_ �p 30 ob --------------------------------------------------------------------------- lieaa P2rc2r,` Error of Estimate: 14.41. appruilat2 SalH,, (9 i@p Pcro=ntila) Error of Estimte: 28,37. atudent5 "T" Test neesalts (99 Percentile): t(29, 0.41) = 2.46 Ho: ud i ,ran difference) t = d - ud - 8.24 - p = 2,11: equals p. S/(N)"p.5 18.831OW0.5 Hi: ad does not equal p, Therefore, 4ccept HG. The difference ir, €eons is not significant at a 99% Confide:ic?, ac, ; m 931f±Z'T. _ a, le ev , 3 m m D ms ' OHUCO'0 • Rm w L Rs e m ') no 2 m mRlm, ! mw : : < m q; E mews w ( ! s ; m yes a2 s m9 E &z s a m ! 22 ; m; 2 3 St 2 : 40m w =, tCP EZIZ an e 2 *m mj mR m2 &s s e w , a ————— ———————— mg : , J ±; . , z7: a =B @m e e m: & cam . .4 ; m m k , R 6 » 2 R m, Ilk HIE MITT �! ill m m , A: mt 2; 2 B 70Z &, e; m; &; + a m Be &= m m R 5e St + 3 »; c 2 2 Gs 'it 21 m= »; R 2 q 2: MITT G & 3; MIL ; ± R 3 I m! m; m k SZ7 SEA G; &: 2n m E 9 &e ) OH 3; m: bn m m m m mI m9 ee m g @ « £; 2, e; 2 R in EWE ms m 2 I m2 m; . G = k S £ m; 21Z mn . G 2 ¥ EM m m; GPI 3; m Lt 2 mZ m m; ms 89.111 3 k m &I R &: MITT mn 2 m g Wzl 2 E m, . a; m m m a= m: m m LEFTmE 7; m m 2 „ S MIT m; 2n m m 2 t mn m m m) »! m; 2 E + WE ¢ 7n &e m: m a y mi ± k2 7 7; m By m m m; 96/7 2: m, g & +; s a; a; 2 3 B ea m &; To I S: & 5 HIEm &n & £; 25 2: HE \ m mZ m rn me 2; m 2s 7 ————————————- ——- —————————— _ e »c •v : m= , dE a a CUB! +! +» 7J 7_ AI ariErVI ,v A-7 TABLE V 1 'dTP 1i? AGT88L EStiutad klazi afs:�d'cC:•_c.' . _ :E":'_ a -cha, aE 0;5_hErge 6[ErCO S`zt=_ '-irE Stat_ __E2 ;.-•:. -::= 0 Co' �10h .Jr F1'.,1w Ca'. Color Ba`e t���: f]1 (G��l fr41 j ;�1 nc Ri ----------------------------------------------- -------_--___----_--___-_--_----_-_-____-_____--_---_--_-__ 1184 41 7i0 499 52 55 4,- 2!34 46 805 a58 1040 798 =2 e6 4 4<34 45.2 a14 675 50 57 5i94 46, 926 116i .40 50 6784 45.5 771 335 71 63 1184 43.7 594 355 52 45 - 8194 45.2 944 352 82 % 1t 91E4 42 735 171 100 110 10/84 44 595 :77 96 114 18 19,3 11iE 4416 a85 266 92 121 12/34 47.2 932 292 95 131 37.. 1185 46 926 304 90 95 2/35 46.6 835 670 50 47 3/E5 43.8 772 350 66 10 4iE5 45.3 8:3 134 71 5? -12 -i`. . r 51@5 45.9 773 275 a1 61 \ , 61a5 44.6 679 172 97 86 7185 45 661 172 a9 108 ;c A 8185 44.7 S09 229 95 34 9/65 431.3 753 137 24 1i18:• 41.6 524 122 ^7 ;47 < - 1i;8: 42.. 835 413 62 71 2165 471,1 885 276 -g; q_ 11B6 43.1 1032 i68 1=3 170 21a6 13.3 1040 289 97 Zn 3da6 43.9 958 Vh c1.4 1^.5? 252 _06 ,1!86 --.- E64 226 f6 - 6iB6 43.4 950 177 130 :iU ------------------------ / .Y A-8 TABLE V (CONTINUED) :v.. / • .:L: 1,nu.t :'hsolcte 'Ja1ua Arithasatic ?=_scant of Fercart p'c:a•enc= Ji'fer�r,Le 2acple Seviaticn 18.55 21.39 12.76 Ta♦v. t= Points • v.V 31^i y� "e�; FErcant Error cf 'Esti;aate: M1" A-r-r_Yi c.= "aa:due? M Ferca "_.'L) Error oi E5tiaL2• 35.1•1 Stc:_^ts Test 4esaits (99 percentile): t(29, 0,01) = 2.46 -o: A (wean di-feren a) t = d - ud - 4.37 - 0 1.29 equals P. S/fNAo.5 18.55/(30)^0.5 rl: ud does rat equal 0. Therefore, Accept Sa. The difference in weans is not signiflcart at a M Corfidance. APPENDIX B RAW DATA c,� Champion International Corporation Pigeon River Data - Monthly Average Summary B_1 Flow Data Color Data } Above Canton HEPCO Above Canton HEPCO— I-40 Bridge Tenn Color (MBB) (NBD) (ppm) (ppm) 1ppm) Ippm) 1982 -- ---- --- -- July 128 260 24 187 a8 — August 99 179 20 206 70 — September 62 128 TI 298 91 — October 61 131 29 279 134 — Noveaber 139 304 27 238 149 — December 361 622 20 98 70 -- 1983 January 189 353 12 140 86 — February 347 663 27 102 97 -- March 555 914 22 86 65 -- April 642 1231 12 83 55 — May 237 1206 10 84 62 — June 131 365 9 Ila 59 — July 81 243 14 163 50 — August 58 155 11 146 52 — September 56 163 10 240 97 — October 86 243 12 175 112 — November 156 353 10 172 108 — ➢ecember 136 975 it 79 66 — 1984 January 195 490 7 92 64 55 February 289 50 8 105 80 85 March 349 798 8 90 65 66 April 333 673 8 •82 .54 57 May 511 1161 12 79 49 50 June 146 353 9 114 67 66 July 149 355 11 102 41 45 August 173 352 10 140 57 71 September 59 171 7 212 70 110 October 67 177 10 211 109 114 November 129 266 9 172 116 127 December Ila 292 6 179 104 131 1985 January 113 304 8 167 95 95 February 303 670 6 55 37 47 March 135 310 9 106 56 70 April 133 334 8 98 . 56 59 May 125 275 10 123 53 61 June 71 177 11 194 47 96 July 79 192 it 176 53 108 August 101 229 11 156 80 94 September 63 137 13 225 45 95 October 51 122 13 233 96 147 November 236 413 12 130 61 71 December 121 276 10 152 90 92 1986 January 66 168 10 232 112 130 February 113 289 10 210 120 130 March 158 490 11 109 57 62 / April 85 232 10 206 74 _ 84 May 91 226 12 161 97 113 June 75 177 14 243 62 110 a Edited 1-40 bridge color: Data collected during CPL Powerhouse operation only. B-2 PIGEON RIVER DATA CHAMPION INTERNATIONAL - CANTON MILL 7/1182 TO 12/31/32 CA.Flow Ca.Cmlor HE.Flow HE.Color 140.Color Tenn Colr DATE ud mg/l mgd mg/1 mg/l mg/l -------------------------------------------------------------------------------------------------------------------------- 1,/1/89- 69.1 14 IS 190 76 - 7/2182 65.2 5 144 218 63 713/82 - - - - 7/4182 - - - _ 7/5/82 63.3 33 141.4 225 23 - 7/6/82 61.4 23 136.3 208 23 - 717/82 70.4 23 134.4 173 23 - 7/8/82 66.5 14 150.5 248 85 - 7/9/82 67.0 14 168 349 63 - 7/10/82 - - - - 7111/82 - - - - - - , 2182 69.1. 14 164 173 33 - 7113/82 301.7 33 550.4 278 03 - 7/14/82 149.9 40 229.3 120 128 - 7115/82 323 14 589.2 120 105 - 7/16/82 156.3 33 284.9 93. 120 - 7117/82 - - - - - _ 1/18/82 7/19/82 249.3 33 410 235 112 - 7/20/K 142.8 14 623.8 93 120 - 7/21/82 118.9 33 221 155 138 - 7/22/82 139.5 33 333 155 112 - 7/23/82 112.4 14 208.1 138 14 - 7/24J82 - - - - 7/25/82 - - - 7J26J82 108.5 14 196.4 200 190 - J27/82 122.7 14 189.3 173 112 7/23/82 12a.8 33 215 248 112 7/29/82 108.5 s0 241 182 93 - 7/30J82 115.6 33 226 147 93 - 1/31/82 - - - - - 8/l/82 8/2/82 156 14 326. 63 85 - 8/3/82 127 23 262 120 76 - 8/4/82 112 23 227 128 23 - 8/5/82 99 33 203 208 6.i - A/6/82 101 14 199 225 85 - 8J7/.32 - - - - - - 8/8%82 - - - - - _ 8/9/"2 91 23 184 248 85 - 8/10/82 101 5 214 128 57 - 8/11/82 93 23 209 208 93 8112/82 119 40 244 248 23 - 8/13/82 87 23 189 147 85 8/14/82 - - - - B-3 PIGEON RIM DATA CHAMPION INTERNATIONAL - CANTON HILL 7/1/82 TO 12/31/82 CA.Flow Ca.Color HE.Flow HE.Color I40.Color Tenn Colr DATE mgd mg/l mgd mg/l \m9/1 mg/l -------------------------------------------------------------------------------------------------------------------------- 8/15/82 - - - - - 8/16J82 /3 14 151 314 76 - 8/17/82 74 23 155 200 57 - 8/18/82 81 14 206 1002 14 - 8/19/82 72 14 157 200 57 - 8/20/82 71 23 153 155 63 - 8/21/82 - - - - - - 8/22/82 - - - - - - 8/23/82 61 14 127 173 93 - 8/24/82 63 14 155 147 63 - 8/25/82 61 33 132 235 105 - 8/26/82 57 14 119 358 85 - 8/27/82 56 23 112 367 112 - 8/28/82 - - - - - - 8/29J82 - - - - - - 8/30/82 - 14 108 173 23 - 8/31/82 323 14 107 297 105 - 9J1/82 69.1 14 142.8 248 23 - 9/2/82 166.7 14 339.2 248 85 - 9/3/82 89.8 14 208.7 105 112 - 9/4/82 - - - - - - 9J5/82 - - - - - - 9/6/82 54.3 . 23 107.2 270 23 - 9/7/82 56.2 14 120.8 349 76 - 9/8/82 56.2 14 116.9 288 33 - 9/9/82 54.9 14 113.1 305 23 9/10/82 56.2 14 116.9 349 85 - 9/11/82 - - - - - 9112/82 - - - - - - 9113/82 63.3 14 126.6 253 93 - 0/14/82 61.4 ' 23 124.7 225 147 - 9/15/82 54.9 14 116.9 288 50 9/16/82 53 14 111.8 316 23 - 9/11182 53 14 104 173 40 - "!18/82 46.5 23 - - - - 9/19182 55.6 33 - - - 9/20J02 61.4 23 117 561 155 - 9/21/82 61.4 33 112 402 173 - 9/22/82 56.2 14 105.3 402 138 - 9/23/82 53 33 104 323 128 - 9/24/82 49.7 33 100.8 248 57 - 9/25/82 - - - - - 9/26/82 - - - - 9/27/82 54.9 14 115 253 335 - 9/28/82 51.7 33 104 349 164 - B-4 PIGEON RIVER DATA CHAMPION INTERNATIONAL - CANTON MILL 7/1/82 TO 12/31/82 CA.Flow Ca.Color HE.Flow HE.Color I40.Color Ten, Col, DATE mad mg/l mgd mg/l mg/1 ag/1 -------------------------------------------------------------------------------------------------------------------------- 9129132 51.7 33 100.8 349 192 9/30/02 47.2 33 96.9 190 164 - 10/1/02 49.7 33 102.7 208 147 - 10/2/82 - - - - - - 10/3/82 - - - - - - 10/4/82 46.5 23 94.3 543 50 - 10/5/82 48.5 33 211.2 305 164 - 10/6/82 47.9 33 206.1 235 57 - 10/7/82 49.7 33 203.5 210 93 - 10/8/82 50.4 23 208.7 253 173 - 10/9/82 - - - - - - 10/10/82 10/11/82 76.2 50 232.6 253 155 10/12/82 57.5 33 115 173 155 10/13/82 62 23 235.1 173 155 - 10/14/82 108.5 50 191.9 270 155 - 10/15/82 62 33 129.6 155 155 - 10/16/82 - - - - - - 10/11/82 - - - - - 10/18/82 54.3 23 98.8 208 155 - 10/19/82 56.2 23 95.6 P/8 128 10/20/82 56.8 23 97.5 288 128 - 10/211 60.7 23 130.5 437 155 - 10/22/82 60.7 14 ' 104 200 138 - 10,,23/82 - - - - 10/24/82 - - - - - 10/25182 74.9 33 162.8 411 138 - 10/26/82 89.1 33 179.6 270 138 - 10/21/82 58.l 23 128.6 208 57 - 18/28/82. 62 23 120.3 323 113 - 10/29/82 56.2 33 118.2 437 155 - 10/30/82 - - - - - - 10i31/82 - - - - - il/l/82 48.8 11 128.6 420 173 - 11/2/82 36.2 23 124.17, 3,14 190 - 11/3/82 60.5 33 140.2 367 200 - 11/4/82 275.4 50 577.5 190 173 - 11/5/82 229.5 33 361.0 112 120 - 11;6/82 - - - - - 11/7/82 - - - - 11j8/82 88.9 33 196.4 248 105 - 11/9/82 - - - - 11/10/82 17.9 33 175.1 260 138 - ll/11/82 - - ( 11/12/82 15 33 161.5 314 190 B-5 PIGEON RIVER DATA CHAMPION INTERNATIONAL - CANTON HILL 7/1182 TO 12/31/82 CA.Flow Ca.Color HE.Flow HE.Color 14O.Color Tenn Colr DATE mgd mg/l mgd mg/l mg/l mg/l -------------------------------------------------------------------------------------------------------------------------- 11/13J82 - - - - - 11/14J82 - - - - - - 11/15/82 95.7 23 221.6 235 164 - 11/16/S2 90.9 33 199 260 155 - 11/17/62 05.6 14 191.8 260 190 - 11J18/82 90.3 33 211.2 340 173 - 11/19/82 161.9 33 308.1 173 190 - 11/20/82 - - - - - - 11/21/82 - - - - - - 11/22/82 166.8 5 310.7 155 23 11/23/82 149.8 23 281.7 190 182 - 11/24/82 131.5 14 267.4 200 173 - 11/25/82 120.9 23 246.9 190 147 - lli26/82 114.6 23 226.7 164 40 - 11/27/82 - - - - - - 11/28/82 - - - - - 11/29/82 532 33 1439 138 105 - 11/30/82 - - - - - - 12/1JS2 354 50 696 164 120 - 12/2/82 339 23_ 669 93 105 - 12/3/82 323 23 554 155 112 - 12/4/82 - - - - - - 12/5/82 - - - - - 12/6/82 1178 33 1580 57 76 12J7/82 420 23 '321 63 57 - 121'81S2 436 14 676 120 6.3 - 12/9/82 319 14 570 85 50 - 12/10/82 299 14 496 120 63 121ll/K - - - - 12/12/82 - - - - 12/13/82 203 23 346 93 57 - 12/14/82 263 23 485 120 57 - 12J15J82 269 23 460 105 85 12/16/82 978 23 1574 63 57 12/17/82 420 23 753 50 63 - 12/18/82 - - - - - 12119/82 - - - - 12/20/82 285 23 527 93 50 - 12/21/82 250 33 474 120 76 - 12J22/82 224 14 417 85 57 - 12/23/82 213 14 413 76 50 - 12/24/82 224 14 397 155 93 - 12/25/82 - - - - - - r'" 12/26/82 - - - - 12/27/82 215 14 413 40 50 - B-6 PIGEON RIVER DATA ' CHAMPION INTERNATIONAL - CANTON MILL 7/1/82 TO 12/31/82 CA.Flow Ca.Color HE.Flow HE.Color 140.Color Tenn Colr DATE mgd mg/l mgd mg/1 mg/l mg/l -------------------------------------------------------------------------------------------------------------------------- 12/29/82 250 14 467 120 105 - 12/29/82 339 14 543 57 50 - 12/30/82 263 5 453 105 76 - 12/31/82 239 5 417 105 50 - — 36.2 5 94.3 40 14 - 11AX 1178 50 1588 561 200 — AVE 143.05 23.31 276.76 215.71 98.73 - �v v to N N N N to'r.J r' to to to I 1�\'�.�.`��._\V..'�\ ti\r F\-. �\..��✓\ I--- H Y- 1-+ t-�. �1 C., tofJ N fJ rJ N P- to POF-• \\\T Y 1 A W N , O +6 1 C +43 Cn A'+. (.1 N CA to CMCn�O w V T A CA toH CMCA-•O •JJ V A LJ to 4J OJ CO 4J �J w m OJ 1,- w 43 CO 4i OJ O w w m A'. w aG dJ 43 w w w cn m cn cn cn cn cnw cn cn w w w cn cm U4 m 1 W CA bJ CN CA CA W W CA 41 W W CA Cnl W CA GI GI W W W W W CA W 41 W W W W W CA CA W W W W W W W W " W CA CA 1 1 to 1 1 1 1 L7 y E3 1 1 W 4J GJ A Ul I 1 I W 1 to N I 1 H CK) 14 N to I 1 1 1 - H h-. t� L.. 1 I I--• PO to N C., I I 1 IP T w VI CD to CD �C. CMH V 4J �D A J>• I--+ w CA4 O l [/r V �O V �O Cm CMV J O fll +O •A `V J> \I A W N w I 1 I I 1 (7 I y I a I I 1 1 t� I 1 I 1 1 1 1 1 IO c9 N N N CA f.n Cn A CA CA CA CA CN Cn 41 A A fn A y U A U L C.n CJl V1 A 4 CA O A A U W Y 1 O 1 t 1 I I I I S m 1 I Cn Cn 1 LN A 1 1 6J W W Y W 1 1 1 N H N H 1 1 W N A A W 1 1 W .0�O GJ CA W CD 1 Ct'T CJ V w [n V N V A N A VI Cm toto W W> p CA w I p I >s 1 I I I S 1 m 1-• I I I I 1--• - N I 1 I I I I-+ N r- 1 1 N �- H r. I I I 1 1 CD _l a C.1 CD Cn o CM Iv CA N •G Cn w O O A O� O w �O i. v N V 41 CA o 1 S[ll ' CM CA CA 41 41 O U VI w qJ O GI O N V CMV •F pJ N CA V W O T OJ Cn CA 1 6 +J 1 1 I O I Z I p I H F+ H H B o M m _ I I I I to � •-• t✓ H C, r. �.- to r i � CJ m � Z<N R• CA C, Cn N O O fJ O I 1 CA V1 N w N I 1 1 P N c, O V L+ C1 A T CA U U U 1 H O_ W 'L O W GI W T V O CA Cn O Cn GJ U G:• U O [n w Cn LII p. to N W O GJ W V V'V 1 a A 1 O --1 •--I H I r Z 3J I H N p CA L7 I o w a I Z I y 1 O 1 Z i s 1 H I r I r I i 1 1 I I I I 1 1 I 1 I I I I I I 1 1 1 I I I I I I I J I. I ' I I 1 1 1 1 01) I 1 1 I I 1 1 1 1 1 1 1 1 1 1 I I 1 1 1 - 1 I I I 1 1 1 I 1 J 1 ' J I H 1 Z 1 O 1 I-� 1 F-- U CA U •-r I C 1 C U 1 s J \ 61 1 r • W Q CJ F- 1 G[ H O 1 O Z' M O •-I I i' V a M ✓> h v'J O V> M b Va M I!! b �[. M1 b V') N f VJ O Ira O f�J Ih M f� N> h [D W \ U •-� 1 1 I 1 1 1 1 1 1 I 1 F'r 1 2 i � O I H 1 CO O O V) .N.t h O O t7 M O V> M I!a S U U 1 .-v h �! M1� O •M-I .Ni .hi 1 1 .N-I .N-r T .H-� 4. 1 I b h O� O CO 1 I CJ �J O V> h +'T Ih tea ' 1 /> C6 CJ O y U • Cq 1 W 1 S I 1 I 3 I O I M ?. ryJ M1 M +O M b N V> M1 �f O 1\ p CO N N N T V> T b@ � •-I M1'C 1 b �t N O. T �f T V CJ CO •-1 T A mil' O b V> 1•! H wO @ VJ V> �} {p N y. b S 1 I 1 1 1 •-� N N Va t7 N N H .-I M N N N - Va N N •S �r N Na N> 17 O \ I 1 1 1 1 1 I I 1 1 I 1 I I I U U I • r 1 ti 1 U 1 1 I 1 :3 I O lJ I OM1 b y. 'y' V> CO ti M T •--1 O Va �O 1\O. !] ," h N Ih T 40 C+I O N N N �Y O 17 N IJ_ U 1 N N I N 1 1 N N V> Iq tq 1 I N M M N N 1 1 V) �D V> CI' Fa I 1 M tq CJ I 4,+ 1 1 iD 'J Crj 'TS C' I 1 h +L• N Va• <i 1 _ Q 1- U 1 1 1 1 I 4 S w Ix, PO w M M M M M M M M M M N9 M M w M M M M co M w M M M M M NJ tq 1^J C6 CA CO iu OJ f%� �C O] CO W OJ OJ G"1 OJ /JO CO 6J O T CiJ _O G7 !L C6 G> O] sJ O'.J OJ CG Cb CO coC� Cii CO 9J CO CO C8 CO W W F- I V] ti M1 T-I O H CJ M K Va +D M1 Cq y CJ Na T V> b M1 CG T O �J N'> zf b CJ ti O CJ 1 CJ N 1 O V) D M1 O T O[n I CQ` C CJ CJ N .Jj N N N N N N N N CJ M�t•�P7 tq M t�> M N> M M t7 M M V> 10 M f� M 1. �� U Cn U Cn U U I- ---\\\ APA AAAAA I O N �--• I--• � H r U A W N W O �p 03 V O. U i+ 41 rJ O V W •J U U A 41 rJ O b w V T U A W CO OCi 4J w w w w 0 W w w tirr w w w w w 43 ]J C CA w w w w w w w w pJ w w CJ CO w w 03 w w W w w w w w w I CAW(d CA CAW CA6J W W CAW CA CA41 4J LJ CA CA 41 W W W W W W W W W W W W [N W W W W W CJ W W W 41 W I I I n a N N N W N I I 4J L! LJ � A 1 1 W W .F. 1 A 1 1 ✓ T V 1 1-+ 1 1 OJ •L A O'. Cn I 1 A I 10 T CM CAJ� N A � U A V L A O W VI N V b N N LJ �J U A VI O A A A U p� (n O b A 1 O 1 E � 1 1 1 1 L7 1 y 1 a . 1 I 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 <T h-• N U U W A U 41 U VI U U U U U A Cn A U U A U U U A A W A W W W 1 O 1 • 1 S 1 m I I P T ti• IX'i w 1 I `i b J~-. 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I i 1 1 I I I I I I I 1 1 1 1 I I I kn I i I I 1 I o wI I I I 1 I I 1 1 ' 1 I I 1 1 1 I I 1 1 I 1 I I I I I I J � 1 z I HU /A U •--• I Q \ \ I 1 1 1 1 I 1 1 1 I I I I 1 1 1 1 1 1 1 1 1 I I 1 1 1 1 I 1 1 I I I I I 1 1 1 I I I I I 1 1 A I C T I 17 C F I CC J \ p) I z 1-t o L I O M O •-'I I Y/) 1\ V'] N VJ M M h u'1 N Y!7 •p �T V] •D u7 V's f� V) 7 n V) -.� 17 M IX) 1� ) VY CA V) h. `. p• I I 1 I I 1 1 1 ..I 1 I I 1 I t-• 1"•.�t O 6 1 2 1 O 1 1 d O 1 CJ f�. V) V] O O O f� �O M O O CO M M u'J Yn O O M Yn N u7 t7 �J O CO Cb W O O] CO K �� 1 i .•--I-• u7 CO 9] Iry 1 I v) v) Yn n M Yn •N-I .Mi .^.• R CO O yJ y T O .~I r..] R. �J N in t.-'-• .Nq .C-•J .Mi U • � 1 W I S 1 I I 3 O I M N N 17 CA n p] 1!J T tb O R. n V t7 T 90 �O N] O V' Y7 � tT p] .•y f� f� y) 11'O I S O �Q D O. O �O �7 O� p0 V) Q] Yr y. �Q N u-] p. f� • N) CJ N h D] M O O. v7 O O�LI- OI 1 •-+ O CO Cb � I I � {O � � O I 1 O 1 R < < 1 1 � d' a t') Iy 1 1 M t7 17 t7 M 1 I N) M N) M N 1 1 N Y7 CJ t3 1 ti •-y W 1 S 1 � 1 1 I 1 ti I � -T u) Yn y v) v] In Yn v] u') V) < 11'l V) ✓) 11) IA vs u'] c V) u] In v) vs u) In V) •aT v) V] O \ I I I I I I 1 I 1 I ~ 1 1 I I ~1 A m 1 U 1 1 I 3 1 O I I\ CO N O CO •-� f� O r` •-r CO .--I �O M A �D {_O 'D CJ V) In 1 O N Q� `.O O C6 y ; .^y +y �J C•V �J M V) O y O CJ R• O 11- OI I N N N N 1 -f Iy N N N I 1 N 1 1 1 ^- -1 I 1 •-• �� .-1 1 I �+ •-• 1 1 • E: I 6 I U I I - 1 1 1 I M M 1.7 M M N) M M M M M M M Iq M M M M M M M{O W O co CO W N) M M M M t9 I•] t0 M N) W) N'] 17 !7 t7 M M tO M M M t0 I CO •]6 G] {O N W CO Q7 {O {O T CA {O 6] OO Op O] CO IX� 10 CG. J) CO 0. Q) O] O O W '] OO CU 0.� T Gi SO CO A CA !L G? F- 1 .�i .^• CO ti O N M c` V) �p r. CQCy t� �? ti �-10 f� M O+ C.^ h �O Cn C 1 N CJ N N N N N N CJ CJ t7 M \-�\�t\\`�1.^�.•-y .-• .-� �� � � N CJ N N N N N N f4 N ✓) IA v) V) L{J 7 �17 Vy IA In v] 7 V) Il) V) V) 'D -6 �• +.O 'il 6 tiY 'C 'tip •i� •.{. ..ii 0 B-11 PIGEON RIVER DATA CHAMPION INTERNATIONAL - CANTON HILL l/l/83 TO 12/31/83 CA.Flow Ca.Color HE.Flow HE.Color I40.Cclor Tenn Colr DATE eigd a9/I 9gd og/l ;mg/1 og/1 -------------------------------------------------------------------------------------------------------------------------- 6/30/83 126 /6 320 138 85 7/1/83 176 23 446 105 23 - 7/2/83 - - - - - .'•/3/83 - - - - - 1/4/83 122 5 428 112 50 - 7/5/83 197 5 394 120 50 - 7/6/83 107 5 335 147 23 7/7/83 - - - - - - 7/8/83 88 5 267 138 ' 63 7/9/83 - - - - - 7/10/83 - - - - 7111/83 - - - - - - 7/12/83 75 5 229 138 50 - 7/13/83 71 14 216 190 85 7J14/83 67 5 211 147 76 - 7/15/83 114 5 211 164 63 - 7/16/83 - - - - - - 7117/83 - - - - - 7/18/83 70 .50 256 147 8s 4 7119183 70 5 214 147 63 - 1/20/83 65 /6 '201 105 /6 - 1/21/83 65 5, 192 113 105 - 7122/83 61 5 164 120 63 - 1/23/83 - - - - - 7/24/83 - - - - - .'/25/83 51 14 194 208 23 7/26/83 64 5 222 190 23 7/27/83 57 14 169 235 5 - 1/23J83 50 5 9/ 218 14 - 7/29/83 53 14 156 297 14 - 7/30/83 - - - - 7/31/83 - - - - 8/1/83 103 14 102 260 57 8/2/83 /0 14 126 305 33 - 8/3/83 57 5 173 210 23 - 8/4/83 59 5 125 190 23 - 8/5183 64 14 165 190 33 - 8/6/83 8/7/83 - - - - - - 8/8/83- 91 5 182 248 63 - 8/9/83 49 5 176 218 105 - 8/10/83 49 14 153 208 128 - 8/11/83 46 14 147 248 128 - 8/12/83 55 14 189 190 85 - 8/13/83 - - - - - - 1 1 1 1 N 1 , I 1 1 1 1 I I 1 1 1 1 I 1 1 1 I I I I 1 ' 1 1 1 I 1 I I J j J 1 S I z o I F� I z 1 a ro o I Q \ ^~ 1 I I I 1 I 1 1 1 1 1 I I I 1 1 1 1 1 1 I I I I I 1 I I I I I I 1 1 1 1 I I I 1 1 1 1 1 1 t O 1 C Or 1 M C FI 1 W Q •Nv F- I H O 1 C H O L 1 W K M U \ 1 1 ~ � M M y M M CJ 17 M M •e-r P. �• y .--1 O � CJ � � P. O H F- .\i O fi3 I I 1 1 1 I 1 1 1 N 1 1 I I CJ I d I O IJ] 1"> N O M M ✓> N O Cp W e N V'> 1`+ V] M Qy V> N M tS N v O CO 1. e h S U p 1 1 N CJ M I 1 M N> N N 1 1 N N N M N I 1 CJ CJ 1 1 CJ M .-r 1 1 M 1�] N N CJ 1 1 !7 CJ U r Ea I W 1 S I 1 , 3 I O 1 O O M b O N O N e e b N r7 M T N O ?. t!> CP M N •D N b b V> p y->"'4 'O I H .e-� y � N> y y M N H y M N] 1\ � h ti b mil' ti r� •�i N O S 1�] ry y O .Ny e !•]la_ OI 1 1 �J 1 1 .-1 CJ N 1 1 •--1 --r 1 1 CJ �J H 1 1 N N 1 1 N 1 I •1 •-r Fv 1 - W 1 S 1 1 1 1 L I OO I •e-1 .e-I 1/1 •e-I .e-1 ,,e,J a •eY V] G !n V] M .e4 y Ih a !f> v> l!] V] V'> � •+ 1n � •+y-r V7 .�4 y V> e \ I 1 H •--I .-r U pr 1 I I 1 I 1 1 1 1 ~ 1 1 I I • Fa I ti I U I I 1 3 I O I e V'> CP CP V> h T V7 T b b !J7 N O 1\ e b •p CJ R• T I!> f+ Cti !r N b N � h� ; e u'> +S e N +S V'] 1\ +O e V O In V] O. IJl 1/> O .rh 1 1 V] +Y •Sl 1`. V7 I .1 +S ^J' In 1'+ IJ7 1 1 1/> �'J'LL P I I 1 I I 1 1 1 1 Q 1 U 1 1 1 1 1 1+> M M NJ M M !q M M M M !q M M M M M Iq M M M M M. r7 M N> w Iq M M !ry M M M M M M N> M M M M M M M 1 9 CP Cp M [O M Cp M N M N P] N N N M CO N W N Cil M CY Cp CJ N W N N N N N A• N N G W CU N M CP CA N N C6 1-+ 1 •c b 1� C'O y. O N M < V7 b h M T O N M O If] b f\ OI. O CJ M at ] b h Q I Mr •-� N N I M CO N N •i3 co N N N N CJ M [O N h] M LO N m_ n_ m_. R• T. _. ?. O• T. n. ?• T ?. R. ?• P U m 1 � .J B-13 PIGEON RIVER DATA CHAMPION INTERNATIONAL - CANTON MILL 1/l/83 TO 12/31/03 CA.Flow Ca.Colar HE.Flow HE.Color 140.Color Tenn Coir DATE mgd mg/1 mgd mg/1 mg/I mg/l -------------------------------------------------------------------------------------------------------------------------- 9/28/83 46 5 130 331 155 - 9/29/83 46 14 127 200 182 9/30/83 50 10 130 220 20 - 10/1/83 - - - - - - 10/2/83 - - - - - - 10/3/83 49 10 121 240 140 - 10/4/83 51 10 119 265 20 - 10/5/83 50 12 134 313 190 10/6/83 50 5 147 360 173 - 10/1/83 49 12 127 275 180 - 10/8/83 - - - - - - 10/9/83 - - - - - - 10/10/83 46 12 121 322 199 - 10/11/83 46 12 125 305 38 - 10/12/83 65 12 171 255 142 - 10/13/83 103 50 702 173 190 - 10/14/83 225 12 572 50 30 - 10/15/83 - - 10/16/83 - 10/17/83 75 12 216 100 83 - 10/18/93 . 71 12 202 ISO lsi 10/19/93 65 12 192 210 120 - 10/20/83 62 5 102 120 83 - 10/21/83 62 12 175 83 100 - 10/22/83 - - - - - - 10/23/83 - - - 10/24/83 225 12 494 38 97 - 10/25/83 134 12 329 75 85 - 10/26/83 110 5 291 50 75 - 10/21/83 99 12 258 85 100 - 10/28/83 86 12 233 100 112 - 10/29/83 - - - - - 10/30/83 - - - - - 10/31/83 /6 5 201 83 50 1111183 72 5 199 30 50 11/2/83 /0 18 192 218 120 11/3/83 49 5 130 130 85 - 11/4/83 73 12 217 255 83 11/5/83 - - - - - - 11/6/S3 - - - - - - 11/7/83 65 5 ISO 162 112 11/8/83 64 5 J8 275 100 - 11/9/83 62 12 171 237 100 - 11/10/83 65 1^< 184 237 30 11/11/83 77 12 216 295 142 B-14 PIGEON RIVER DATA CHAMPION INTERNATIONAL - CANTON HILL 1/1/83 TO 12/31/83 ' CA.Flow Ca.Color HE.Flow 'HE.Color I40.Color Tenn Colr DATE mgd mg/l mgd mg/1 mg/1 mg/l -------------------------------------------------------------------------------------------------------------------------- 11/12/83 11/13/83 - - - - - 11/1'4/R3 61 5 162 350 151 - 11/15/83 95 5 435 237 112 - 11/16183 61 5 160 97 132 - 11/17/83 95 12 262 142 132 - 11/18/83 86 12 147 190 151 - 11/19/83 - - - - - - 11/20/83 - - - - - - 11/21/83 188 12 432 162 142 - 11/22/83 122 5 295 120 120 - 11/23/83 109 12 276 190 151 - 11/24/83 313 18 717 199 151 - 11/25/83 435 5 481 38 83 - 11/26/83 - - - - - - 11/27/83 - - INSF - - - 11/28/83 589 30 1370 83 83 - 11/29/83 397 12 789 38 83 - 11/30/83 290 5 591 57 57 - / 12/l/83 229 5 504 50 57 - 12/2/83 203 12 308 100 83 - 12/3/83 - - - - - 12/4/83 - - - - - 12/5/83 463 5 1079 30 50 - 12(6/83 .921 50 1882 97 85 - 12J7/83 523 5 1032 3R SO - 12(8/83 413 5 000 50 50 - 12/9183 339 12 597 1 2 57 - 12/10/83 - - - - - 12(11/83 - - - - 12/12/83 963 5 2006 ,o 38 - 12/13/83 572 5 1137 50 75 - 12/14J63 467 5 904 50 38 12/15/83 382 5 753 83 38 - 12(16/83 325 5 641 75 38 - 12/11(83 - - - - - 12(!9/83 234 12 512 97 50 U128/83 217 5 477 83 75 - 12%21/83 200 5 449 100 57 12/2L/33 12/23/83 12/24/83 - - - - - •12125/83 - - - - 12/26/83 B-15 PIGEON RIVER DATA CHAMPION INTERNATIONAL - CANTON HILL 1/l/83 TO 12/31/83 CA.Flow Ca.Color 4E.Flow HE.Color I40.Color Tenn Col, DATE :mgd mg/l mgd mg/l mg/1 mg/l . --------------------------------------------------------------------------------------=----------------------------------- 12/27/83 160 5 394 190 83 - 12/28/83 1060 57 3240 112 83 - 12/29/03 435 5 1032 50 97 - 12/30/83 284 5 696 97 142 - 1'2/31/83 - - - - - - , -------------------------------------------------------------------------------------------------------------------------- HIN 44 4 97 30' 0 - MAg 1988 155 3240 360 218 - AVE 243.77 13.32 546.54 143.30 75.17 - • N IV IV N to I to to to to to N to N N\+,\\\I\\\\^•-\ti I\-• r\ I\� r\� --• \-. t� I.-. 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O O v) I N _ U O I • F3 1 U I 1 I 1 3 O I R R VJ co `O M b M T b CO M N CO T! 1 CA CO 14•--I b .N-I .`--1-I ly .My •f `JJ b V) 7 1 CJ N � 1 1 I I 1 1 1 1 1 I 1 1 1 6 1 U I 1 I I q I @ •Y < R @ V R C @ @ R R @ @ R R @ R . . . . . . . . . . . . 1 CC CO CO w w UJ qJ M Cp OJ M W W O? M O OG 0.') w w Co OJ {O LC• w CO Co Co K. Co W w CO CO Cu d3 W x. W m w •CC. Co G CG N M R CO T O CA M R u7 f� CO T O CA ly y .M-� �p fI. O: ti O N NJ V) b Q I ^' `--1 •-+ N N N N N N CJ N N N M M \1�_\T\�_\—.\ .-I — N N N CJ N CJ N _ CO OC •JJ C. CO F OJ •a CO CO {O W CO CO T CO CO N W B-22 PIGEON RIVER DATA CHAMPION INTERNATIONAL - CANTON HILL 111/84 TO 12/31/84 CA.Flow Ca.Color HE.Flow HE.Color I40.Colm' Tenn CoIr DATE mgd mg/l mgd mg/1 mg/1 mg/l -------------------------------------------------------------------------------------------------------------------------- 9127184 43 5 155 55 - - 9/28/84 45 5 157 30 - - 9/29/84 - - - - - - 9/30/84 - - - - - _ 10/l/84 55 5 149 65 100 100 10/2/84 47 5 129 152 143 - 10/3/84 45 12 123 200 95 - 10/4/84 43 12 119 195 95 95 10/5/84 42 12 177 170 88 - 10/6/84 - - - - 10/7/84 - - - - - - 10/8/84 47 5 173 478 93 93 10/9/84 55 12 119 329 115 - 10/10/84 57 5 143 231 103 103 10/11/84 52 12 127 290 135 - 10/12/84 48 12 121 260 115 115 10/13/84 - - - - - - 10/14/84 - - - - - .10/15/84 46. 5 115 340 110 110 10/16/84 47 12 117 402 103 103 10117/84 52 12 121 260 145 - 10/18/84 58 12 119 230 153 - 10/19/84 50 12 140 260 48 - 10/20/84 - - - - - - 10/21/84 - - - - - 10/22/84 61 12 196 207 152 152 10/23/84 130 12 293 230 130 1-0 10%24/84 " �-130 12 305 115 134 - 10/25/84 94 12 276 115 38 - 10/26/84 76 5 270 93 125 125 10/27/84 - - - - - - 10/28/84 - - - - - - 10/29/84 149 12 293 133 125 - 10/30/84 85 12 ' 244 85 125 125 10/31/84 68 12 206 31 31 - 11/1/84 61 12 224 125 133 133 11/2%84 57 5 224 100 125 125 11/3/84 11/4/84 65 12 197 215 - - 11/5/84 133 12 395 78 113 113 11/6/84 36 12 192 130 110 - 11/7/84 78 5 164 134 105 105 11/9/84 71 5 155 151 105 - 11/9/84 68 12 151 230 112 - ( 11/10/84 - - - - - _ B-23 PIGEON RIVER DATA CHAMPION INTERNATIONAL - CANTON MILL 1/1/84 TO 12/31/84 CA.Fiow Ca.Color HE.Flow HE.Color I40.0o1or Tenn Colr DATE mgd ma/1 mgd mg/1 mg/1 mg/1 -------------------------------------------------------------------------------------------------------------------------- 11/11/84 - - - - - 11/12/84 111 12 264 151 112 - 11/13/84 90 12 238 114 125 - 11/14/84 83 5 ' 214 222 112 - 11/15/84 78 7 206 152 85 - 11/16/84 74 5 187 168 12 - 11/17/84 - - - - - - 11/18/84 - - - - 11/19/84 87 12 401 180 133 133 11/20/84 100 12 285 198 144 - 11/21/84 79 12 222 133 125 - 11/22/84 74 5 203 198 112 - 11/23/84 71 25 194 222 93 - 11/24/84 - - - - - - 11/25/84 - - - - - - 11/26/84 67 5 192 346 145 - 11/27/84 63 7 180 330 152 152 11/28/94 996 12' 867 178 145 - 11/29/84 257 5 508 62 125 - 11/30/84 169 5 365 151 133 - 12/1/84 - - - - - - 12/2/84 - - - - - - 12/3/84 200 5 384 198 133 133 12/4/84 123 5 296 168 104 - 12/5/84 128 5 317 189 114 114 19/6/84 330 5 619 114 114 - 12/7/84 172 12 397 145 133 - 12/8/84 - - - - - 12/9/84 - - - - - - 12/10/84 133 5 314 198 125 - 12/11/84 - - - - - - 12/12/84 117 5 279 260 133 12(13/84 109 5 267 260 106 - 12/14/84 103 12 256 250 114 - 12/15/84 - - - - - - 12/16/84 - - - - - 12117/84 90 5 233 189 70 - 12/18/84 89 5 225 205 50 - 12/19/84 85 5 224 133 5 - 12/20/84 87 5 233 198 151 - 12/21/84 96 5 258 189 12 - 12/22/84 - - - - 12'123/84 - - - - - - 12/24/84 87 5 244 125 143 - 12,/25/84 83 12 305 144 133 - B-24 PIGEON RIVER DATA CHAMPION INTERNATIONAL - CANTON MILL F� 1/1/84 TO 12/31/84 CA.Flow Ca.Color HE.Flow HE.Color I40.Color Tenn Colr DATE mgd mg/l mgd mg/1 mg/l mg/l -------------------------------------------------------------------------------------------------------------------------- 12/26/84 89 5 264 151 145 - 12/27/84 85 5 253 105 151 151 12/20/84 81 5 241 161 151 - 12/29/84 - - - - - - 12/30/84 - - - - - - 12/31/84 76 5 224 206 125 125 -------------------------------------------------------------------------------------------------------------------------- MIN 36 5 115 8 5 5 MAX 1935 50 5062 478 180 180 AVE 210.63 8.899 474.70 131.03 73.60 70.47 B-25 PIGEON RIVER DATA CHAMPION INTERNATIONAL - CANTON MILL i/l/85 TO 12/31/85 CA.Flow Ca.Color HE.Flow HE.Color I40.Color Tenn Colr DATE mgd mg/l mgd mg/1 mg/1 mg/l -------------------------------------------------------------------------------------------------------------------------- 1/1/85 67 5 216 187 123 - 1/2/85 74 12 346 214 125 125 1/3/85 154 5 570 79 104 - 1/4/85 224 12 597 62 85 85 1/5/85 - - - - - - 1/6/85 - - - - - 1/7/85 143 20 368 95 79 79 1/8/85 123 5 336 92 18 78 i/9/85 114 5 314 95 78 - 1/10/85 109 5 305 70 79 79 1111/85 107 12 299 85 70 70 1/12/85 - - - - 1/13/85 - - - - - - 1/14/85 87 12 267 250 85 85 1/15/85 78 5 247 180 93 93 1/16/85 73 5 219 179 94 94 1117185 94 12 282 230 93 93 1/18/85 89 5 267 208 114 114 1/19/85 - 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B-31 PIGEON RPiER DATA CHAMPION INTERNATIONAL - CANTON HILL 1/1/05 TO 12/31/85 CA.Flow Co.Ccior HE.Fiow HE.Color I40.Color Tenn Coir DATE gd mg/1 igd 9g/1 mg/l wg/l -------------------------------------------------------------------------------------------------------------------------- 9/28/85 - - - - - 9/29/85 - - - _ 9/30/85 46 8 106 210 40 - 10/1/85 45 8 106 295 40 - 10/2/85 37 15 121 250 135 135 10/3/85 59 a 136 340 150 - 10/4/85 52 15 151 265 155 155 10/5/85 10/6/85 - - - - 10/7185 43 is 103 265 15 - 10/8/85 46 8 102 210 15 - 10/9/85 46 8 102 238 15 - i0/10/85 46 15 102 310 170 - 10/11/85 43 8 104 265 135 135 10/12/85 - - - - - - 10/13/85 - - - - - 10/14/85 40 8 101 230 8 - 10/15/85 46 15 99 265 140 - 10/16/85 46 15 110 275 30 - 10/17/85 45 15 104 255 25 - 10/18/85 43 15 97 265 128 - 10/19/85 - - - 10/20/85 - 10j21/85 43 15 102 200 25 - 10/22/85 72 25 189 245 30 10/23/85 50 15 149 180 120 10/24/85 46 15 138 180 148 148 10/25/85 47 8 136 200 12a 10/26/85 - - - - - 10/27/85 - - - - - 10/28/85 46 15 115 95 128 - 10/29/a5 43 8 115 220 148 148 10/30J85 41 15 112 210 155 155 10/31/85 145 15 211 148 155 15s 11/1/05 1530 s0 2937 40 170 170 11/2/85 - - !1/3J85 - - - - - I1/4/85 272 a 456 55 85 85 11/5/8s 32! 15 570 30 15 - 11/6/85 241 a 421 55 55 55 1117185 117 is 384 48 48 48 il/8/85 220 8 371 68 30 30 11/9/85 - - . - 11110/85 - - (✓ !1/11j85 138 8 313 95 68 68 B-32 PIGEON RIVER DATA CHAMPION INTERNATIONAL - CANTON HILL - 1/1/85 TO 12/31/85 CA.Flow Ca.Color HE.Flow HE.Color I40.Color Tenn Colt- DATE ^igd mg/1 mgd mg/1 mg/1 ag/l -------------------------------------------------------------------------------------------------------------------------- 11112/85 120 8 262 135 48 48 11/13/85 116 8 250 128 55 55 11/14/05 88 8 216 120 55 55 11/15/85 83 15 206 135 55 55 11/16/85 - - - - - 11/17/85 - - - 11/18/85 76 8 196 188 48 48 11/19/85 85 8 206 200 68 68 11/20/85 83 8 157 238 75 75 11/21/85 81 17 164 222 108 108 11/22/85 615 17 962 126 98 98 11/23/85 - - - - - - 11/24/85 - - - - - 11/25/85 154 9 276 145 17 - 11/26/85 138 17 250 193 17 - 11/27/85 130 9 264 193 17 11/28/85 133 9 262 203 71 - 11/29/85 199 17 424 126 71 - ll/30/85 - - - . - - - 12/l/85 - - - - - - 12/2/85 292 9 623 71 69 89 12/3/85 - - - - - 12/4/85 202 9 428 108 80 80 12/5/85 - - - - 12/6/85 168 17 368 117 80 80 12/7/85 - - - - 1216ias - - - - - - 12/9/85 133 9 299 164 6s0 80 12/10/85 120 17 287 145 71 71 12/11/85 116 9 273 154 80 80 12/19/85 160 9 311 108 80 00 12/13/85 140 9 384 89 89 89 12/14/85 - - - 12/15/85 - - - - 12/16/85 107 9 270 164 44 12/17/85 100 9 253 173 89 12/18/85 98 9 238 145 62 - 12/19/S5 92 9 222 164 53 53 12/20/85 88 9 224 126 BO SO 12/21/85 - - - - 12/22/85 - - - - - - 12/23/85 88 9 233 164 108 108 12/24/85 85 9 214 164 117 - 12/25/85 81 9 203 183 108 - ( 12/26/95 94 9 138 183 108 108 B-33 PIGEON RIVER DATA CHAMPION INTERNATIONAL - CANTON HILL 1/1/85 TO 12/31/85 CA.Flow Ca.Color HE.Flow HE.Color 140.Color Tenn Colr DATE mgd mg/l mgd mg/l mg/l mg/l -------------------------------------------------------------------------------------------------------------------------- 12/27/85 96 9 187 193 100 108 12/28/85 - - - - 12/29/85 - - - - - - 12/30/85 79 9 175 222 117 117 12/31/85 74 9 191 203 154 154 -------------------------------------------------------------------------------------------------------------------------- MIN 37 5 97 25 8 20 MAX 1530 48 2037 340 275 170 AYE 127.23 10.23 288.20 152.93 64.60 80.01 t ' i I � I m I W I 1 I I 1 ' I ' 1 1 1 I 1 I I 1 1 I 1 1 I 1 I I 1 1 J i J 1 Z 1 z i O I Z 1 U 00 U 1 CA � 1.7i •N-I •Q-I .b-' ti Yy .Qi cn FQ- 1 O C � 1 ' 1 I 1 1 1 1 1 1 1 1 1 1 1 � 1 1 1 1 1 1 I I 1 ^a 1 1 1 1 1 1 ti t •bi 1 � 6 M C !9 I W O O I - O 11; Q b 1 Cn •h-1 O •-+ ICJ h In b CJ T T V V' M S W C' 'a 1 �J N CA M CA .-a y CC O I yJ y ••-1'y d' �A r� r .- 1-1 CJ O co OW •`i U pi 1 1 1 •• •--1 1 1 •-y 1 1 •--r 1 1 1 I 1 •+ I 1 ^a 1 ^ I 1 W H \ o t3 1 C7 1 H P_ .C'i 1 M N < M W fh M M N N O M O CA N CA C, N] V co Ca +r 1� Vl CA N N N CJ C`1•-a I •tea y .�+ CO O y O CO M h V7 O C. h CA ar Cn .J ! CO ^J N) +Y T CA ^\ b b CA CAC \ 1 1 1 ^ CJ 1 1 CA N N M CA 1 1 CA N N FJ F) 1 1 I 1 1+) .- .J 1 1 M Iq V) 1 CA 1 1 .J CA Cl CA N T. U CII 1 U )?d 1 W 1 S 1 1 1 3 1 ,O 1 O < +S +S M O V9 M OD N N f\ N IJ'Y M M u) CO O `S N 1\ N +r N < •-a Op C 1 h •Cnr .P.y� tib-a M IA !� O ti P. -'ni •M-I .M-r T tti n -Di •aC-I V'J �J y y -ryli CA vI y ls_ Cll 1 N 1 1 •--I •�-1 1 1 1 ^+ 1 1 ^a •-� I 1 CJ -+• Ed I W 1 S I 1 1 • I 1 V T W 'd. O•. T Cn r± T d. n •hi d` P. R. ?. P. T T _y 1 U tT 1 • d 1 A 1 U 1 3 O I CO N N tlJ CO V7 v"J CO N h h .-a C. P3 •D 03 CO- � I _. 1\ 1\ b b vp b J) VJ +•r b �O b b Y7 V') V).ti) 1`.. •.d '.P IR) IJ) r-. V7 .< V7 r., .N:. LL pl I 1 1 1 1 1 1 1 I 1 1 1 1 I 1 I • Q I Q 1 U I I i 1 b b b W b b V) +O 1 co CC W CJ CA CA O] QJ CP CC CO Cb CP 9J N CO W CO CP CO OJ CO Co OJ CO dJ CC, /1_• CO N W CO . CO CO C> CO Cow CC CO CC A CC• W N 1^1 h CO d• O n-1 CA ty .ti •--1 b y CO CA M CT `Ci 1\ Cd d'. � •- CA -r �h �Ci Co P• CA C '2 I H •ti la ly y 1-I .n CA N CA CA CA a N r.J CJ CA 1•3 t'> C.I CA CA C C /=J I '" lea ..y ti•` ��`r yla 1-1 :1.y .�;�; .'.;1\`�. CA 4^A C•.1 FJ C.1 (A \1 CA CA IC-1 CA I B-35 PIGEON RIVER DATA CHAMPION INTERNATIONAL - CANTON HILL 1/1/86 TO 9J30/86 CA.Fiow Ca.Color HE.Flow HE.Color I40.Color Tenn Coir DATE ITO wg/I ©9d hq9/l m9/l ii9/l -------------------------------------------------------------------------------------------------------------------------- 2J15/£5 - - - - - - 2/16/86 - - - - - - 9/17/86 65 9 189 212 183 183 2/18/86 555 17 1067 108 164 164 2/19/86 193 9 539 11 117 117 2/20/86 148 9 417 71 108 108 2/21/86 127 17 359 183 173 173 2/22J86 - - - - - - 2/23/86 - - - - - 2/24/86 96 9 273 105 69 69 2/25/86 - - - - - - 2/26/86 8£ 9 244 154 62 62 2/27/86 - - - - - 2/28/86 94 9 279 126 53 53 3/1/86 - - - - - 3/2/86 - - - - - - 3/3/86 83 9 269 173 89 89 314/86 /9 9 254 183 71 71 3/5/86 58 9 247 145 89 - �' 3/6/86 76 9 - - - 3/7/86 67 9 227 212 98 98 3/£/86 - 3/9/86 - - - - - 3/10/86 - - 3/11/86 - - - - 3(�_/86 - - - - - - 3l13/86 94 9 300 135 126 126 3/14JCb 401 9 1003 .35 93 98 - 3/16/86 - - - 3/17/86 245 17 577 71 35 35 3/18/86 292 17 500 71 35 35 7/19/86 206 9 1396 R9 53 53 3/20/86 253 9 691 44 35 35 3(../86 209 9 5/8 53 53 53 3;23/86 - - - - - 3/24/06 160 9 432 71 9 3/25/86 148 17 410 89 35 35 3/26/86 135 9 390 98 35 35 3121/86 !33 17 378 108 44 44 3/28./86 123 9 352 !OC 26 - 3/29/86 - - - - - - 3/30/86 - - - 3111/86 107 9 314 173 35 801 SO! V9I 96T 6 t1 93/SI;S 3£1 S£I d1Z 8£Z 6 3L 98/Vr/S IT Z8Z 131 6 T3 98/£1/3 9ZI 9Zt £t£ 6V1 6 69 98/161/9 98/OT/C LT ZSZ TIT 1r £9 98/6/9 - - - 9818/S Li 9Zt 891 6 r9 98/L/S _ _ _ 98/913 S£i 9£1 IT £11 O £9 98/S/3 - - 98/t/3 - - - - 931S/S VSi VSI 9Z 681 .6 39 98/Z/S - - S£ 03T IT 99 96/T/S - 691 Z61 91 89 98/0£/0 - ON 9TZ 91 11 98/6Z/V - - Z£Z Z61 6 69 98/8Z/V - - - 98/Ld/V - - - - - 98/9Z/V - LT ZT'c TOZ 6 ZL 98/90 68 £0£ Z61 6 ZL 98/VZ/V 86 8b ZVd SIT 6 9I 98/£Z/V 80t 801 Z8Z £0Z 6 98 98/ZZ/V 801 801 ZSZ ZZZ 6 LOT 98/10 - - - - - WOO 98/61/V 08 Z8Z SIT 6 61 98/81/t I1 iL ZVZ SIT 6 61 98/111V 86 86 201 BIT 6 98 98/91/V 68 68 UZ £SZ 6 .6L 98/91/V 68 68 ZVZ - 6 T8 98/VI/V 98/£r/V - - - 98/Z1/V S£ £81 - 6 98 98/11/V IL VSi VTZ 6 06 98/01/V - IT 9Zr 88£ 6 18 98/6/V 001 801 9ZI V6£ IT 06 98/8/V 86 86 9ZI 89£ IT Z6 98/11V - - - - - - 98/9/V 98/S/V TL TL £II Z£V 6 06 98/0 Z9 Z9 S£r L8Z 6 86 98/£/V VV ' VV £LI £6Z 6 001 98/Z/V VV VV VSi 66Z 6 ZOI 98/Th -------------------------------------------------------------------------------------------------------------------------- I/6w i/u 1160 p60 1/60 p6v, 31V0 JIu3 u0a1 J0I00.OVI JO100.3H M013.3H J0I00'e0 00I3'V0 98/0£/6 01 93/r/i J 11IH NOINVO - lYHOIIVN831HI NOIdNVHO V1V0 83AI8 N039Id C1 P a •T T T P T T a O• J. T T P a o. T T P O P \\\\\\+�\\'�.\F r V 1--• 'i 1\-•\ �\-.� P ()\ T O� P• T P. p• P�\\�1 t���\\i��\Y\ �+ 1 b J 03 V P U A (.1 N ✓ 1-. O •L w V P U A 1 1 1 1 i a 1 EV It �O P w �O W tit �G U m A U O 03 0. •O W W V w W O N W W � N w I O I £ 1 j 1 L7 1 N 1 1 1 1 1 1 1 1 1 1 11 1 1 1 0 r--• 1- !.. N V r� H 1--. N r 1-•. 1--• W 1--• 1 1--•V `O •O V `G V T `J V V •� +1 �6 �J T �Cr �O •� V U �O �G. •J �O V �O �p �O O �p V �O 1 O 1 1 1 1 x 1 rn 1 1 r N N W 1--• 1 1 N H 1--• N N 1 1 N N til W N 1 1 N 1--• N W 1--• 1 1 67, 1 �c.J A U a W 1--• m A m O •O �O 1-+ 1--. V O m P 1-+ O �O W N .O P 1 2 H O U V W •L 1--• U P W VI O �O •8 N N V W A U A O P P m U V A P V '•O P �O 1 O 1 >z 1 1 S 1 m ® J 1 .a c3 x W 1 1 CN W <<I N 1 1 1 fJ N A J 1� 1 1 �-+ h-• N 1 1 N N 1--• 1. 1 N 1 1 1--• F� N 1--• 1 1 N 1 � 0 a O N N tJ A 4 G O 4J O �O �O A r N �O O W P m U V W m O U P P N O tiI T 1 1 1 H 1 O 1 2 1 1 w: 1 1 �--• 1--• N am ! 1 � 1 1 1 1 1 1 1 1 �-- ! 1 �--• 1 \ (7 \ � t'tl O 1- O 1--• U •G W O N N •,O 1--• �O N O fJ 1V-. �O m W O O 4+ 1 �-+ O W O rr � V Vu �J m V mv3 .o +lom cnw •OPT �! wPmT w +l JnT rs V 1 �-. Pa z L O y I ^I ti H as 1 CJ O H 1 = < ! -y •a a rn ! m \ r x 1 ® e w 1 1 1 1 1 1 N 1 1 1 t� 1 H I 1 1 1 1 1 1 1 1 F+ 1 1 1 1 1 1 1 V+ 1--• I 1 1--• 1 \ O \ 1 b W O O m -O tl fJ N '•6 N O N V `O w O O H I �--• CJ m CJ ti m w o w m 1 6 I � 1 1 1 - 1 H 1 r 1 r i 1 1 1 • 1 i i 1 1 1 1 1 i 1 • 1 1 1 1 1 I I 1 i W I North Carolina Department of Natural Resources &Community Development a PIGEON RIVER INVESTIGATION 1980 1 ^ Division of Environmental Management Water Quality Section Monitoring and Technical Services Branch 1 Acknowledgements The principal investigators involved in this evaluation were staff members of the Monitoring and Technical Services Branch, Water Quality Monitoring Unit. We would like to acknowledge the support and assistance of the staff of the Western Regional Office with special thanks to Mr. Jack Wingate and Mr. Jay Davies of the Division of Inland Fisheries and Mr. Doug Harned and Mr. Joe Freeman of the Tennessee Valley Authority. Cover-: Hydropsychid caddisfly larva. Redrawn from Anker Odum, in; Wiggins, Glen B. 1977. Larvae of the North American Caddisfly Genera (Trichoptera) . University of Toronto Press i Pigeon River Report 1980 Table of Contents Page Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1 Chemical-Physical Section . . . . . . . . . . . . . . . . . . . . . . 1 Chemical-Physical Station Locations . . . . . . . . . . . . . . . . . . 4 Dye Study . . . . . . . . . . . . . . . . . . . . . . . . . . . . 12 Cross Sectional Study . . . . . . . . . . . . . . . . . . . . . . 25 Chemical/Physical . . . . . . . . . . . . . . . . . . . . . . . . 30 Model Development . . . . . . . . . . . . . . . . . . . . . . . . . . 56 Introduction/Biological . . . . . . . . . . . . . . . . . . . . . . . . 71 Fisheries Investigation . . . . . . . . . . . . . . . . . . . . . . 72 Benthic Surveys . . . . . . . . . . . . . . . . . . . . . . . . . 77 Bioassays . . . . . . . . . . . . . . . . . . . . . . . . . . 86 Biological Station Locations . . . . . . . . . . . . . . . . . . . 90 Apendix I - Tissue Results . . . . . . . . . . . . . . . . . . . . 103 Appendix II - Benthos . . . . . . . . . . . . . . . . . . . . . . 125 Appendix III - Benthos . . . . . . . . . . . . . . . . . . . . . . 129 ii LIST OF TABLES TABLE PAGE 1. Station Locations - Physical/Chemical Study . . . . . . . . 4 2. Discharge Measurements on the Pigeon River and Selected Tributaries . . . . . . . . . . . . . . . . . . . 8 3. Pigeon River Time-of-Travel Study . . . . . . . . . . . . . 13 4. Intensive Survey Sampling Schedule . . . . . . . . . . . . 32 5, pH, D.O. , Temperature, Fecal Coliform, Solids and P&N Series Data for Stations P-0, P-1, P-2, P-4, P-5 . . . . . 33 6. BOD5, Metals, Sulfate, Chloride, Conductivity and Color Data for Stations P-0, P-1, P-2, P-4, P-5 . . . . . . . . 34 7. pH, D.O. , Temperature, Fecal Coliform, Solids and P&N Series Data for Stations P-6, P-7, P-7A, P-8 . . . . . . . 35 8. BOD5, Metals, Sulfate, Chloride, Conductivity and Color Data for Stations P-6, P-7, P-7A, P-8 . . . . . . . . . . 36 9. pH, D.O. , Temperature, Fecal Coliform, Solids and P&N Series Data for Stations P-9A, P-10, P-11, and P-11A . . . 37 10. BOD5, Metals, Sulfate, Chloride, Conductivity and Color Data for Stations P-9A, P-10, P-11, and P-11A . . . . . . 38 11. pH, D.O. , Temperature, Fecal Coliform, Solids and P&N Series Data for Stations P-12, P-13, P-4A, P-5, P-9 . . . . 39 12. BOD5, Metals, Sulfate, Chloride, Conductivity and Color Data for Stations P-12, P-13, P-4A, P-5, P-9 . . . . . . . . . 40 13. pH, D.O. , Temperature, Fecal Coliform, Solids and P&N Series Data for Stations P-11B, P-12A, P-12B . . . . . . . . . . 41 14. BOD5, Metals, Sulfate, Chloride, Conductivity and Color Data for Stations P-11B, P-12A, P-12B • . . . • • • • • • 42 15. Long Term BOD Data for Stations P-0, P-1, P-2, P-4, P-4A, P-5, P-5A, P-6, P-7, P-7A . . . . . . . . . . . . . . . . 47 16. Long Term BOD Data for Stations P-8, P-9, P-9A, P-10, P-11, P-11A, P-12, P-12A, P-12B . . . . . . . . . . . . . . . . 48 17. Long Term BOD Data for Station P-13 . . . . . . . . . . . . 49 18. 30-Day P7N Series for Stations P-0, P-1, P-2, P-4, P-5 50 19. 30-Day P7N Series for Stations P-6, P-7, P-7A, P-8; P-9A 51 20. 30-Day P&N Series for Stations P-10, P-11, P-11A, P-12, P-13 52 I TABLE PAGE 21. 30-Day P&N Series for Stations P-4A, P-5A, P-9, P-11B, P-12A, P-12B . . . . . . . . . . . . . . . . . . . . . 53 22. 30-Day P&N Series for Station P-12B . . . . . . . . . . 54 23. 91-Day P&N Series for Stations P-1, P-2 . . . . . . . . 55 24. Measured Point-Source Flows for Calibration and Allocation Models . . . . . . . . . . . . . . . . . . 61 IL LIST OF FIGURES FIGURE PAGE 1. Map of the Total Study Area with Station Locations . . . 5 2. Map of the Canton Area with Station Locations . . . . . 6 3. Map of the Clyde Area with Station Locations . . . . . . 7 4. USGS Flow Gage on Pigeon River at Canton . . . . . . . . 9 5. USGS Flow Gage on Pigeon River near Hepco . . . . . . . 10 6. Pigeon River Flow Model . . . . . . . . . . . . . . . . 11 7. Dye Concentration Curve at Station P-4 . . . . . . . . . 14 8. Dye Concentration Curve at Station P-5 . . . . . . . . . 15 9. Dye Concentration Curve at Station P-6 . . . . . . . . . 16 10. Dye Concentration Curve at Station P-7 . . . . . . . . . 17 11. Dye Concentration Curve at Station P-8 . . . . . . . . . 18 12. Dye Concentration Curve at Station P-10 . . . . . . . . 19 13. Dye Concentration Curve at Station P-11 . . . . . . . . 20 14. Dye Concentration Curve at Station P-11A . . . . . . . . 21 15. Dye Concentration Curve at Station P-12 . . . . . . . . . 22 16. Dye Concentration Curve at Station P-13 . . . . . . . . . 23 17. Pigeon River Dye Study - Average Velocity vs Distance . . 24 18. Conductivity Cross-Sections taken on 14 May 1980 . . . . 26 19. Conductivity Cross-Section Taken at the R.R. Bridge Below Champion Outfall on August 14, 1980 . . . . . . . . . . . 27 20. Conductivity Cross-Sections Taken on 26 August 1980 . . . 28 21. Temperature Cross-Sections Taken on 26 August 1980 . . . 29 22. Pigeon River D.O. Profile . . . . . . . . . . . . . . . 43 23. Pigeon River P&N Series . . . . . . . . . . . . . . . . 44 24. Pigeon River 5-Day BODS . . . . . . . . . . . . . . . . 45 25. Pigeon River 90-Day Long Term BODS . . . . . . . . . . . 46 III List of Figures - continued FIGURE PAGE 26. Organic Nitrogen Calibration . . . . . . . . . . . . . . 63 27. Ammonia-Nitrogen Calibration . . . . . . . . . . . . . . 64 28. Oxidized Nitrogen Calibration . . . . . . . . . . . . . . 65 29. CBOD Calibration . . . . . . . . . . . . . . . . . . . . 66 30. Dissolved Oxygen Calibration . . . . . . . . . . . . . . 67 31. Champion Allocation, D.O. = 6 mg/1 . . . . . . . . . . . 68 IV Introduction The Pigeon River, in North Carolina, is used as a water supply for Champion Paper Company near Canton, North Carolina, and at times, the entire flow of the river is diverted through the plant. After treatment, wastewater from the paper mill is discharged to the river. The effluent is characterized by elevated levels of color, dissolved solids, tannin compounds, and temperature not normal in streams located in this section of the State. Based upon previous investigations and data review, it is possible that the original loading (BOD) from the mill is suf- ficiently high to have depressed instream oxygen levels to or below the water quality standards limits in North Carolina and perhaps in Tennessee. The uncharacteristically high color, dissolved solids and temperature may also be affecting biological productivity of the river and thus not providing for the intended uses of the river according to water quality standards. The Pigeon River from Canton, North Carolina to its confluence with the French Broad River in Tennessee is adversely affected by the industrial discharge from Champion International Paper Corporation. The use potential of the river is thereby restricted for water supplies and recreational activities. This situation has resulted in a cooperative agreement between TVA, EPA, NCDLM and the State of Tennessee to assess the impact of the water temperature, color, dissolved solids, and BOD on water quality and biological productivity of the Pigeon River. As a part of this agreement the Technical Services Branch of NCDEM performed a time-of-travel tracer study and an intensive physical/chemical water quality study to calibrate a DO - BOD Model. This model will be used to determine allocation limits for BOD5 and effluent DO for Champion Paper's NPDES permit. The NPDES permits of the towns of Clyde and Waynesville will also be reviewed at this time. The Pigeon River originates in western North Carolina in Haywood County at the confluence of the West and East Forks of the Pigeon River. It then flows north for 69 miles to its confluence with the French Broad River at Lake Douglass, 5 miles north of Newport, Tennessee. One of the main physical features of the river is Waterville Lake, which was constructed in 1929 by Carolina Power & Light for hydroelectric Power. The lake has a capacity of 8.27 billion gallons and is located 20 miles below Canton. Except under high flow conditions, the entire flow of the river is diverted through a hydroelectric tunnel to Waterville, Tennessee, thus bypassing almost 8 miles of riverbed. The reach of the Pigeon River from Canton to the headwaters of Water- ville Lake was the main concern of this study. This segment includes five major tributaries: Beaverdam Creek, Richland Creek, Crabtree Creek, Jonathan's Creek and Fines Creek. It has an average slope of 15.3 ft/mile and a drainage area at Canton of 133 square miles and at Hepco of 350 square miles. The sampling stations are shown on Table No. 1 and in Figures 1 through 3. There are 12 river, 6 tributary and 3 effluent stations. The Pigeon River is seriously affected by Champion Paper Corporation in Canton. During low flow conditions up to 90% of the river may be diverted through the plant and discharged as effluent. This effluent is characterized by high levels of color, dissolved solids, and elevated temperatures. The Champion discharge also has a small percentage of domestic waste present. Other significant dischargers to the river are the towns of Clyde and Waynes- ville. The town of Clyde has a secondary treatment plant with a design capacity of .128 MGD and is entirely domestic. The town of Waynesville has a secondary treatment plant with a design capacity of 6 MGD and receives domestic and industrial waste. One of the industries which discharges into the Waynesville Plant is a tannery, A. C. Lawrence Company, which adds an 2 additional amount of color to the river. Continuous flow data for the Pigeon River from the 24th through the 31st of August was obtained from the USGS gage stations at Canton and Hepco. The Canton station is located 0.8 miles above station P-1 while the Hepco station is located 2 miles upriver from station P-13. This data is presented in Figures 4 and 5. Discharge measurements taken during the intensive sampling runs on the tributaries are reported in Table 2. A flow model of the total river segment showing points of water uptake, discharges, and tributary confluences is presented in Figure 6. 3 TABLE 1 - Station Locations Physical/Chemical Study August 25 - August 28 Distance (Miles) From Champion Discharge Station Location - 6.07 P-0 Pigeon River below the confluence of the two forks .05 P-1 200 feet upriver of Champion Paper outfall 0 P-2 Champion outfall .15 P-3 RR Trestle .40 P-4 Pigeon River at N.C. Hwy 215 - P-4A Beaverdam Creek at N.C. Hwy 215 .50 P-4B Pigeon River at confluence of Beaverdam Creek 1.9 P-5 Pigeon River at bend at River Mile 61.2 - P-5A Thickety Creek at SR - 1550 3.75 P-6 Pigeon River at bend at River Mile 59.3 5.35 P-7 Pigeon River at SR - 1642 (Clyde) 5.80 P-7A Clyde 194-LP 7.35 P-8 Pigeon River at SR - 1533 - P-9 Richland Creek at SR - 1519 8.2 P-9A Waynesville WWTP 9.2 P-10 Pigeon River at SR -1625 10.5 P-11 Pigeon River at SR - 1649 12.75 P-11A Pigeon River at confluence with Crabtree Creek - P-11B Crabtree Creek 100 yards above mouth 14.2 P-12 Pigeon River at SR - 1363 (Ferguson Bridge) - P-12A Jonathans Creek 100 yds below Ilwy 276 - P-12B Fines Creek at SR - 1338 19.2 P-13 Pigeon River at SR - 1396 (Hepco) 4 Q•e • llama .�,� t`�1" . .�\ •>r. ln,a ^S ef]sfrs GAP1]ail) %C, v ) r Ian •Swn GwY Jbv N xE40 MM.fIEV S.�B7D/3 l., f L,,,•JiM1 Sa C, ��J_ I n,1 I a ] I B ��? P 13 FIGURE 1 O.K M]N. •^ qif. 1 yal • /L ^• .} y "Aeoe[ um � .^ y Study Area and o Station Locations nax use •J ii. J \ ` ..1?r SP VaV • 1 Z 'Y Nsa Iwo M Q J •1> F v-1 G -' 1 ♦�r{.e i P/GEO.° i�„\ In _ Um ( .eEwvEUDIw. C GAP ` Z IS Ile]A llas • � I an � ,�� <a.e CrepY •1 �l v pie ��GuOa so] ^ `` �3.'] ' t us,J , Inca •` b d • \ G] r 1 Z LOS P�2 A, !>1 � s tlm 5i °bL••+ a uor IpN ; �Y.rn 7 f „a ♦ I Iall rale� Ieav r � Ilfi min_ � n �mnl u]K 4- Iaev Ali^ 'T 35°35' �a pU r� •- Nar '.Or.]V.J }al]Yi brgaallal] Ljt•'] r •/�Wf IO]ND G. ..aTon 1Q4 .c IeaLe 1.1 _fa r}n , m J ) eu ♦IIN • ,y ITO CNANefNS __ .. ,.]q A_v "At - Y I Iw. ,J i !n / , Vi.N dM � '' GBASSY ]OP Y1°9 J iCA Rt- / lea\1 TO wY E� J 19 14 IAI 10—_ o°kP-9 rds �� 4�0 4j�e. Q Y' '/a N.! !• s __l _ _ a D es' � ll ll �,�]'^ CVOE, rµ PnnIIPSVIIIf UN]Orl 6 1 r� • ].] rorvoD LNrK1 ror n]e 1 L.k SNATHftS NTN, ;TI DW4E tOP.uM. _ rs N. $ENtELL 1i % n rss •e rV WW-TOP Tw-w O'Q= TOP r5 G A H , l•'WO PIN TN. ]•(YD leea .\ Z J'r „ado.Gm.v / l wATNE VREE/ Na115 a •;' n•e v �"� __r� a j' a I ° I I°a' � �a• Irn rl ♦ }a1'1 fJ NATIONAe dlc nsc. L j^• `� e \ n ."STONE SAID ] EIEV 5,]TI -Z' ^ 'T ro •1 .. F n y Srnbvn ✓J, $ ,{ COLD MOUNTIIN F O R E S T n 1 A ].° c !AI v� ` 511ING 1� Ui l`� I �1 ee • IYYINOPAN rn 'CO,,d M ANOO HE`45,asOD SIGN to, I �M iGNFT iOtK yLD z ' Ice 'Z"r 54� N`J sT.lvs NTN.: l.q FIGURE 2 Canton Area o-.•4�',�° :] G i Station Locations /71 p p7j 1111 Hp lil •d I � Iwl 1Ll " 6 0� e w ) _ rce �• 1� life •'} g ISffi h L ) / um <a} r :we » 1 R�w�*.•^�`'s�"' -s8 r"3' '�?e �!]ro le �f nn N.r }) lqG PHIWM IIIE ! y n IuruKl �'6ri X,'y ror esu,°Pv ff I >°°y. Z f Iw! i0 •N Q4 ' S7,... ule 4i nu I t pa }1° d CANTON f° � A lr _ �ee A IN. 9ti y POI•. 5.158 ) e Y E }1 fer pf V 9 O] • ] 'S fvl \yn I! rb ll °I 07 r6 ' M. • s � CR]. r o I 1 ur ws p µQq— un fa lMe leu � L Figure 3 N/O Clyde Area Station Locations n _ V o _ e � d = O 8 e` 5 K' Co ry > � Arun � l' UN 3 � � Q� r - 8 g -b qG - F � b W TABLE 2 DISCHARGE MEASUREMENTS On the Pigeon River and Selected Tributaries REACH: Pigeon River Station Velocity Are Cross-Sectional Number Location Date Time ft/sec (FT ) Width Discharge 100 ft. upriver of P-1 Champion outfall 800514 1140 1.1 132 108 170 P-1 200 ft upriver of Champion outfall 800828 1035-1100 .39 10.73 40.5 5.04 P-4A Beaverdam Creek 800826 1510-1525 .615 3.97 12.0 2.73 at Hwy 215 P-5A Thickety Creek at SR-1550 800826 1555 .39 1.71 6.5 .70 P_9 Richland Creek 800826 1650 1.78 20.29 26.5 40.00 at SR-1519 P_9 Richland Creek at SR-1519 800827 1400 1.67 18.42 27.0 33.30 P-11B Crabtree Creek 100 yds above mouth 800826 1750 .33 18.55 29.0 6.19 P-11B Crabtree Creek 800827 1455 .37 19.72 29.0 6.57 100 yds above mouth P-12A Jonathan Creek 800826 1849-1970 1.02 30.95 52.0 36.28 100 yds below Hwy 276 P-12A Jonathan Creek 100 yds below Ilwy 276 800827 1550-1617 1.02 31.14 52.0 35.73 P-12B Fines Creek off 800826 2000 .62 9.52 9.52 6.09 of SR-1338 P-12B Ines Tree- o f of SR-1338 800827 1635-1646 .69 10.31 14.50 6.59 338 mmq __=�. _���rye— --'—_'� —_— ••:7:5.��.--_-_��__--:•_..'wC���C Y:.--.•.•._---�•_—_^. =.—_.C............_.—. _....:..............._......_._.. ..................... .............................. __........_.............. .._._—. ::::::::::....._............�:::.._......._:_......................__....._..::..::.^.:.:....:—..-L•:C::::::::::::::�:::::::: ' 'ire:. ..-....,., '-':_•�==� ..... .:�e.:. •^:.—_.: _�'.__—...' :- 't 7 '.N� 'w:�.CRF:�:::: ::f .CCU �S H. «.:: :Zr::�.--� _My..:::::::::::7.^.:.—_.:C:�::=C::::::::::...... .^:�::•te e::::�::�:M:: �� _ m:t: :� -e� �.'w _ M. _ .. - _ _ - - ..<� _ .v:f.f:Cill •• .::-7C'::::M.C'': ..7..... : ..................^: :7: 7:7 7:::: ::::::M::�C'•C�•CC: :C :.9�w'::M .-.::Y:: ':: ...........• :::w :^7: 5 : C: .. 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The study was divided into two segments because of an estimated time-of- travel of two days. The first was from P-2 through P-10, a 9.12 mile reach, and the second was from P-10 through P-13, a 10.54 mile reach. Four liters of Rhodamine WT, a red fluorescent dye tracer, were slug injected at each dose site. Samples were then taken at the downstream stations from mid river by hand samplers. Samples were run on a Turner Model 111 Fluorometer to determine peak and total dye concentrations. This information was then used to establish time intervals for slug sampling during the water quality sampling runs. The results are presented in Table 3. The first segment, P-2 through P-10, had a time of travel of 23 hours and 30 minutes and a velocity of .57 feet/second. The second segment P-10 through P-13 had a time-of-travel of 21 hours and 10 minutes and a velocity of .73 feet/second. The total time-of-travel was 44 hours and 40 minutes with a velocity of .65 feet/second. The dye curves for the various stations are shown on figures 7 through 16. A velocity vs distance relationship is presented on Figure 17. 12 TABLE 3 REACH: Pigeon River Time of Travel Study Dist. from Stream Travel Cum. Veloc- Injec- Dis- Sta. Peak Time, Time, ity, Length, tion, charge, Slope No. Location Date Time hrs. hrs. ft/sec. mi . mi . cfs ft/mi . P-2 Champion outfall 800825 0745 Dye Dose P-4 NC Hwy 215 800825 0817 32 min 32 min .96 .35 .35 P-5 Bend at R.M. 61.2 800825 1205 3 hr 48 min 4 hr 20 min 58 1.50 1.85 P-6 Bend at R.M. 59.3 800825 1645 4 hr 40 min 9 hr .58 1.85 3.70 P-7 SR - 1642 (Clyde) 800825 2050 4 hr 5 min l5 min .57 1.58 5.28 P-8 SR-1533 800826 0210 5 hr 20 min 18 hr 25 min .55 2.00 7.28 P-10 SR-1625 800826 0715 5 hr 5 min 23 hr .53 1.84 9.12 30 min SUB-TOTAL 23 hr 57 9.12 30 min I : P-10 SR-1625 800825 0730 DYE DOSE2 hr P-11 SR-1649 800825 0945 2 hr 15 min 15 min 87 1.34 1.34 P-11A Pigoen River just up- 800825 1505 5 hr 20 min 7 hr „62 2.25 3.59 river of Crabtree Cr 35 min P-12 SR-1363 800825 1820 3 hr 15 min 10 hr .64 1.42 5.01 ; 50 min P-13 SR-1396 800826 0440 LO hr 20 min 21 hr .78 5.53 10.54 110 min SUB-TOTAL I0 hr min .73 10.54 TOTAL 44 hr 40 min 65 19.66 i11!E#Ii III 11 !I[IIIli 1111!!IIlllllillilli ifil'!i1111i!liilfl=#i1[iilil�f 1i I#li#lEP1 I!E#i !ll 111111 : I I1I1II i# 11l11111 !iIl l I I1111!!_€I1[!: !!!'# 1 _E:EIIIPlfEl#:° # #llllii_[P1 111 [( ::!Ilullllilll (IIIIIIPIIIEIIIIIIIII(IIi::[[(IEIIIIGIIIIII[IIIII11111 #1 111 [1G1PI_ 1! !I!l0 :E11l1i#!##!€E#PEE111 ll [[!illlf€€E€#€!!!!!PIlI[!{{IIIIIIII{I{IIII !11!1[Ii! : IIIIl111P[111##!!##l1111!#PI!#1f#!!!##!!ElIE!!II!!!Il!1!{IIIII I!f i I !#!#!I I I IP#Ef#1111[IIlI !E(1111 !IIII III IIII PIEI!##!Pl1PlI !II!!Ifi#illl(II(I III I III#PIP 1!!! !11 i!lPlfilEf!f!'ilf1P1 I1P!{1if'll [fE!!Pf!!IE!![[!{#I !flliEEP 1EP[1!I€[ IIIIIIil11lPllPIIIIIIl1PIE11lIIIiilifllllIIIIEllGlIIIIIIPIIIf11GPll[III11E1iilllllf111 IIIIIIIGlllIIIIIII1111lPE11Ellli[IIPPlIIl:!!!{([!i{llPli#�IIE1PGf I!f!H 111111I11[###!EliEi[1111IP1lII!ilii:= '° ! ! °`I;€� :III=..lillllll�.ii(.1[P!I:#1!!PI[EI111l:IIII !I#I!!IE Ili III 1111111111111 11 I1111 IIIlI!lIIII I I!(i[Illi!lflll I(111! !PIIE[I I II[I I ! 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' Conductivity Cross-Sectional Measurements Conductivity and temperature cross-sections were taken at downriver stations to determine the extent of the mixing zone of the Champion effluent under average and low flow conditions. The Pigeon River at Canton has an average flow of 324 CFS (52 year average) and a 7/10 low flow of 52 CFS. On May 14, 1980 the Pigeon River had a flow of 237 CFS. Conductivity cross-sections were taken at Station P-3, 200 feet downstream of P-3, and Station P-4. The results are graphed in Figures 18 and 19 and show that mixing was almost complete by Station P-4. The conductivity ranged from 950 umhos to 1025 umhos with a 14% increase from the lowest to highest value. Conductivity and temperature cross-sections were taken at a flow of 81 CFS on August 26, 1980 at stations P-3 and P-4. These results are pre- sented in Figures 20 and 21. They indicate that the mixing was almost complete at station P-4. 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There were four slugs begun every four hours using the times determined in the dye study. The sampling schedule for the river stations is presented in Table 4. The tributary stations were sampled twice on consecutive days and Station P-0 was sampled once, as a check on the main upriver station, P-1. The parameters taken in the sampling runs were D.O. , Temperature, pH, Solids, BOD5, BODlt, Fecal Coliform, Metals, Sulfate, Chlorides, Color, Conductivity, and a P&N series. Sulfate, Chlorides, Color, Conductivity, and Metals results are shown in Tables 6, 8, 10, 12 and 14. The metals sampled were Chromium, Cadmium, Copper, Iron, Lead, Nickel, and Zinc. Chromium, Cadmium, Copper, Lead and Nickel were all below normal reporting limits. Iron levels were all below state standards. Zinc levels increased at Station P-4 but fell off quickly. Chlorides, Conductivity, Sulfates and color all increased substantially at Station P-4. At Station P-13 they were all still considerably higher than background values, the chlorides as high as 35 times background. The highest sulfate value of 165 mg/l at stations P-4 and P-11A was lower than the state standard for A-2 waters of 250 mg/l. There are no state standards for Chlorides, Conductivity and Color. D.O. Temperature, pH, Solids, Fecal Coliform and P&N Series Data is tabulated in Tables 5, 7, 9, 11 and 13. A D.O. profile shows that the sag occurs at Station P-5. There is also a small sag which occurs at Station P-11 which is a result of the Waynesville WWTP. The reason for the sag occurring at Station P-11 instead of Station P-10 is due to the incomplete mixing of the Waynesville effluent at Station P-10. Downriver of Station P-11 the D.O. continued to increase and by Station P-13 there was complete D.O. recovery. 30 Only D.O. readings taken on the Dissolved Oxygen meters were accepted, because the Champion wastewater interferred with the Winkler Method's operation. Temperatures increased from 23 to 320C from Stations P-1 to P-4, but by Station P-13 had returned to upstream levels. Total Residue in- creased substantially at Station P-4 from 92 to 2440 mg/l and only de- clined to 688 mg/l by Station P-13. Total Suspended Residue was insignificant ranging from 2 to 28 mg/l. The BOD5 and BOD 30 results are presented in Tables 15 through 17. A BOD5 plot is shown in Figure 24 and the 30 day P&N values in Tables 18 through 22. The highest in-river BOD5 was 6.0 mg/l and a BOD30 of 29 mg/l. An earlier set of BODlt of the Champion effluent were taken on May 14, 1980. This set of samples was run for 91 days and the data is shown in Figure 25 and Table 23. The 91 day BOD was 75 mg/l. 31 TABLE 4 Intensive Survey Sampling Schedule Slug #1 Slug #2 Slug #3 Slug #4 P-1 0745 1145 1545 1945 800826 P-2 0800 1200 1600 2000 P-4 0832 1232 1632 2032 P-5 1230 1630 2030 0030 P-6 1705 2105 0105 0505 800827 P-7 2035 0035 0435 0835 P-8 0245 0645 1045 1445 P-10 0715 1115 1515 1915 P-11 0930 1330 1730 2130 P-11A 1440 1840 2240 0240 800828 P-12 1750 2150 0150 0550 P-13 0415 0815 1215 1615 32 TABLE 5 Fecal RESIDUE SERIES (mg/1) N SERIES (mg/1) P SERIES (mg/1) R.P. D.O. Temp. Coliform Tot. Tot. Vol. NO3-N+ Station Date Time (ft. ) PI1 (mg/1) (oC) (#/100 ml) Tot. Vol. Sus. Sus. NH3-N TKN NO2-N Tot. P Ortho- P P-0 80082E 1130 7.9 8.4 19.8 27 2 .05 .1 .19 .OS P-1 800826 0740 6.8 6.4 20.0 <.05 .1 .18 4 .05 P-1 800826 1130 7.5 8.3 23.0 160 60 1 1 c.05 .1 .16 .05 P-1 800826 1540 1 8.7 8.6 26.0 79 4 < .05 .2 .15 .06 P-1 800826 1940 7.0 7.7 23.0 137 2 •05 .2 .14 .06 1 -1 MEAN 7.5 7.75 23;0 92 2 .05 .15 .16 .06 P-2 800826 0800 7.1 1.4 34.0 1.5 .6 .05 81 P-2 900826 1200 7.2 .9 34.0 330 (TUBE 2610 18 1.2 .1 < .05 .80 P-2 800826 1600 7.2 1.014 36.0 2920 21 1.2 1 .OS .79 P-2 800826 2000 6.8 3.3 33.0 3000 23 1.7 .1 �.05 .82 -2 MEAN 7.1 3.4 34.0 2843 21 1.4 .5 <.05 .81 II P-4 800826 0832 7.2 2.3 29.5 1.2 .0 ,� .05 .65 I P-4 800826 1232 7.45 1.5 33.0 50 2150 12 1.0 .7 0.05 .65 II P-4 800826 1632 7.5 4 2.4W 33.0 2360 11 k14 .0 0.08 .64 P-4 800826 2032 7.2 4.3 33.0 2810 19 .2 -, .05 .73 -4 MEAN 7.3 32.0 2440 14 .0 .06 .67 P-5 800826 1230 7.05 1.5W ' 30.8 .8 0.33 .62 P-5 800826 1630 7.25 3.7 33.4 280 2140 15 .7 0.39 .60 P-5 800826 2030 7.4 3.55M 30.5 2240 15 .5 0.39 .59 P-5 800827 0030 7.55 3.65 28.7 2610 18 1.1 .9 0.37' .65 P-5 MEAN 7.3 3.675 30.9 2330 16 .94 .0 0.37 .62 w w I TABLE 6 BOD COD HETALS (ug/1) Station Date Time ( /1) (m /1) Tot. Cr Cd Cu Fe Pb Mn Ni Zn SO4 Cl Cond P-0 800828 1130 1.5 <50 <40 < 10 <100 <50 < 5 1.0 26 1 P-1 800826 0740 .8 13 8.0 P-1 800826 1130 1.5 7 P-1 800826 1540 1.4 15 4.0 80 P-1 800826 1940 <50 < 40 • 500 4100 <100 50 135 P-1 MEAN 1.2 14 6.0 91 18 23 P-2 800826 0800 13.0 2 750 P-2 800826 1200 7.2 <50 <40 400 <100 <100 140 P-2 800826 1600 6.8 180 200 cil on inn 71f) P-2 800826 2000 <50 440 400 <100 <100 60 P-2 MEAN 9.0 <50 140 400 <100 <100 100 190 100 P-4 800826 0832 6.8 160 � 760 0 P-4 800826 1232 6.2 13680 I P-4 800826 1632 6.5 170 980 4150 0.0 P-4 800826 2032 <50 <40 400 <100 <100 80 14800 P-4 MEAN 6.5 6 P-5 800826 1230 5.4 180 740 3190 7nn 7nnj P-5 800826 1630 5.1 120 900 P-5 800826 2030 5-2 150 P-5 800827 0030 <50 <40 500 < 100 50 150 863 3553 700 700 P-5 MEAN 5-2, w r i TABLE 7 Fecal RESIDUE SERIES (mg/1) N SERIES (mg/1) P SERIES (mg/1) R.P. D.O. Temp. Coliform Tot. Tot. Vol. NO3-N+ Station Date Time (ft.) H (mg/1) ( C) (#/100 ml) Tot. Vol. Sus. Sus. NH3-N TKN NO'-N Tot. P Ortho- P P-6 800826 1705 7.3 1.7W 31.4 .77 1 1.4 0.56 .56 P-6 800826 2105 7.2 3.65 28.9 220 1950 11 .60 1.4 0.62 .56 P-6 800827 0105 7.5 3.85 27.6 2140 14 .60 1.2 0.57 .54 P-6 800827 0505 7.4 3.60 26.0 2370 21 .68 1.7 0.61 .56 i P-6 MEAN 7.4 3.7 28.5 2154 15 .66 1.4 0.59 .56 I P-7 800826 2035 7.35 4.OM 28.5 .68 1.3 0.68 .54 P-7 800827 0035 7.45 4.1 27.5 3600 1930 18 .53 1.4 0.72 .54 P-7 800827 0435 7.50 4.0 26.0 2100 9 .40 1.4 0.65 .54 P-7 800827 0835 4.3 25.2 .52 1.2 0.73 .56 P-7 MEAN 7.4 4.1 26.8 2015 14 .53 1.3 0.70 55 P-7A 800826 2100 7.1 5.6 23.0 7.1 1.0 < .05 7.5 P-7A 800827 0100 6.9 5.9 21.0 < 1.8 (TUB ) 285 77 3.7 1.0 �< .05 7.1 P-7A 800827 0500 7.0 7.4 20.5 248 58 5.7 8.1 .07 6.0 P-7A 800827 0855 7.0 5.7 20.4 6.6 2.0 .05 6.6 -7A MEAN ' 7.0 6.15 21.2 267 68 5.8 0.5 6.8 P-8 800827 0250 7.6 1 5.1 25.0 .52 1.3 .76 .49 P-8 800827 0645 7.7 4.9 25.0 1860 11 .42 11.0 . .76 .52 P-8 800827 1045 2.63 7.5 5.65 24.5 2040 11 .29 1.4 .75 1 .51 P-8 800827 1445 7.5 5.1 28.0 2120 12 .40 1.3 .83 .52 P-8 800828 1245 2.62 P-8 MEAN 7.6 5.19 25.6 2007 11 .41 1.3 .78 .51 TABLE 8 BOD COD METALS (ug/1) Station Date Time ( /1) (m /1) Tot. Cr Cd Cu Fe Pb Pln Ni Zn SO4 Cl Cond P-6 800826 1705 4.3 150 810 1100 P-6 800826 2105 4.7 100 P-6 800827 0105 4.0 110 880 3250 700 '700 P-6 800827 0505 3550 P-6 MEAN 4.3 130 845 2700 7nn P-7 800826 2035 4.3 120 690 282700 P-7 800827 0035 1 4.0 I ! P-7 800827 0435 3.9 200 600 700. P-7 800827 0835 3410 P-7 MEAN 4.1 135 820 3120 600 700 P-7A 800826 2100 16 150 34 3101 60 70 P-7A 800827 0100 8 I 290 P-7A 800827 0500 6 26 88 38 268 35 60 P-7A 800827 0855 1 290 P-7A MEAN 10 36 290 481 65 { P-8 800827 0250 3.4 130 710 2700 600 600 P-8 800827 0645 3.8 2730 P-8 800827 1045 3.6 180 810 2930 600 700 j P-8 800827 1445 < 50 <50 c 40 600 <100 50 3400 P-8 MEAN 3.6 155 760 2940 600 650 rn � TABLE 9 Fecal RESIDUE SERIES (mg/1) N SERIES (mg/1) P SERIES (mg/1) R.P. D.O. Temp. Coliform Tot. Tot. Vol. NO3-N+ Station Date Time (ft. ) ;; (mg/1) (0C) (#/100 ml) Tot. Vol. Sus. Sus. NH3-N TKN NO2-N Tot. P Ortho• P P-9A 80082 0500 7.3 6.1 21.0 3.5 5.5 .79 6.4 P-9A 80082 0915 7.3 6.8 21.6 <1.8 (TUBEPI 628 19 2.2 3.6 1.2 4.6 P-9A 80082 1300 7.0 7.0 24.5 630 23 .98 1.9 1.8 4.4 P-9A 80027 1700 6.8 1.5* 26.0 493 14 .23 1.0 1.9 4.0 P-9A MEIN 7.1 6.6 23.3 584 19 1.73 3.0 1.42 4.9 P-10 80082 0715 7.5 6.0 22.6 .49 1.1 .69 .59 P-10 80082 1115 3.15 7.6 6.3 24.5 770 1370 13 .34 .9 .72 .55 P-10 80082 1515 7.7 6.0 27.0 1420 13 .28 .9 .72 .59 P-10 80082 1915 3.15 7.5 6.3 24.5 1450 14 .19 .8 .69 .57 P-10 800828 1300 3.17 P-10 ME 7.6 6.2 24.7 1413 13 .33 .9 .71 .58 P-11 800827 0930 7.6 5.7 22.5 .44 .2 .73 .63 P-11 800827 1330 7.7 6.3 26.3 4000 * 1300 20 .30 .4 .76 .60 P-11 800827 1730 7.6 6.0 27.7 1320 16 .22 .8 .74 .62 P-11 800827 2130 7.8 5.8 25.0 1490 17 .16 .8 .73 .58 P-11 ME 7.7 6.0 25.4 1370 18 .28 .1 .74 .61 P-11A 800827 1450 7.3 6.25 26.1 .30 .4 .78 .65 P-11A 1800827 1840 7.6 6.20 26.9 480 1280 12 .23 .9 .81 .59 P-11A 800827 2240 7.8 6.40 24.0 1340 15 .17 . .7 .79 .59 P-11A 800828 0240 7.7 1 6.30 23.0 1 1370 14 .14 .7 .75 .57 P-11A ME N 7.6 6.29 25.0 1330 14 .21 93 .78 .60 TABLE 10 BOD COD METALS (ug/1) Station Date Time ( /1) (ME/1) Tot. Cr Cd Cu Fe Pb Mn Ni Zn SO4 Cl Corid P 800827 0500 3.5 81 220 930 180920 800827 0915 2.5 800827 1300 2.5 80 230 910 1150 150 800827 1700 50 40 100 100 100 110 680 P-9A MEAN 2.8 81 225 860 P-10 800827 0715 4.8 110 550 1910 400 600 P-10 800827 1115 3.5 1 ! 2000 P-10 800827 1515 4.0 110 610 2200 400 450 P-10 800827 1915 2000 P-10 MEAN 4.1 110 580 • 2028 0 I � I i P-11 800827 0930 4.3 120 1 390 11820 5 0 i P-11 800827 1330 4.1 P-11 800827 1730 5.2 20 540 ; 2200 350 . .350 P-11 80082 2130 2400 , P-11MEAN 4.5 120 465 2130 350 350 P-11A 800827 1440 4.0 140 420 1900 350 400 P-11A 800827 1840 3.5 I 2000 I P-11A ' 800827 2240 3.2 I 190 520 2100 400 300 2100 P-11A 800828 0240 " P-11A MEAN 3.6 I165 470 2025 375 350 w TABLE 11 Fecal RESIDUE SERIES (mg/1) N SERIES 69/1) P SERIES (mg/1) R.P. D.O. Temp. Coliform Tot. Tot. Vol. NO3-N+ Station Date Time (ft. ) PFI (mg/1) (oC) (#/100 ml) Tot. Vol. Sus. Sus. NH3-N TKN NO -N Tot. P Ortho' P P-12 800825 1730 1.97 P-12 800827 1750 7.7 6.60 26.5 .23 .8 .81 .62 P-12 800827 2150 7.9 6.30 23.0 600 1190 P-12 800828 0150 1.89 7.7 6.50 23.0 1310 18 .14 .8 .78 58 P-12 800828 0550 1.87 7.75 6.65 22.6 490 1360 21 .12 .7 .76 .57 P-12 800828 1313 1.89 P-12 MEA1 7.76 6.51 23.8 545 1287 20 .17 .78 .79 .59 P-13 800828 0415 7.6 7.7 21.5 .06 .5 1 .56 .19 P-13 800828 0815 7.65 8.0 20.4 .20 .8 .62 .49 P-13 800828 1215 7.7 8.0 22.0 .20 .0 .58 .60 P-13 800828 1615 7.35 24.9 1100 688 28 .05 .6 .53 .41 P-13 MEA 7.65 7.76 22.1 .13 .7 .57 .47 P-4A 800826 1510 7.85 8.6 24.7 20 78 22 <.05 .2 .19 .05 P-4A 800827 1310 7.1 8.7 22.8 72 6 .05 .2 .19 .05 P-4A MEA 7.48 8.7 23.8 75 14 k-5A800826 1555 6.95 7.7 22.5 320 94 8 --.05 .3 .34 .05 800826 1715 7.6 7.4 22.4 140 114 8 .07 .4 .14 <.05 800827 1400 7.5 7.9 24.8 115 9 .08 .3 .14 � .05 7.7 23.6 115 9 .08 .4 .14 ,05 TABLE 12 I� BOD COD TALS (ug/1) CQIQR Station Date Time ( /1) (m /1) Tot. Cr Cd f Cu Fe Pb Mn Ni Zn SO4 Cl Cond P-12 800827 1750 3.5 150 420 1790 350 350 P-12 800827 2150 3.3 1900 P-12 800828 0150 3.3 120 550 2000 350 Ahn P-12 800828 0550 4.2 2000 P-12 MEAN 3.6 135 485 1923 350 325 P-13 800828 0415 2.5 60 1210 93 1150 150 P-13 800828 0815 4.2 910 P-13 800828 1215 5.4 910 P-13 800828 1615 11100 P-13 MEAN 4.0 ! 6 i P-4A 800826 1510 2.1 < 50 <40 600 <100 <50 < 5 7 I P-4A 800827 1310 0.8 P-4A MEAN 1.45 i 66 P-5A 800826 1555 0.8 < 50. ;c40 500 4100 <50 8 3 91 15 35 P-9 800826 1715 2.2 < 50 <40 700 <100 <50 32 3 131 20 45 ' P-9 800827 1400 2.2 115 P-9 MEAN 2.2 123 a o � , I ' TABLE 13 Fecal RESIDUE SERIES (mg/1) LNH3 SERIES (mg/1) P SERIES (mg/1) R.P. D.O. Temp. Coliform Tot. Tot. Vol. NO3-N+ Station Date Time (ft.) H (mg/1) (0C) (#/100 ml) Tot. Vol. Sus. Sus. -N TKN NO,-N Tot. P Ortho• P P-11B 800826 1800 7.65 7.8 23.0 2300 90 11 �.05 .3 .26 .17 P-11B 800827' 1455 7.6 8.1 22.7 84 6 .25 .6 .34 .26 P-11BMEAN 7.65 8.0 22.9 87 9 .5 .30 .22 P-12Z 800826 1845 7.3 7.9 23.2 230 52 13 �.05 .2 .26 .05 P-12A 800827 1545 7.1 8.4 23.0 48 12 .05 .2 .27 .05 FN 7.2 8.2 23:1 50 13 .2 .27 .05 800826 2000 7.1 7.1 23.3 1200 82 13 .10 .5 .14 .24 800827 1635 7.0 6.5 25.0 95 16 .25 .0 .17 .64 N 7.1 6.8 24.2 89 15 .18 .8 .16 .44 I i TABLE 14 BOD COD METALS (ug/1) Station Date Time ( /1) (m /1) Tot. Cr Cd Cu Fe Pb !(n Ni Zn SO4 Cl Cond P-11B 800826 1800 1.2 50 <40 500 e.100 50 �5 2 73 25 P-11B 800827 1455 1.8 P-11B MEAN 1.5 74 l . P-12A 800826 1845 1.1 .c 50 <40 500 400 450 45 2 40 20 25 P-12A 800827 1545 2.2 29 P-12A MEAN 1.7 35 I ' P-12B 800826 2000 2.6 50 <40 700 �100 t50 <5 2 69 40 40 P-12B 800827 1635 5.6 61 P-12B MEAN 4.1 65 I , � I I I j I I I F ... . ... ... i gg. .3 ..... .! Q 3 ':::::E33E _• •3 : : .:�.. .-Mil .!°EE........ ... ... i ?=iEi3i6ile _.. :._.•I.o€e•... ... 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I°66°li!,.I! aIIIIIIIIIIIIIEIiIIIIIIIIIIIIlIli6lllllEal161IIIIEEIfii, e • , ,9:1I:16ff66•E::,::: Ili! e • 11i16,6::., �l6l�IIIIIIIIIIIIIIIIIIIIIIIIIII IIIIIIIIEfldilllllllli!lIIIIII 6 III ilifli!!l11 IfI111 EI IIIII ':Ili illliE°•.III'EIIIIiIIlflllilillliflffflldllli u-nu, III11Ei191lIIEIIIIIIiiii ��'gIUlIOIIgIN�;Wllit6lli1116166!a99lI.aIa.: 66 {�Qj -�--___ " — Ice,IIIIII11111eneee.Le+enn..,.n�.auunn Il..i..Len■■nnN..n..■ra.........N II III 0 'Ci°'.•••:':. al '1: iiE�at!!!i!!!iTliiiiiiii elel6�:#i66i 6999i 66E€€9E€9966.i#6EI#I6966969966I66i#a:lllEllilf9fl€991 TA LE 15 BODS BOD BODult. BOD]t STA 1 - P-0 800828 1130 100 1.70 2.32 2.2 0.25 P-1 800826 1130 100 1.97 4.34 3.8 0.12 3.0 0.23 13.5 .01 P-1 800826 1940 100 1.53 2.83 2.4 0.13 P-2 800826 1200 100 7.57 28.73 35.3 0.05 P-2 800826 2000 100 7.14 29.50 48.2 0.03 P-4 800826 1232 100 6.20 23.47 28.4 0.05 9.3 0.22 72.2 .01 P-4 800826 2032 100 5.95 21.90 27.0 0.05 P-4A 300826 1510 100 1.33 2.80 2.5 0.11 1.5 0.34 7.4 .01 P-4A 800827 1310 100 1.00 2.52 2.1 0.09 1.4 0.25 8.2 01 P-5 800826 1630 100 5.13 25.69 95.9 0.01 P-5 300827 0030 100 5.43 27.01 : 101.9 0.01 P-5A 800826 1555 100 0.83 3.37 4.4 0.04 1.9 0.13 6.5 .02.. P-6 800826 2105 100 4.50 25.24 99.8 0.01 P-6 800827 0505 100 3.23 21.79 81.2 0.01 P-7 800827 0040 100 3.93 21.60 48.2 0.02 P-7 300827 0835 100 3.40 21.73 83.7 0.01 P-7 300827 0835 100 3.43 21.36 82.6 0.01 P-7A 00827 0100 100 6.67 74.16 229.4 0.01 P-7A 800827 0855 100 6.33 71.07 100.1 0.04 P-7A 800827 0855 100 9.83 68.48 122.0 0.03 47 TA LE 16 STA I % BODS BOD30 BODUI I. K BOD lt. P-8 800827 0645 100 3.77 20.91 46.50 0.02 P-8 800827 1445 100 3.37 21.0 45.30 0.02 P-9 800826 1700 100 1.60 6.34 8.60 0.04 P-9 800827 1400 100 1.53 5.42 7.30 0.04 3.6 0.11 18.0 .01 P-9A 800827 0900 100 8.30 19.64 19.10 0.14 17.9 0.16 28.5 01 P-9A 800827 1700 100 1.87 57.13 57.20 0.15 P-10 800827 1115 100 2.80 16.00 35.50 0.02 P-10 800827 1915 100 3.80 15.96 23.00 0.04 P-11 800827 1330 100 3.00 15.12 33.60 0.02 P-11 800827 2130 100 3.17 14.77 21.10 0.04 P-11A 800827 1840 100 3.57 14.91 19.40 0.05 P-11A 800826 0240 100 3.07 12.97 19.00 0.04 P-11B 800827 1800 100 2.13 4.97 4.80 0.11 P-11B 800827 1450 100 1.25 5.98 9.70 0.03 P-12 800827 2150 100 3.10 13.04 16.60 0.05 P-12 800828 0550 100 3.30 113.17 16.90 0.05 P-12A 800826 1845 100 1.03 2.49 2.30 0.09 P-12A 800827 1545 100 •73 2.60 2.80 0.05 1.3 0.18 7.8 .0 P-12B 800826 2000 100 3.03 7.83 8.40 0.09 P-12B 00827 1635 100 5.47 16.33 17.40 0.08 48 TA ME 17 STATLION % BODS BOD BODUIt. tC I ITIt.-C, KC BODUIt. KN P-13 800828 F1215 100 3.86 12.56 14.10 0.07 4.5 0.37 12.8 0.12 . P-13 800828 100 6.47 17.73 18.8 0.09 P-13 800828 1615 100 3.90 10.90 11.0 0.09 49 TABLE 18 PIGEON RIVER 30 DAY P & N SERIES 26 - 28 AUGUST 1980 N SERIES (mg/1) P SERIES (mg/1) Fecal RESIDUE SERIES (mg/1) NO3-N+ Temp. Coliform Tot. Tot. Vol. Station Date Time Day D.O.(D.O. (oC) (#/100 ml) Tot. Vol. Sus. Sus. NH3-N TKN N0--N Tot. P Ortho- P P-0 800828 1130 0 < .05 .1 .19 <• .05 30 K .05 .2 .27 - .05 P-1 800826 1130 0 < .05 .1 .16 " .05 30 .05 .1 .26 .05 P-1 800826 1940 0 .05 .2 .14 .06 30 < .05 .2 .21 < .05 P-2 800826 1200 0 1.2 2.1 < .05 .80 30 1.3 1.9 .05 .65 1.7 3.1 < .05 .82 P-2 800826 2000 0 1.8 2.3 .08 .73 30 1.0 .7 .05 65 P-4 800826 1232 0 .99 .2 .20 .59 30 P-4 800826 2032 0 1.4 .2 <.05 .73 30 1.3 .0 .07 .63 P-5 800826 1630 0 .84 .7 .39 .60 30 .12 .9 1.2 .56 P-5 800827 0030 0 1.1 .9 0.37 .65 30 .07 .7 1.6 .55 r i o TABLE 19 Fecal RESIDUE SERIES (mg/1) N SERIES (mg/l) P SERIES (mg/1) D.O. Temp. Coliform Tot. Tot. Vol. NO3-N+ Station Date Time Day (mg/1) (oC) (#/100 ml) Tot. Vol. Sus. Sus. NH3-N TKN NO2-N Tot. P Ortho P P-6 800826 2105 0 .60 1.4 0.62 .56 30 < .05 .5 1.30 P-6 800827 0505 0 .68 1.7 0.61 56 30 0 .54 .53 1.4 0.72 .54 P-7 800827 0035 0 OS 1.0 1.30 .47 30 P-7 800827 0835 0 .52 1.2 0.73 .56 30 .05 0.6 1 .35 .48 P-7A 800827 0100 0 3.7 11.G < .05 7.1 30 .06 3.9 7.5 7.2 P-7A 800827 j 0855 0 6.6 2.0 .05 6.6 30 .05 .6 9.3 6.4 P-8 800827 0645 0 30 <.OS 6 1.3 .45 P-8 800827 1445 0 .40 .3 .83 .52 30 .05 .6 1.3 .45 rP-9A00827 0900 0 2.2 .6 124630 .06 .6 3.6 5.4 00827 1700 0 .23 .0 1.9 4.0 ; 30 t.05 .9 2.1 4.0 TABLE 20 Fecal RESIDUE SERIES (mg/1) N SERIES (mg/1) P SERIES (mg/1) D.O. Temp. Coliform Tot. Tot. Vol. h03-N+ Station Date Time Day (mg/1) (0C) (#/100 ml) Tot. Vol. Sus. Sus. NH3-N TKN NO,)-N Tot. P Ortho P P-10 800827 1115 0 =.9 .72 .55 30 .05 .6 1.2 .49 P-10 800827 1915 0 .19 .8 .69 .57 30 P-11 800827 1330 0 .30 1.4 .76 .60 30 .05 .7 1.2 .54 P-11 800827 2130 0 .16 .8 .73 .58 30 .06 .8 1.0 .53 P-11A 800827 1840 0 .23 .9 .81 .59 30 .09 .5 1.EF 53 P-11A 800828 0240 0 .14 .7 .30 .09 .6 .9754 P-12 800827 2150 0 .18 .8 .80 .57 30 .11 .9 1.1 .52 P-12 800828 0505 0 .12 .7 .76 .57 30 .10 .8 .97 M ! P=13 800828 0815 0 .20 .8 .62 30 G .05 .3 1.1 P-13 800828 1215 0 20 .0 .5830 G.05 5 1.3 13 800828 615 0 .05 6 .53 30 <. .3 .7; TABLE 21 Fecal RESIDUE SERIES (mg/1) N SERIES (mg/1) P SERIES (mg/1) D.O. Temp. Coliform Tot. Tot. Vol. R03-N+ Station Date Time Day (mg/1) (oC) (#/100 ml) Tot. Vol. Sus. Sus. NH3-N TKN N0I-N Tot. P Orth'o P P-4A 800826 1510 0 .4.05 .2 .19 .05 30 .4 .05 1 2 < P-4A 800827 1310 0 -e-.05 .2 1 < 30 4.05 2 -32 P-5A 800826 1555 0 .05 30 -4.05 .1 .60 < 05 P-9 800826 1700 0 .07 .4 .14 -<.05 30 4.05 .1 .46 <.05 P-9 800827 1400 0 .08 .3 .14 �.OS 30 4.05 P-11B 800826 1800 0 30 4.05 .2 3.4 .14 P-11B 800827 1450 0 .25 .6 :34 .26 30 .11 7 .63 .23 P-12A 00826 845 0 .05 2 .26 .01; 30 ' 05 1 .38 <.05 P-12A 00827 t245 0 OS 2 .27 OS 30 < 05 1 8 < 0 P-12B 300826 2000 j 0 .10 5 .14 .24 30 _ ' 05 2 .60 .17 i TABLE 22 Fecal RESIDUE SERIES (mg/1) N SERIES (mg/1) P SERIES (mg/1) D.O. Temp. Coliform Tot. Tot. Vol. NO3-N+ Station Date Time Day (mg/1) (oC) 0/100 ml) Tot. Vol. Sus. Sus. NH3-N TKN NO2-N Tot. P Ortho P P-12B 80082 1635 0 .25 1.0 .17 .64 30 .05 .3 1.0 .52 F i d i TABLE 23 PIGEON RIVER 91 DAY BOD P&N'S RESIDUE SERIES (mg/1) N SERIES (mg/1) P SERIES (mg/l) - Tot. Tot. Vol. NO3-N+ Station Date Time Tot. Vol. Sus. Sus. NH3-N TKN NO2-N Tot. P Ortho P P-1 800514 1100 0 Day 31 8 1 0 �.05 <.1 .25 < .05 P-1 800514 fter 91 Days 100% No 02 < .05 <.1 .61 < .05 P-1 800514 fter 91 Days 100% 02 <.05 .1 .60 1 < .05 P-2 800514 1030 0 Day 2080 419 23 13 3.6 4.8 -- .05 .77 .47 P-2 800514 After 91 Days 1001 <.05 1.0 5.1 .74 P-2 800514 After 91 Days 75% Uncorrected Val e <.05 .6 3.6 .48 P-2 800514 After 91 Days 50% Unco recte Valu < .05 .8 3.3 .50 Model Development A. Introduction In August of 1980, a fluorescent dye time-of-travel study and an intensive water quality survey were performed in the Pigeon River in western N.C. between the Towns of Canton and Hepco. Data collected during these studies were used to calibrate a water quality model to determine a wasteload allocation for the Champion Paper Mill in Canton. The resulting allocation curve for a waste D.O. of 6 mg/1 is shown in Figure 31 of this report. Any combination of BOD5 and NH3-N on or below the curve represents an acceptable allocation for Champion. A reasonable combination would be a BOD5 of 4 mg/l and a NH3-N concentration of 1 mg/l. At these concentrations, the D.O. of the modeled 20 mile reach of the Pigeon River will not fall below 5 mg/l if the River conditions are less restructive or the same as design conditions used in the model. B. Model Development The EPA stream quality model (QUALL II) uses a combination of the hydraulic characteristics of a stream and the system's chemical and biological reaction rates to predict in-stream trends in water quality parameters. The hydraulic portion of the model requires functions describing the relationships between flow, velocity, depth and reaeration (K2) . Developed to predict measured conditions in the stream, these functions theoretically adjust velocity, depth and K2 to changes in stream flow. Calibration of the model's chemical parameter predictions involves adjusting oxidation rates for organic nitrogen, ammonia nitrogen and CBOD to best predict the observed in-stream decay of these substances. These rates are assumed to be independent of stream flow but vary with changing temperatures. The calibrated Quall II model is adjusted to 7/10 low flows and design temperatures for the final allocation calculations. The Pigeon River hydraulic model was primarily based on data collected 56 by the N.C. Dept. of Natural Resources and Community Development (NRCD) in August of 1980. This information was supplemented by data from a 1965 report by the Department of the Interior on a biological investigation of the Pigeon and a 1980 N.C. Wildlife Department report by Wingate and Davies. Pigeon River calibration flows were calculated from measured tributary discharges, self-monitoring data from Champion Papers and the Towns of Clyde and Waynesville and conservative substance mass balances. Table24 shows the measured tributary and waste flows used to calibrate the model. Additional stream flow contributed by small tributaries and land runoff was estimated from mass balances of measured concentrations of total dissolved solids and chloride at the various stream stations. The Pigeon River's velocity at the time of the survey was calculated from data collected during a fluorescent dye time-of-travel study on the 25 and 26 of August. The River's velocity changes only slightly over the twenty miles modeled reflecting the relatively constant slope of 15 ft/mi. The average measured velocity was 0.65 fps. Time-of-travel data from a 1965 Dept. of the Interior study of the Pigeon River was combined with the 1980 data to develop a power _ function relationship between velocity and flow. Between 1965 and 1980, the introduction of secondary waste treatment at the Champion Plant has changed the water quality of the Pigeon River considerably. Despite these improvements in water quality, the flow-velocity relationships measured in the two studies were reasonably consistent. The constant velocity of 0.76 fps measured in 1965 reflected flows somewhat greater than those measured in 1980. The two sets of data were combined to calculate the velocity power equation : V = 0.143 Q(0.310) The reaeration constant (K2) for the Pigeon model was calculated using Owen's relationship between K2, velocity and depth: K2 = 2.31 (9.41 (Velocity)0.67/(depth)1.85) Cross sectional areas between stations were estimated from velocity and flow data. These were combined with widths measured for a 1980 N.C. Wildlife Study of the River's fisheries to calculate average depths along the modeled reach. The resulting 57 K2 of 2.01 day-1 was assumed to be constant for the entire model. A relationship between depth and river flow was calculated with the following relationships: V A Wxd d = 1/VW (Q) d = 0.026 Q Where: V = average river velocity Q = average river flow A = average cross-sectional area W = average width d = average depth Temperatures measured in the Pigeon during the intensive survey ranged from 330C at the outfall to about 250C at the downstream stations. Therefore, three design temperatures were employed: 310C for miles 21.0 to 17.9, 280C for miles 17.9 to 15.9 and 250C for miles 15.9 to 0. Decay rates for organic nitrogen, ammonia nitrogen and CBOD (K1) were developed using average chemical concentrations measured at each station (Table 25) . Dissolved oxygen concentrations were corrected to the design temperatures using an analysis based on percent saturation. The decay of all modeled constituents was assumed to follow first order kinetics. Rate constants were determined by applying the X2 goodness of fit test. Chemical concentrations measured at the river stations were compared to concentrations predicted by the Quall II model with various reaction rates. The rate of organic nitrogen decay was determined first, since its decay produces ammonia and thus directly affects the ammonia decay rate. The best fit organic nitrogen rate was then incorporated into the model and a best fit rate for ammonia decay was determined. Finally, a decay rate for CBOD was found by fitting the rate to the dissolved oxygen data. 58 CBOD concentrations in the stream are affected by numerous reactions. The Kl rate theoretically reflects CBOD oxidation rates. However, settling and resuspension of bottom sediments also remove and replace CBOD in the overlying water and influence the oxygen demand of CBOD. A rate fitted to dissolved oxygen data incorporates these complex interactions and models the stream system as a whole. Calibration of the Pigeon River model produced the following rate constants: Kl = 0.17 day 1 K2 = 2.01 day 1 Korg-N = 0.0 day 1 KNH3 = 0.8 day 1 The results of the calibrated model are illustrated in Figures 26-30. The solid line shows the constituent concentrations predicted by the model. The three crosses correspond to the measured maximum, average and minimum concentration at each station. The scatter in the organic nitrogen data (Figure 26) made accurate fitting difficult. The pictured calibration shows the decrease in organic nitrogen concentration caused solely by dilution. Ammonia nitrogen (Figure 27) decayed smoothy with travel down the Pigeon River. A decay rate of 0.8 day 1 fit the data well. Although high for most systems, this rate seems reasonable for the Pigeon River. The warm, turbulent, riffled reaches of the river provide an excellent environment for nitrifying bacteria. The metabolise of these organisms is primarily responsible for. the decay ammonia in aquatic systems. Oxidized nitrogen (NO2 + NO3) is produced from the oxidation of ammonia. The calibrated model (Figure28) underestimated the measured concentrations of nitrite and nitrate for most of the river. This is probably due to additional runoff input to the river not accounted for in the model. Although the CBOD oxidation was fitted to dissolved oxygen data, the resulting predictions (Figures 29 & 30) fit the measured data well. C. Allocation The calibrated model was adjusted to 7/10 flows for the allocation determinations. USGS data was used to calculate 7/10 flows on the Pigeon and all the major tributaries. Design waste flows were used for the Champion, 59 Clyde and Waynesville Wastewater Treatment Plants. Allocation flows are included in Table 24. Wasteload allocation calculations are routinely made at a calculated design temperature. The design temperature calculated for Champion Papers was 220C (71.60F) . However, the elevated temperature measured in the Pigeon below the Champion outfall are produced by the plant's heated discharge. It seemed unreasonable to adjust the model to a calculated temperature never seen in the river. The calibration model temperatures were therefore used for the allocation determinations. Other boundary conditions were established as follows : Upstream temp. = 71.6aF Upstream D.O. = 7.9 mg/l (90% saturation) Upstream CBOD = 3.0 mg/l Upstream NH3 = 0.05 Champion waste D.O. = 6 mg/l - A standard allocation procedure is employed for all Level C models. With all boundary conditions set, the NH3-N in the waste is set equal to zero and the CBOD concentration is varied until the resulting D.O. in the simulated stream reach does not drop below 5 mg/l. The CBOD is then set to zero and the NH3-N is varied until a D.O. = 5 mg/l minimum is maintained. The CBOD is then converted to BOD5 using the CBOD/BOD5 ratio determined for the waste (3.65) . These two points then define the allocation graph shown in Figure3l. Any combination of NH3-N and BOD5 on or below this line respresents an acceptable allocation for Champion Paper. 60 Table 24. Measured Point-Source Flows for Calibration & Allocation Models Calibration Allocation Source Flow (cfs) Flow (cfs) Pigeon River upstreau of Champion Paper 81.66 76.1 Champion Influent 71.66 76.0 Champion Effluent 67.17 75.17 Beaverdam Creek 2.73 1.39 Thichety Creek 0.70 0.36 Clyde WWTP 0.21 .198 Richland Creek 36.60 20.8 Waynesville WWTP 4.43 9.3 Crabtree Creek 6.38 3.0 Jonathans Creek 36.01 29.6 Fines Creek 6.34 5.20 61 Pigeon River Water Quality Data August 26 and 27, 1980 Table 25. Avg. D.O. @ Design Design River Temp Temp CBOD Org-N NH3-N NO2+NO3 Station Mile oC mg/1 mg/l mg/l mg/1 mg/1 P-1 63.31 31 6.75 2.20 0.1 0.05 0.16 P-2 63.21 31 4.5 35.40 1.1 1.40 .05 P-4 62.91 31 4.55 23.73 0.88 1.12 0.06 P-5 61.41 31 3.63 21.37 1.06 0.94 0.37 P-6 59.51 28 3.67 22.40 0.74 0.66 0.59 P-7 57.91 25 4.23 21.48 0.77 0.53 0.70 P-8 55.91 25 5.24 18.79 0.89 0.41 0.78 P-10 54.11 25 6.11 17.30 0.57 0.33 0.71 P-11 52.81 25 5.99 19.39 0.82 0.28 0.74 P-11A 50.55 25 6.28 13.82 0.72 0.21 0.78 P-12 49.11 25 6.37 13.39 0.61 0.17 0.79 P-13 43.71 25 7.36 7.20 0.57 0.13 0.57 62 Figure 26. Organic Nitrogen Calibration, K = 0.0 day-1 r � m + QI �- m r, to + � + Vr m + td M + Q + $ + � m F- td z V T + Z PD d Ln m n m to m 19.m 1 7.21 15.0 13.® 11 .0 i3m 7.0 S.m 3.0 MILES RE30VE HEPCO rn w I RMMONiRCDNCENTRRTfDN CMG/L] 0.10 0.20 0.30 0.40 0.60 0.60 0.70 090 0.30 I90 1.10 1.20 1.30 1.40 + + !! + + + H + + + IiIH, I 6 r m _ m W + i c n • B m < @ + + 7 fq w z I H m ° ov + + w n w rt 0 O H � x n 0 co a w i r + + + Figure 28. Oxidized Nitrogen Calibration E7 t + J + + $ + U' + + u + N t Z t° + W + + W fY N Z s m W N_ 4 ory ei 1 M.0 17.0 1 S.0 13.0 1 1 .0 5.0 7,0 5.0 3.0 MILES RBOVE HERCO rn Figure 29. CBOD Calibration h� m + +\ + ry + + 4. n + L VI + + u + 0 + Cp Vm + i i + + 1 Man 17,ti1 1 s.m 1 :9.0 t t ja 9.m 7.m S.m 3.0 MILES R130VE HEPC0 rn rn Figure 30. Dissolved Oxygen Calibration ai J + M + E tq + L 4' Ld } In $ + + X 0 + + c] W 7 J ` m * ++ 12H.M I7.Ul 1 : .Ja 13.1" 11 .0 0.In 7.0 irm 3.0 MIl_E�E RES13VE HE:PCO Figure 31. Champion Allocation, D.C. = 6 mg/l L-9 2: 1 LL IE ru s.O M VI 17.M7 E1.0 n.vi 1 Ct�lJli—S] CMri L7 rn CO LIST OF TABLES TABLE PAGE D2.1 Checklist of fish species collected in the Pigeon River, 1980. 79 D2.2 Distribution of fish species in the Pigeon River. 80 D2.3 Standing Crop (kg/ha) and number of fish/ha in the Pigeon River. 81 D2.4 Water quality data of fish sample stations on the Pigeon River. 82 D3.1 Fish analyzed for complex organics and heavy metals. Pigeon River, August 1980. 83 D4.1 Pigeon River Discharge (CFS) at Canton, North Carolina. 84 D4.2 Temperature Data (oC) , Pigeon River stations. 84 D4.3 Dissolved Oxygen (mg/1) , Pigeon River stations. 84 D4.4 Taxa Richness Values, by group, for Pigeon River collections. 85 D4.5 Comparison of Station 4 with the Mountain River Control (MRC) Data Set. 86 D4.6 Taxa Richness Values, by group, for the Pigeon River 87 tributaries. D4.7 Level I Data 88 69 LIST OF FIGURES FIGURE PAGE D2.1 Station location, fish survey Pigeon River, Haywood County, North Carolina, August, 1980 77 D4.1 Effect of Champion's effluent under varying flow and temperature patterns. 78 70 D. Biological Surveys 1. INTRODUCTION The North Carolina Division of Environmental Management agreed to cooperate with the Tennessee Valley Authority in the development of work plans for implementing water quality studies. A work plan to determine the current impact of Champion Paper Company's discharge into the Pigeon River at Canton, North Carolina was submitted to TVA for review in July of 1980. The biological integrity of the Pigeon River, as outlined in the work plan, was evaluated using several accepted biological methods. The first was an evaluation of the composition of the indigenous fish populations of the Pigeon River above and below the discharge point. The survey was conducted by the North Carolina Wildlife Resources Commission. As part of this in- vestigation several representative fish species were sent to the EPA laboratory in Athens, Georgia for analysis of heavy metals and complex organic compounds within the fish flesh. A supplemental survey of benthic macroinvertebrates was also conducted. Biologists with the North Carolina Division of Environmental Management were responsible for the results of this survey. Additionally, a series of static bioassays were conducted on Champion Paper Company's effluent. Also, in-situ acute bioassays were conducted using live boxes and indigeous fish species to determine acute in stream toxic effects. Bioassays were conducted by biologists with the North Carolina Division of Environmental Management. Each of these surveys are reported upon separately in the following sections of this report. Because several groups and individuals were responsible for this report, there may be some overlap of information. 71 2. FISHERIES INVESTIGATION a. Introduction The Pigeon River is a tributary of the French Broad River in Tennessee. The river flows for 63 km in North Carolina before entering Tennessee and has a mean width of 24.4 m and an estimated surface area of 293 ha (Fish 1968) . This surface area includes the 138 ha Waterville Reservoir located 16 km up— stream from the Tennessee state line. The ecological classification of the Pigeon River ranges from brown trout upstream from the Canton water supply intake to smallmouth bass in the rest of the river in North Carolina (Fish 1968) . Many of the river's tributaries downstream from Canton have a trout ecological classification (Fish 1968) . The Pigeon River, downstream from the Champion Paper Company's effluent discharge, is severely degraded and the smallmouth bass ecological classification is not being attained. The Division of Environmental Management (DEM) and The Tennessee Valley Authority (TVA) assisted the North Carolina Wildlife Resources Commission in collecting qualitative and quantitative fish samples on the Pigeon River. This work was part of a major study DEM was conducting on the Pigeon River to determine the parameters to be included in a new discharge permit for Champion Paper Comapny. b. Methods and Materials Four sample sites were selected on the Pigeon River (Figure D2.1) . Sample- station 1 was located approximately 300 m below the confluence of the East and West Forks Pigeon River. An island splits the river in approximately equal halves with the east side channel being sampled. This corresponds to river mile (RM) 69.2 for TVA. The sample area was 100 m in length and averaged 17.2 m in width. This station served as the control since it was located above the Champion Paper Company's effluent discharge. 72 Sample station 2 was located approximately 1.6 km downstream from the paper company's effluent discharge in Canton. This site was at a bend in the river approximately 500 m beyond the end of Haywood County SR 1552. This corresponds to RM 62.2 for TVA. The sample area was 75 m in length and averaged 15.6 m in width. Sample station 3 was located approximately 8.9 km downstream from the paper company's effluent discharge. The site was adjacent to Haywood County SR 1513 northeast of Clyde. The Champion Paper Company landfill was adjacent to and on the opposite side of the river. This corresponds to RM 59.1 for TVA. The sample area was 100 m in length and averaged 20.0 m in width. Sample station 4 was located approximately 22 km downstream from the paper company's effluent discharge. It was located adjacent to Haywood County SR 1355 approximately 1 km downstream from the Haywood County SR 1363 bridge ------crossing. The nearer side channel of the river was sampled. This corresponds to RM 47.7 for TVA. The sample site was 100 m in length and averaged 16.6 m in width. Rotenone fish toxicant was used to collect all fish samples. All stream measurements (width, depth, flow, etc.) were taken four days prior to the actual sample. The depth was measured with a meter stick at 7-15 equidistant points on transects across the river and the data averaged. Depth transects were taken every 25 m in each sample area. At each depth transect, the stream width was measured and mean stream width for the sample calculated. Stream velocity'was calculated in meters per second (m/s) by determining the average time for a partially submerged object to traverse 10 M. A minimum of three drifts were timed and the results averaged to determine stream velocity. 73 Volume of stream flow was calculated from the following formula: V = wdfc; wherein V = volume in cubic meters per second (m3/s) ; w = average width in m; d = average depth in m; f = velocity in m/s; and c = coefficient of roughness (0.8 for a rough bottom) (Bayless and Smith 1962) . The amount of rotenone required to yield a 1 ppm concentration in the stream for 5 min was then calculated. Immediately upon entering the sample site, a downstream block net (0.64 cm stretch mesh) was placed across the channel and securely anchored. An upstream block net was unnecessary because of the high stream velocity. Five percent emulsifiable rotenone was applied at the upper end of the sample site area to provide for a 1 ppm concentration of the toxicant over a period of 5 min. Potassium permanganate was applied immediately above the block net to neutralize (oxidize) the rotenone. Fish were collected, identified, measured and weighed at each sample site. Fish not identifiable at the site were preserved and later identified by TVA personnel (Joe Freeman) . All fish identified in the laboratory are located in either the TVA or University of North Carolina — Charlotte ichthyology collections. Water samples were collected and analyzed by DEM at each sample station. These parameters included: dissolved oxygen, turbidity, temperature, total hardness, methyl orange alkalinity, pH, suspended residue, total residue, fecal coliforms and BOD. c. Results and Discussion An evident change in the ecosystem of the Pigeon River occurred between stations 1 and 2. Compared to station 1, fish species diversity (Tables D2.1 and D2.2) , fish relative abundance and standing crop (Table D2.3) and water quality (Table D2.4) were greatly reduced at station 2. Centrachid species 74 collected at both stations exhibited a significant reduction in relative abundance, standing crop, condition and a mean size at station 2 as compared to station 1. An exception was the redbreast sunfish, Lepomis auritus, which exhibited a slight increase in abundance and standing crop at station 2. The elevated water temperature at station 2 probably afforded the redbreast sunfish a competitive edge. Both stenothermal and eurythermal fish species were collected at station 1, while only eurythermal species were found at stations 2, 3 and 4. Black bullhead, Ictalurus melas, and carp, Cyprinus carpio, which are typical warmwater species, first appeared station 2. The lowest fish standing crop, relative abundance and species diversity occurred at station 3 (Tables D2.2 and D2.3) . No game fish species were collected at this station. The dissolved oxygen sag recorded near station 3 (see DFM chemical study report) and possible seepage from an adjacent Champion Paper Company landfill are suspected causes of this degradation. The Pigeon River appears to begin recovering from its pollutional load near station 4, as species diversity, relative abundance and standing crop of game and nongame fish increases (Tables D2.2 and D2.3) . Part of this recovery might be attributed to the inflow of higher quality water from tributary streams of this section which carry a trout ecological classification (Fish 1968) . In addition, the natural regenerative processes within the stream begin having a positive effect on water quality. This study indicates that the Pigeon River is severely impacted at stations 2, 3, and 4. While the theory of longitudinal succession predicts natural changes in the fish population along a stream's course, such an abrupt demarcation, as exists in this section of the Pigeon River can only be the result of unnatural influences on the aquatic system. Since the Champion 75 Paper Company discharge is the only significant pollutant entering the river between stations 1 and 2, this would strongly indicate that this discharge is a major limiting factor to a healthy fish population in this stretch of the Pigeon River. The Pigeon River downstream from the Champion Paper Company outfall presently has a carp-catfish ecological classification. This section would have an ecological classification of smallmouth bass (Fish 1968) if it were not for the elevated water temperatures associated with the discharge from Champion Paper Company. This elevated water temperature has resulted in a change in fish species composition. The Pigeon River has the regenerative capacity to become an excellent smallmouth bass stream if the chemical, thermal and solid effluents that are presently being discharged into the river were reduced or eliminated. 3. FISH TISSUE ANALYSES a. Introduction Another part of the overall biological assessment of the Pigeon River was to determine if complex organic material (including pesticides) and heavy metals were being concentrated in fish flesh. During the fish survey conducted by the NCWRC, several representative whole fish were preserved and shipped to the EPA laboratory in Athens, Georgia for analysis. Station location and water quality were similar to that reported in section D2 of this report (figure D2.1 and table D2.4) . An additional station was added by the Tennessee Division of Water Quality Control. b. Methods and Materials Ideally, it would have been best for the project if we could have collected similar size class fish from different feeding groups from each station. At the upstream station, it was decided to preserve several hogsuckers (Hypentelium nigricans) and several redbreast sunfish (Lepomis 76 auritus) from two size classes. We had assumed that of all the fish we would collect these would be most representative. Table D3.1 lists the fish sent to EPA for analysis. Fish taxa used in the organics analysis were double wrapped in aluminum foil and iced for delivery, specimen used in the heavy metal analysis were double wrapped in plastic bags and iced for delivery. EPA preparation procedure and extraction are included in Appendix I. C. Results and Discussion The results from both scans can be seen in Appendix I. Very little bioconcentration of most parameters are detected. This is particularly true for pesticides and other chlorinated hydrocarbons, purgeable organic compounds and extractable organics. High concentrations were recorded for several metal compounds (Sodium, Aluminum, Calcium, Magnesium and Zinc) . Because whole fish were used in the analysis, we would expect these higher concentrations. However a previous survey (Tedder et al, 1980) reported detectable concentrations of three of these compounds (Sodium, 420 mg/l; Aluminum, 1.40 mg/l and Zinc 0.11 mg/1) in the water. Certain ionic forms of these metals may be toxic to juvenile fish. At this point it isn't clear, or statiscially valid, to evaluate or to corrolate these observations. The only conclusion we can make at this point, is that we found higher concentrations of several metals in flesh of redbreast sunfish at station 2 immediately below the discharge. Chronic bioassays using indigeneous fish species should be performed. 4. BENTHIC SURVEYS a. Introduction One specific purpose of the TVA-EPA Subagreement was to develop the water pollution control needs required to improve the quality of the Pigeon River in North Carolina and Tennessee. The North Carolina Division of Environmental Management agreed to develop and carry out biological water 77 quality studies of the Pigeon River. NCDE14 assisted the NCWRC in the fisheries investigation and conducted both the benthos and bioassay surveys. The Division has utilized and supported the use of aquatic community structure, especially for benthic macroinvertebrates, in environmental assessment. It is the intent of this report to review the results from previous benthic surveys on the Pigeon River and to comment on current benthic integrity as part of the overall Pigeon River investigation. b. Methods and Materials Several benthic surveys have been conducted to determine the biological integrity of the Pigeon River. We will concentrate only on the most recent surveys in this report. This first two collections were made by the Operations Section of the Division of Environmental Management (October 1978 and June 1979) . The results of their investigations were reported in Tedder et al. (1980) . A third collection was conducted only at five sites in May of 1980. These sites were the same sites as reported in Tedder et al. (1980) and are numbered accordingly. The most recent survey, complying specifically with the sub-agreement between NCDEM and TVA, was conducted in August of 1980. Four stations were sampled. These four stations were located at the fish collection points, but do not compare precisely with prior benthic surveys. The station numbers were assigned to each station on the basis of its proximity to previous benthic stations. For example, during the August 1980 survey a control station was located above Champion's effluent and near station 4 from a previous survey. The only exception to this is station 4A where there is no prior benthic data. Station 4A is located approximately 1.6 km down- stream from Champion Paper Company's discharge. Precise station locations are described for previous benthic surveys in Tedder et al. (1980) and for the most recent survey in the Methods and Materials section of the fisheries in- vestigation of this report. 78 Benthic collections were made either with a surber sampler (Tedder et al. 1980) or by a "kick" technique (Penrose et al. 1980) . Both techniques involve physically disrupting a known area of stream substrate and allowing the organisms to drift into a collection net. The samples are then preserved and brought back to the lab for processing and identification. Sample processing and data analysis generally follow the techniques described in Penrose et al. (1980) . Data summary tables include both Level I (single number summaries, table D4.7) and Level II (data summarized for major groups, tables D4.4, D4.5 and D4.6) . More complete data for May and August, 1980, is included in Appendices II and III. Fish collection techniques did not facilitate effective fish stomach content analysis. This part of the survey was not completed. c. Results and Discussion Survey I October 1978 (Station locations as of Tedder et al. 1980) Identification procedures improved after this collection period, therefore comparisons with other collections must be made with caution. However, the general pattern is still quite obvious. Ephemeroptera disappear completely at stations 6 through 8A (Table D4.4) indicating severe stress at all areas above Waterville Lake. The most degraded conditions were found at Station 6, an area dominated by the snail Physa and tubificid worms. These organisms are typically associated with very low. dissolved oxygen conditions. A limited recovery was observed at stations 8 and 8A, where tolerant caddis- flies (Hydropsyche spp) became dominant. Station 9 was located in an area of the river that receives little Champion effluent. The tunnel from Waterville Lake bypasses this area, therefore this area is largely fed by groundwater and several streams. This area was diagnosed as unstressed. 79 Station 10 was located below the bypass tunnel, and the community was similar to that recorded at Stations 8 and 8A. Survey II: June 1979 (Station locations as of Tedder et al. 1980) Conditions are still assessed as excellent at control Station 4 (Table D4.4) . This area was characterized by a diverse assemblage of Ephemeroptera and Trichoptera (11 taxa each) . Both groups are sharply reduced at Station 6 and Tubificidae become abundant. As in October 1978, there was an increase in tolerant Hydropsychidae at Station S. There was a gradual recovery through Station 9, although recovery was not complete. Station 10, at the North Carolina state line, was very severely stressed. All taxa occur in very low density at this station. Further field investigations should be planned to determine the causes of such deterioration. Survey III: May 1980 (Station location as of Tedder et al. 1980) May 1980 was a period of high flow and low temperature. Under these conditions, Champion's effluent had less effect on river biota than observed during other surveys. A diverse mayfly fauna was found at all stations above Waterville Lake (Table D4.4) , although a decline was evident at stations 6 and 8A. Also note the absence of stoneflies at Station 8A. Recovery was complete at Station 9, but Station 10 was found to be severely stressed. During this survey there was a 76% reduction in average density of organism at Station 10 compared to Station 8A and a 59% reduction in total taxa richness, indicating severe stress according to criteria developed by DEM biologists (Penrose et al. 1980) . Note that the dominant oligochaetes are not "sludgeworms", but lumbriculidae. 80 Survey IV; August 1980 (Station locations as of Section 2 of this report) This survey was conducted in conjunction with the fisheries survey. It in- cludes only the areas above Waterville Lake. Physical conditions appeared very similar to the first survey conducted in October 1978. The benthic fauna was also very similar and most differences between these two surveys can be attributed to differing levels of taxonomic identification. This data indicates that there has been no significant changes in the effects of Champion's effluent since 1978. It is interesting to note the similarity between benthic data and fisheries data (Table D4.4) . Champion Papers (1981) conducted their own study of the river during this period. Their results generally agreed with the DEM studies. Level I data for these four station and three tributary streams can be seen in Table D4.7. General spatial trends Station 4, above Champion's effluent was typical of a clean mountain river. A comparison of data from station 4 (using only the last 3 dates) with the Mountain River Control (MRC) data set (Table D4.5) showed very good agreement. Station 6, just below Champion's effluent, was generally in very poor condition. Sensitive mayfly - stonefly taxa are found only during high flow - low temperature conditions. Dominant taxa are usually organic pollution "indicator" species, i.e. , those taxa tolerant of low dissolved oxygen conditions. These include Limnodrilus hoffineisteri, Nais, and Physa. The leech Mooreobdella melanostoma was often very conspicuous in benthic collection. Prior records of Helobdella elongata, Glossiphonia sp, etc. are 81 probably referable to the above species. _ Stations 8-8A These stations were located approximately 15-18 miles below Champion's effluent. They vary from fair to poor depending on flow and temperature. Some recovery was indicated by the increase in moderately tolerant filterfeeders, esp. Hydropsyche — Symphitopsyche. These organisms build cases on the upper surface of cobble — rubble substrates. Therefore, they are less affected by the clogging of the interstitial habitat with organic particulates. In fact, organic matter in the effluent may be an abundant food source for these few tolerant organisms. Taxa richness in this region was usually depressed by 40-55%, relative to the control station. This suggests severe stress. The population structure at this station does not suggest simple dissolved oxygen problems. Long—term (chronic toxicity) may also be a problem. The benthic community at this area was similar to that described by Winner at al (1980) for areas recovering from a toxic (heavy metal) stress. This may, in part, reflect the impact of Richland Creek water. Station 9 This station was located below Waterville dam and receives no effluent during low flow. During these periods flow from Waterville Lake completely bypasses this section of the river in a 1 mile tunnel used in the generation of hydroelectric power. This area was usually very similar to the control station. Station 10 Station 10 was located below the tunnel discharge from Waterville Lake. This area was usually in very poor condition. All taxa are very low,with Lumbriculidae dominant. An investigation conducted by the Tennessee Department of Public Health (1978) also indicated that the problem continues well into the state of Tennessee to a point at least 13.8 miles from the state line. The severity of the problem suggests that the states cooperate in assessing the effectiveness of management practices. A 82 possible source of the problem is Waterville Lake. Flow from Waterville Lake comes from the hypolimnion, an area of the Lake often anaerobic, potentially high in HZS and other toxic materials. This type of system may modify and reconcentrate Champion's effluent so as to increase potential toxicity. Temporal Patterns 1. Seasonal Natural seasonal changes in temperature and/or flow may tend to mitigate the effects of Champion's effluent. The four collections can be roughly separated into three flow—temperature classifications: A. Low flow/high temperature This is the normal late spring and summer conditions. It includes collections from October 1978 and August 1980. B. High flow/high temperature This situation includes one potential mitigating factor, i.e., the dilution effect of high flows. This conbination of flow and temperature was observed during June 1979 collections. C. High flow/low temperature This normal winter condition includes two potential mitigating factors. This combination of flow and temperature was observed during the May 1980 collections. Figure D4.1 illustrates the effect of Champion's effluent for these three flow and temperature categories. The benthic community has been classified into five categories: A. Good Community similar to control station and/or control data set. Many taxa present, including a high proportion of intolerant species. 83 B. Good-Fair Many intolerant taxa present, but total taxa richness below that expected from comparisons with controls. C. Fair Community dominated by moderately tolerant species although intolerant species still recorded. D. Poor Taxa richness very low, especially within the mayfly - stone- fly groups. Highly tolerant species present in substantial numbers. E. Very Poor Highly tolerant taxa dominant, sensitive species absent. The low flow - high temperature combination results in poor, or very poor, conditions for most of the Pigeon River within North Carolina. Only the bypassed segment below Waterville dam is unaffected. High flow - high temperature conditions improve conditions at most Pigeon River stations, but note that Station 9 (below Waterville dam) has been downgraded-from good to good-fair. Under high flow, water is released over Waterville dam and.the normally by-passed river segment can be affected. High flow-low temperatures results in further water quality improvement. Only station 10 remains in poor condition. The above flow-temperature combinations should not be thought of as single point measurements, but rather as flow and temperature regimes averaged over 1-2 months prior to sampling. Even during high flow/low temperature periods the benthic populations undoubtedly reflect stresses from earlier periods. 2. Comparison with 1965 data Champion upgraded its waste treatment facilities in 1973 adding a clarifier, improved their sludge dewatering process and improved biological treatment of suspended solids. An additional clarifier was also added in 1977. The effects of these changes can be .assessed by comparing DEM data with the data of Kemp & Stewart (1966) . They sampled in 84 July - August with high temperatures and low flow conditions. They found - the entire North Carolina section of the Pigeon River to be grossly polluted (Figure D4.1) . Mayflies, stoneflies and caddiflies were absent all the way to the N.C. - Tennessee border; five river miles were barren of life with the remainder dominated by tubificidae (sludgeworms) . Under similar flow and temperature conditions during 1978 - 1980, considerable improvement can be observed; although the river is still in "poor" condition the barren zone of life has improved and the zone dominated by sludgeworms is reduced to a region of 2-5 miles below the effluent. Tributary streams (Table D4.6) Four Pigeon River tributaries have been sampled. Palmer Creek, an unimpacted stream in the Pigeon River water- shed, was sampled once in May 1980 as part of a survey of mountain "control" areas. Three other streams (Richland Creek, Crabtree Creek and Fines Creek) were sampled during the August 1980 survey. Richland Creek was found to be in poor condition with the sensitive mayfly - stonefly group being extremely rare. A tolerant community of grazers (Hydroptilidae, Orthocladiinae) and filter-feeders (Hydropsychidae, Rheotanytarsus) was dominant. No organic "indicater" groups were present in high numbers, suggesting that toxicity from industrial effluents is of greater importance than sewage SOD. This stream enters the Pigeon River between Stations 6 and 8, adding to the pollution load at Stations 8 and 8A. Kemp and Stewart (1966) also indicated poor conditions in this stream. The other two streams were assessed as "clean" by Kemp & Stewart, but current data suggests some water quality problems. In addition to the data in this survey, these streams were sampled by Champion Paper Company (1981) and by the Division of Environmental Management as part of a recent (Un- published) qualitative survey. These areas were dominated by highly tolerant diptera and oligochaeta suggesting "fair" conditions. 85 5. BIOASSAY a. Introduction A series of on-site toxicological tests were performed on the Pigeon River in relation to Champion Paper Company's industrial discharge at Canton, North Carolina. The objectives of these tests were to evaluate the extent of acute toxicity which may occur as a result of the discharge. There are many forms of environmental impact for which an industry of this type may be responsible. The test series as designed here, were performed specifically to measure or eliminate the role of acute toxicity as one form of degradation. b. Methods and Materials Two types of techniques were employed to achieve the stated goals. These were: (1) static Daphnia pulex effluent bioassay and (2) in-stream bioassay using both rainbow trout and channel catfish. A static toxicity test using Daphnia pulex was performed on June 18-20 (48 hours) in order to measure the acute toxicity of the Champion Paper Company discharge. The effluent was obtained as a composite sample taken every 15 minutes for a six hour period. The bioassay included test con- centrations of 95, 90, 80 and 75% effluent . Dilution water was obtained from an upstream control station. This water was also used for control tests. Each test concentration was replicated with 15 test organisms per chamber. Average test conditions were: Temperature 210C, D.O. 7.6 ppm, pH 7.6. Caged rainbow trout were placed at various points along the Pigeon River and two tributaries to measure relative mortality. Replicates were established at each station with ten fish in each trout cage (20 fish per station) . The trout in these tests (21z inches) were subject to all existing environmental conditions including high temperature and low dissolved oxygen. In-stream tests were also conducted during low flow conditions in late 86 ,summer using channel catfish. Two stream stations (Richland and Crabtree Creeks) in addition to seven river 'stations were located. These stations are listed below: The control station is located off of Hwy. 215 on the Pigeon River, 300 yards below the confluence of the East and West Forks. The Pigeon River at this point is approximately 25 meters wide and 1 meter deep. There are no major point source dischargers above this station. Station CE is located on the Pigeon River off of Hwy. 215, 400 yards below the discharge point for Champion Paper Company in Canton. * Station #6 is located on the Pigeon River at 01d Thickety Road near Clyde, North Carolina. Station RC is located on Richland Creek at Hwy. 209 above the creek's banks are approximately 6 meters wide and the depth averages 2 meters. Station 7A is located on the Pigeon River at Hwy. 209, .8 miles from the junction of Hwy. 209 and I-40. Station CC is located on Crabtree Creek at Riverside Road, in Haywood County, N.C. This Creek is a tributary of the Pigeon River. Station BC is located on the Pigeon River at Riverside Road, .5 miles below Crabtree Creek's confluence with the River. * Station 8A is located on the Pigeon River at Fines Creek exit off of I-40 where the river and the Interstate cross. Station BD is located on the Pigeon River below the dam on Waterville Lake at Harmon Den exit (#7) off of I-40. * An asterix indicates the same sample station as in Tedder et al 1980. 87 c. Results and Discussion Daphia pulex Effluent Bioassay. Test results revealed 100% survival at all concentrations. This would indicate minimal acute toxicity can be associated with the effluent if this effluent sample is typical. Effluents of. the type dealt with in this study are difficult to quantify with respect to toxicological impact. Typically, an industry will discharge an acutely toxic waste which is diluted by the receiving waters. Through several toxicological methods, the toxic effects may be measured. When these effects are examined with respect to dilution ratios, a judgement may be made as to the chronic toxicity within the receiving waters. This method works well for an industry discharging acutely toxic waste at high dilution rations. The series of tests performed by the Division of Environ- mental Management indicates a different situation exists in the case of Champion Paper Company. The effluent is not significantly toxic (acutely) , but is discharged at such high volumes as to make chronic toxicity-(expvsure- for entire life cycles) a possible factor in the decrease in benthic community health found downstream from the waste discharge (Tedder at al 1980) . Other factors such as habitat distruction (through sedimentation) , or physical stress such as low dissolved oxygen and high temperature may be primarily responsible. In-stream bioassay. Three of the nine stations had partial mortality after 68 hours exposure using rainbow trout. These were stations BE (10% mortality) , 6 (30% mortality) and CC (10% mortality) . The highest mortalities correspond to the station with the lowest dissolved oxygen measurements (station6) , More in-stream tests during low flow conditions (September were also performed using channel catfish. These warm water 88 fish were more tolerant of the high temperature, low dissolved oxygen than the rainbow trout. No mortalities were recorded at any sites. The worst temperature/oxygen conditions were recorded at Station BE with a temperature of 290C and a dissolved oxygen value of 4.2 ppm. Upstream control values were 8.4 ppm oxygen and 190 water temperature. 89 a • ] o eP]sTTS GAPFigure D2. 1 Location of Pigeon a 'le e3 NBR wM.B'.5.895 3e, ` ` / River biological _ Sampling Stations A OAK AM CWTRK 5,e80 o G ti O R .]S'� { B 'J e` Iz99. 1 0 ]e 1 •���PIGEO GAP ` Z �MMls:r fb.e GmY i .It9i 3 spy 13e.� lu In. e� a zA J .9 NO xm MM N TOP 1]]e ti MY1 MM 4 1W ] � .r tW 1Lsz ' �Ne9PouNG GAP IL v .may / Lr •� {�. VGx Mrrl! \ ay s ru ro ].o .] IJgi 'ZJ'rGNG55v TOP rw .UtO .aLIM1P- 1 ]00 1 Z' ` ✓ r, 'ATOSN ANW � e � o rAs �O li A• er. i9 7 ws ti sr• '1 ii .1 i.,r �. 7.5iaC /'��� Pxu1P!iVM G.xrON rls ve a.] Ni 9WIIM.NCI ror.5.lse r / LoFe ror.l,]]9 Y swA]Nm AM r 111 'As ¢ ^ I OOUAIE TOP AM ST MM W1'R1691 � 1^ N V 4 ' ror a Pe110 C1 rs PLGE a r.• / i rOIX kNOB NV x ror. /rwa9 0604 TOP 4,930 wcN]OP ` P I S G A ] rs W ' edew,Grme 1 It \ Z J iewc9Y wAYNs 215 / d' NO.i (P Isar \ ] iy v ,Fl�iai N A T 1 O N A L ! c : , sPP_ NO ESGAx\. 5].9 �. FNoe /TONE resin .'[�Z G� 'n'>�' \ ,, i° a f le '�. • 6 TAC[! II]e t: . 3,W FATC FOR E S T �m HAV 7 V O®® COUNTY s 215 gn OS s / `" NORTH CAROLINA_ r 1 ; NO rW i 9� ._ .. M UNft POET EALO, Figure D4.1 Effect of Champion's Effluent Under Varying Flow & Temperature Patterns. 1978-1980 A. Low Flow, High Temperature (Oct.'78,Aug.'80) GOOD VERY POOR POOR GOOD VERY POOR B. High Flow, High Temperature(Jun:79) ` GOOD POOR FAIR GOOD-FAIR POOR C. High Flow, Low Temperature(May'80) GOOD FAIR GOOD VERY POOR 1965 A. Low Flow, High Temperature(Jul.'65-Aug.'65)(Keup and Stewart, 1966.) - GOOD VERY POOR ? VERY POOR Tunnel STATIONS 4 4A 6 7 8 I 8A r 1 uuuuunumw i u�uuuuuuuu ununuuuIII i Ill wffunffuuufi i uuuuu�unuuuuunuuuuuwAumuuuunuunuuuumumw� RIVER MILES: S 10 A 20 30 40 CHAMPION RICHLAND CR. WATERVILLE NC/TN LAKE k rr Table D2.1. Checklist of fish species collected in the Pigeon River, 1980. Common Name Scientific Name* Brown trout Salmo trutta Stoneroller Campostoma anomalum Goldfish Carassius auratus Carp Cyprinus carpio River chub Nocomis micropogon Golden shiner Notemigonus crysoleucas Warpaint shiner Notropis coccogenis Whitetail shiner Notropis galacturus Saffron shiner Notropis rubricroceus Mirror shiner Notropis spectrunculus White sucker Catostomus commersoni Northern hogsucker Hypentelium nigricans Black redhorse Moxostoma duquesnei Shorthead redhorse Moxostoma macrolepidotum Black bullhead Ictalurus melas Channel catfish Ictalurus punctatus Rock bass Ambloplites rupestris Redbreast sunfish Lepomis auritus Bluegill Lepomis macrochirus Smallmouth bass Micropterus dolomieui Tuckasegee darter Etheostoma blennioides gutselli Greenfin darter Etheostoma chlorobranchium Tangerine darter Percina aurantiaca Mottled sculpin Cottus bairdi * After American Fisheries Society, Special Publication Number 6, 1970. 92 Table D2.2. Distribution of fish species in the Pigeon River Station* Species 1 2** 3** 4** Brown trout X Stoneroller X X Goldfish X Carp X X River Chub X X Golden shiner X X Warpaing shiner X Whitetail shiner X X X X Saffron shiner X Mirror shiner X White sucker X X Northern hogsucker X X X X Black redhorse X Shorthead redhorse X X Black bullhead X Channel catfish X Rock bass x % X Redbreast sunfish X X X Bluegill X Smallmouth bass X X Tuckasegee darter X Greenfin darter X Tangerine darter X Mottled sculpin X See Figures 1 and 2 for station locations. ** Located below Champion Paper Company outfall. 93 Table D2.3. Standing crop (kg/ha)a and numbers of fish/ha in the Pigeon River. Stationc 1 2d 3d 4d Fish collected during sampling kg (number) Game fish 3.4 (57) 0.6 (24) 0 0.3 (54) Nongame fish 37.4 (1,910) 2.4 (34) 3.0 (91) 3.7 (34) Total 40.8 (1,967) 3.0 (58) 3.0 (91) 4.0 (88) Calculated standing crop kg/ha (Number/ha) Game fish 19.8 (331) 4.7 (205) 0 1.6 (325) Nongame fish 217.6 (11,105) 20.9 (291) 14.9 (455) 22.2 (205) Totalb 237.4 (11,436) 25.6 (496) 14.9 (455) 23.8 (530) aPounds/acre = kg/ha x 0.8924. bCalculated on the basis of kg of fish collected and the area of the sample. cSee Figure 1. dLocated below Champion Paper Company outfall. 94 Table D2.4 Water quality data of fish sample stations on the Pigeon River.* Station 1 2 3 4 130D (mg/1) 0.7 2.9 2.9 3.6 Fecal coliform (per 100 ml) 140 190** 1,700** 1,600** Total residue (mg/1) 40 1,120 972 924 Suspended residue (mg/1) 5 19 24 74 pH 7.0 7.5 7:4 7.7 Methyl orange alkalinity (mg/l) 8.0 90 77 77 Total hardnesg (mg/1) 4.0 310 250 220 Temperature ( C) 21.0 29.0 27.5 27.0 Dissolved oxygen (mg/1) 8.0 3.9 3.8 - Turbidity (FTU) 2.1 11.0 15.0 44.0 *Collected and analyzed by Division of Environmental Management. **Many non—fecals present. 95 Table D3.1. Fish Analyzed for Complex Organics and Heavey Metals. Pigeon River. August 1980 Size Class (cm) Taxa Analysis Pigeon River 1 201-225 3 Hogsucker Metals 201-225 3 Hogsucker Organics 2 @ 100-225 and 1 @ 125 3 Redbreast Metals 1 @ 75 3 Redbrease Organics Pigeon River 2 100-125 1 Redbreast Metals 125-150 1 Redbreast Organics Pigeon River 3 226-250 3 Hogsucker Metals 226-250 2 Hogsucker Organics Pigeon River 4 125-150 1 Redbreast Metals 125-150 1 Redbreast Organics Pigeon River (Tenn) 102 1 Hogsucker Metals - Organics 135-218 7 Redbreast Metals - Organics 96 Table D4.1 Pigeon River Discharge (CFS) at Canton, NC. From USGS Data. Discharge (CFS) Comment 12 Oct. 78 83 Base Flow 6 June 79 240 High 14 May 80 237 High 15 Aug. 80 76 Base Flow Table D4.2 Temperature Data (0C) , Pigeon River Stations. 4 4A 6 8 8A 9 10 12 Oct. 731 22 - 30 16 14 12 16 6 June 791 20 - 22 24 26 25 21 14 May 80 16 - 22 - 18 16 15 15 Aug 80 21 29 28 27 - - - Table D4.3 Dissolved Oxygen (mg/1), Pigeon River Stations. 12 Oct 781 8.3 - 3.3 7.7 8.3 9.5 9.6 6 June 791 9.3 - 7.0 7.2 5.4 5.6 5.4 14 May 80 7.0 - 6.0 - 9.8 9.2 9.1 15 Aug 802 8.0 3.9 3.8 - - - - 1from Tedder at. al (1980) 2from Wingate and Davies (1981) 97 Table D4.4 Taxa Richness Values, by group, for Pigeon River benthic collections. October '78 Group Station: 4 6 8 8A 9 10 Ephemeroptera 4 0 0 0 6 2 Plecoptera 1 1 1 0 1 2 Trichoptera 2 1 3 3 5 2 Coleoptera 4 0 0 1 3 1 Diptera 2 3 3 1 5 3 Other 6 11 4 3 6 9 TOTAL 19 16 11 8 26 19 June '79 Ephemeroptera 11 4 2 7 8 2 Plecoptera 4 2 0 2 3 1 Trichoptera 11 6 3 4 6 2 Coleoptera 4 2 1 0 1 1 Diptera 16 11 15 14 14 5 Other 5 5 3 3 4 3 TOTAL 51 30 24 30 36 14 1Oct. '78 and June '79 data from Tedder at al, 1980 May '80 Group Station: 4 6 8A 9 10 Ephemeroptera 17 11 11 14 2 Plecoptera 5 5 0 4 0 Trichoptera 11 5 4 10 3 Coleoptera 2 0 1 2 1 Diptera 20 20 20 23 5 Oligochaeta 4 4 3 3 3 Other 2 0 0 2 2 Total 61 43 39 58 16 August '80 4 4A 6 8 Ephemeroptera 14 0 0 1 Plecoptera 3 0 1 2 Trichoptera 11 4 4 8 Coleoptera 3 2 4 1 Diptera 12 3 7 12 Oligochaeta 0 5 1 3 Other 6 4 4 5 Total 49 19 22 33 #Fish species2 18 8 5 10 98 2from Wingate and Davies (1980) Table D4.5 Comparison of Station 4 with the Mountain River Control (MRC) Data Set. Group 4 MRC Ephemeroptera 14.0 14.8 Plecoptera 4.0 6.7 Trichoptera 11.0 9.1 Coleoptera 3.0 3.4 Diptera 16.0 19.2 Other 5.6 1.9 Total 53.6 55.1 99 I Table D4.6 Taxa richness values, by group, for Pigeon River Trib. Palmer Richland Crabtree Fines Creek Creek Creel: Creel: MSC* May 80 Aug 80 Aug 80 Aug. 80 Ephemeroptera 9.7 14 3 12 9 Plecoptera 6.5 11 0 4 1 Trichoptera 7.8 10 6 5 5 Coleoptera 2.5 1 0 1 2 Diptera 14.5 27 13 11 18 Other 2.6 1 6 4 4 Total 44.5 65 29 37 39 Keup & Stewart (1966) — 8 20 21 Champion Paper Company 26 37 35 (1981) 14SC = .fountain Stream Control 100 Table D4.7. Level I Data (Single Number Summaries) May 80 Stations 4 4A 6 8A 9 10 Avg. Density (N) 1294 - 272 248 379 59* Taxa Richness (S) 61 - 43* 39* 58 16* Biotic Index (BI) 2.3 - 3.0* 2.3 2.5 2.8 Diversity (H) 2.8 - 3.6 3.4 3.6 1.6* August 80 Richland Crabtree Fines 4 4A 6 8 Creek Creek Creek Avg. Density (N) 182 683 112 324 587 68 294 Taxa Richness (S) 49 19* 22* 33* 29* 37 39 Biotic Index (BI) 2.7 4.2* 3.9* 2.3 3.0* 2.5 2.6 Diversity (H) 3.0 1.5* 2.3* 3.0 1.9* 3.2 3.3 *Comparison with control indicates stress 101 REFERENCES American Fisheries Society. 1970. A list of common and scientific names of fishes from the United States and Canada. Am. Fish. Soc. , Spec. Publ. No. 6. 150 pp. Bayless, J. D., and W. B. Smith. 1962. Survey and classification of the Neuse River and tributaries, North Carolina. Div. Inland Fish., N.C. Wildl. Res. Comm., Raleigh, 94 pp. Champion Paper, 1981. Pigeon River benthic study, unpublished data. Fish, F. F. 1968. A catalog of inland fishing waters in North Carolina. Div. Inland Fish. , N.C. Wildl. Res. Comm., Raleigh. 94 pp. Keup, L. E. and R. K. Stewart, 1966. Effects of pollution on biota of the Pigeon River, North Carolina and Tennessee. Federal [dater Pollution Control Adm., 35 pp. Penrose, D. L., D. R. Lenat and K. [d. Eagleson. 1980. Biological evaluation of water quality in North Carolina streams and rivers, N. C. Division of Environmental Management, Technical Services, Biological Series #103. 181 pp. Tedder, S. W. , J. Sauber and L. Ausley. 1980. Pigeon River Investigation, N. C. Division of Environmental Management. Operations Section, 83 pp. Tennessee Department of Public Health, 1978 Biological Assessment and Inventory, Chemical and Bacteriological Sampling Pigeon River, Newport Cooke County. Wingate, P. J. and J. H. Davies. 1981. An evaluation of stream degradation in the Pigeon River. N. C. Wildlife Resources Commission, 10 pp. Winner, R. W. , M. W. Boesel and M. P. Farrell. 1980. Insect Community structure as an index of heavy metal pollution in lotic ecosystems. 102 DES/PCB'S AND OTHER C.HLORINATICD COMPOUNDS Athens,a CA PESTICI , L P.40.1ECT_Ncrth Carolina Dept nf CILEXIST E. W. Loy, Jr. -rEC'D. 10/16/80 CO*XPL'D. 3/23/81 Natural Resources 1430 Raleigh NC SAD NO. SIC0075 BLC0076 -810077 81C0078 Pigeon River Pigeon River Pigeon River Pigeon River SOURCE 6 STATION #1 51 -2 43 Hogsucker Redbreast Redbreast Hogsucker DATE/TIME COMPOUND Concentra- Concentra- Concentra- Concentra- tion mg/kg 11 7ng/kg Fti-'n mg/kg tion mg/kg 89. aldri, 34680 0.008U O.Olu 0.02U 0.03U 90. dieldrin ZI 39404 O.Olu 31. chlordane (tech. mixture 0.009C O.OIU 0.02U metabolites) 34682 0.2U 0.07U - 0.2U O. r-���92. 4,,4'-DDT (p, '-DOT)- 39302 0.01 0.01- O.03U. 23: -DDE ( DDE)=1 39J22 0.022=' 0.01 0.04U 4!�4;ZDDD ( 'o'-TDE) 39312 0. vau 0 , 1 3U 95. a-endosulfan 'Inha - 4365 0.0111 O.Olu U.UIU .0 0.02U 96- b-endosul:an-Seca 34360 0-0211 O.01U U.Uzu endasulfan sulfate 7T 34355 O.Olu O!D� 97. - ,,, 93. endrin Z, 34685 2 O.Olu 0.02U 0.03U 99a encrin aldehyde 41 34370 NA NA NA NA 100. heptachlor i_l 34687 0, U D-EM 2!1 2U !'3U101. heptachlor eooxide 34686 56N O.O 0625 O33U 102. a-BF.C-Alpha 41 j-UI4 0.008U 0.05U 7:: 34258 103. b-BHC-Beta 2/ 0.008U 00-0,),2 UU 0.03U 104. Y-3F.C::,IjiLdan721-G- V 39785 0.008U I O.OIU 0.02U I O.Olu 105. &-BHC_ el'a I O.Olu 0.02U 0.03U I O.Olu 106. PCB-1242 (ArOC107 1-24-2-)-T/ 34689 O.lu 107. PCB-1254 (Aroclor 125 0.2U 0.08U 3U I 0.3U 108. PCB-122. (....... ....):S, 14AA4 O.lu �-N- 0.4U 0.6U 110. PCB-124d U 0.3U 109. PCB-1232 (Aroclor 1232)4 34617 O.lU 0 udu 0.3U 5Z;Z� 0.3U �Arocicr 1Z48)zI O.lu 5.08U 0.3U 0.3U eLB-1400 kArocior IZbuW 34670- 0.2U U.ZU T.-4u 14 r" IU4 oclor 1016)LI 34674 O.IU Iff n2!13178,U 2-3U 34691 U.ZU 1 0 TU Prouaclor (Ramrod) NA TA- A NA --- - Prometon NA -NA NA NA 2 4-D 39734 NA NA "A iA- Silvex NA NA TA ----WA-- 2.4-5-T NA NA I NA NA 129. 2,3.7 ragh-8= - 0- - - -- _dijelt.- r�!)jgro iTbenz 34679 NA NA NA NA NA - Not Analyzed. J - Estimated value. K - Actual value is known to be less than value given. L - Actual value is known to tie greater than value given. U -.Material was analyzed for but not detected. The number is the Minimum Detection Limit. Tentative identification. On NROC List of Priority Pollutants. 103 rV �.• _ i'ESTICIUESi?CS'S, ,%D OTHER CHLOAIIIATL'D CC'QUUN0S Athens, CA '�:�^ ����-^`:' •�s.•"r"� PROJECT Notch Carolina Deot. of CIIEYISt E. G. Loy, Jr. 1:=C1D. 10/16/80 CU:L°L'D. 3/23/81 *K�_ - , Natural Resource. - - Ra ei h N - - _ . SAD NO. 81C0079 8100080 Pigeon River Pigeon River SOURCE 6 STATION 04 @ Tennessee - - ''� Redbreast Redbreast 6 - ;� Hagsuckers .. DATE/TIME COMPOUND Concentra- Concentra- Concentra- Concentra- -3 Lion mB/kB [ion mB/kB tion -A Lion 39. aldrin 2 34a n 0.02U I -- - . - - )0. dieldrin _ 394U4 0.02U 91. chlordane (tech. mixture 6 #�I metabolites) 2Z/ 3468- 4.2U 3� 92. 4 4'-DDT ( ,.'-DDT)_) 3933= O.OJU - - )3. 4,4'-DDE (a P'-DDE)_ 393'__ 0.03U 0.03U 94. 4,4'-pDD ( o'-TDE)_ 3z31< 0.02C 0_Q3U _1 35. a-endosulfan-Alpha _41 34365 0.02U 0.02U 6. 6-endosulfan-Beta 34360 0.03U 0.04U '- 17, endosulfan sulfate _ 34355 0.03D 0.O4U '- S. endrin - 3468i 0.04U 0.02U I 3. endrin aldehyde 4 34373 NA NA DO. heotachlor _ :. 67 0.02U 0.008U _ - - 41. hen tachlor epoxide _ 34686 0.02U O.OOBU - - ;a )2, a-BHC-Aloha -/ o.asu o.olU 03. b-BHC-Beta 2 341 0.02U 0.008U •' :04, Y-BHC-(lindane -Gamma _ 7 5 0.02U 0.008U .05. 6-BHC-Delta 2 4[v D.02U O.OlU --- 106. PCB-1242 (Aroclor 1242)_ 34689 0.2U I O.lU i07. PCB-1254 (Aroclor 1254)_ 46c0 0.3U 108, PCB-1221 (Aroclor 1221)_. 4 0.2U O.lu _ W9. PCB-1232 (Aroclor 1232)_ 34667 0.2U OJU (LO. PCB-1248 (Aroclor 1248)_ 34669 0.2U O.jU :11. PCB-1260 Aroclor 1260)_ 34670- 0.4U 0.3U -- -- 42 PCB-1016 (Aroclor 1016)_ 34674 0.2U O.lU 13. Toxa hene _ 34691 0,4U I 0.3U I Pranaclor Ramrod NA NA. Prometon NA NA 2 4-D 39734 NA !IP Silver NA NA 2 4 5-T NA NA 2 3 7 8-Tetrachlorodibenzo- dioxin TCDD - 34679 NA NA N 1 - Not Analyzed. d - Estimated value. TC - Actual value is known to be less than value given. _ L - Actual value is known to lie greater than value given. U -.Material was analyzed for but not detected. The number is the Minimum Detection Limit. Z1- Tentative identification. On NROC List of Priority Pollutants. 104 FISH - - DSPA R'_YVRTLNG JH c::I A.""NS, .Al PURCEABLE ORGANIC ANALYSIS 4/30 1 PROJECT Ril- CHEMIST E. W. L v. ir_ P,EC'D. 10-16-RO CC1'PI.ET'D• 1-17-91 North Carolina SAD :.'0. 81CO075 81CO076 81CO077 Pigeon River Pigeon River Pigeon River SOURCE S STATION - O1 O1 02 (Hogsucker) (Redbreast) (Redbreast) DAT'/TINE ... ... _ Connound mg' kg mg/kg mg/kg dichlorodifluoromethane 34335 E' 0.025L' methyl chloride2 34422 0,015110.0251: --- mz chyi-bromide_ 34417 0 2 0.025U vinvl chloride) 34693 0.025U 0.025U cbloroethaneV34315 0.025U U.D25U Lenz chloride2 34427 0.023•• 0.025C _ tr icS'_arofluara ethane- 34492 0.025U I 0.025U 1,1-dich to roe th-:1ene_ 34505 0.025U 0.025E 1,1-dichloroechane_ 500 0.025U 0.023U 1 2-mans-dichloroeth lene_ 4555 0.025U Not Analyzed 0.025L' _ chloroform _ 3431 0.025U Insufficient 1 0.220 1 2-dichloroethane= 45 55 0.025U Sample 0.023U 1,1 1-cri chloroe 7 010 0.025U 0.0251., carbon tecrachloridj7 34300 0.025U 0.025U dichlorobromomet:iane_ 1 0.025U 0.025U 1,2-dichlorovrooareit J4343 0.025U 1 0.025U ._.. - ...... 1 3-d ichlor0oroo lene 0.025U 0.025U trichlaroechvlene_ 00251T 0.025C benzene_ 0.025LI 0.025U chlarodibromomethane_ i 0.025U 1 0.025U 1 1 2-trichloroethane_ 34515 0.023U 0.0251: '-chloroechvl vinvl ether (nixed)_ NA b:oaoform_ 34291 0.025U 0.025L' 1 1 2,22 tetraehloraethane_ 34520 0.025U 0.025L' rrachloroe thyl'ne_ 34479 0.025U 0.025U toluene_ 34484 0.025U 0.025U dhlorobenzere_ - 34305 I 0.025❑ 0.025U et vlbenzene 34375 0.025U 0.025C_ acrolein_ 34214 0.5000 0.5000 acrvlonitrile-/ 34219 0.5000 0.5000 -" propanal jJ 1.9001 0.570J butanal 1/ 1.000J O.lOOJ pentane l/ 0.3001 O.IOOJ _ pencana l/ 0.400J 0.300J exana 1 2.200J 2.600J total unknow alkyl hydrocarbons 0.200J 0.025K =35arF?�X.a�4ari[KF?rcQ'.�icrl�i�„� J - Estimated value. K - Actual value is known to be less than value given. L - Actual value is known to be greater than value given. 'j U - Material as analyzed for but not detected. The number is the Minimum Detection Limit. •- NA - Not analyzed. Tentative identification. �/- On NRDC List of Priority Pollutants. n. . .... .. 105 FISH DATA .',dt0i:C7:C ..dzEr .\[kd:,9,•uA 2 PURCEABLE ORC NEC ANALYSIL G/80 - PROJECT Pigeon River CHEMIST E. v. Loy, Jr. -,F.C'D.10-16-80 CO:!?1.ET'D•3-30-5 or aro ina SAD N0. I 81C 0078 81C 0079 81C 0060 Pigeon River @3 Pigeon River 84 Pigeon River a SOURCE S STATION - (Hog Suckers) (Red Breast). Tennessee (Red Breast 6 Hog y Suckers) DATE/TIME Comoound mg/ky mg/kg mg/kg + ' dichlorodif luoromethane-2/ 34335 .025U 1 025U methvl chloride2 74422 - .025U ,025U methvfbromide= 34411 vT .025U vinvlvinvl c�� 34693 1 0191, .025U .025U y. ch.loroech.ue2 34315 .025U UZtu I .025U meth^lene chloride 3442; aZ -r .023:: _ ,3 crieS'_ororluoroczchane= 344Y2 I _DL 2 .025L sj 1,1-diehloroe chelene= 45U5 �G .025U1 1-dichloroechane_ 345UU G _ -015C .025C 1 2-craps-dichlo roe th lens_/ 34550 ,025L' .025L' 'R chloro Eor:n _ j4jiv .080 OZ5U .025❑ 1 2-dichloroechane_ 34535 .025L 02 .025U 1,1,1-trichloroethane Al1 .025C .0291, .025L• ' carbon tetrachloride= .025U .02 : .025L' dichlorobromomechane= .025I' 02 .0251: a� 1 2-dichloroorooanen .025U .025U .025U 1 3-dichloro°ro vl a .025U .025U .025U trichloroethvlene_ ° .025U .025U .025L' & benzene_f .025U .025U .025U (k. Shlorodibromomethane_ n .025D .025U .025U 1 1 2-trichloreathane_ 34515 .025L' I .025L• .025U -W N 2-chloroethvl vinvl ether (mixed)- - A NA NA Y\ bromofor� 34291 .025U .025U .025C + 1 1 2 2-tetrachl°roethane_ 34520 .025U 1 .025 C' .025U - - - --- • - recrachloroeth lcne_ 34479 .025L' .025U .025U toluene_ 34484 .025C .025U .025L' 4 chlorobenzene_ 34305 .025U ,025L' .025L eth lbenzene_ 34375 .0251: .025L .025L acroiein_ 34214 .5000 .50OL• ac lonitrile_ 34219 .5000 .50OU .5000 ro anal 1 .900J .700J .500J butanal 1 .1001 .200J .100J pentane .20OU .100J .100J s entanal 1 .3001 .200J .2 J hezanal _/ 2.7001 1• J I 1.400J 'z total unidentified alkyl hydrocarbons .100J 2 K .025K Aft a J - Estimated value_ ' K - Actual value is, known to be less than value given. yy L - Actual value is known to be greater than value given. U - Material was analyzed for but not detected. The number is the Minimum Detection Limit. NA - Not analyzed. Tentative identification. �/- On NKDC List of Priority Pollutants. .'1o6 FISH - L DATA FEPOR"li::c SHEET idA• SAD, 'r.GN. iC EXTRACTABLE ORGANIC ANALYSIS Athens, CA 4/60 PROJECT a r no., of Natural Resources CHEMIST E. V. Loy, Jr. REC'D. 10-16-8t'MPL'D. 2-26-81 Raleigh, N.C. SAD NO. 81C 0075 Pigeon River #1 SOURCE 6 STATION (Hogsucker) DATE/TIME Compounds on NRDC List of Priority Concentration Concentration Concentration _>-;rwr-,n:�._,.�.,..;.::-.:.=.,.�.:.•.:« Pollutants k m /k mg/kg 17. bis chlorometh 11 ether lU . 61. N-nicrosodimethv Laraine 34442 1U 1 2-dichlorobenzene 34540 lU 26. 1 3-dichlorobenzene 34570 lU 27. 1 4-dichlorobenzene 34575 lU It. bis(2-chloroethvl) ether 34277 lU 12 hhexachloroethane 34400 lU 42. bis(2-chlorofso roovl) ether 34287 lU - 63. N-nitrosodi-n-pro2ylamine 34417 2U 56, nitrobenzene 3445E lU 52. hexachlorobutadiene 34395 lU C. 1.2 4-trichlarobenzene 34555 1 lU z5. naohthalene 34446 1 1K' 43. bis(2-chloroethoxv) methane 34282 lU 54. isonhorone 34412 2U 53. hexachloroc clo entadiene 0 lU 20. 2-chlprona hthalene 34585 lU 77. acena hth lene lU I. aeenaohthene 34209 1 111 ' 71. dimethvl phth.late 34345 lU 35. 2 4-dinitrotoluene 14615lU --- 36. 2 6-dinitrotoluene 34630 lU 40. 4-chloro hen 1 henyl ether 34645lU 80. fluprene 34385 113 . .. --• - . . . 70. diethyl phthalate 34340 111 2-diphen lh drazine _ 34350 LU oz. N-nitrosodiohenvlanineli 34437 lU 9- hexachlorobenzene 34688 LU 41. '4-bromo henvl ohenvl ether 34640 lU . 81. ' 34465 78. anthracene_/ 34224lU - -' 68. di-n-but 1 hthalate 34683 lU _ 39. fluoranthene 34380 lU _ 84. pyrene 34473 lU •- _ 67. but 1 benz 1 Phthalate 34473 lU . - 5. ' benzidine 34241 2U 66. bis(2-ethvlhez 1) ohthalate 39099 lU It. chr sene _DI 34374 72. 1 2-benzanthracene _ 34530 lU -- 3'-dichlorobenzidine 34635 lU 69. di-n-oct 1 Dhthalate b lU 14. 3 4-benzofluoranthene _ 75. 11 12-benzofluoranthene_ 4246 lU - -.z�•+ :; �4y.�; -benzopyrene 34251 83. indeno (1.2.3-cd) pyrene 34407 1U dz- 1 2 5 6-dibenzanthracene 34560 lU • 79. 1 12-benzo er lene 34525 lU 24. 2-chloro henol 34590 811 57. tro henol 34575 BU 65a. Phenol (CC/MS) 4468 8U 34. 2 4-dimeth 1 henol 34610 8U 31. 2 4-dichloro henol 34605 BU 21. 2 4 6-trichlorp henol 34625 8U 22. paracnlprampra cresol 34456 8U 59. 2 4-dinitzo henol 34 b20 64U 60. 4 6-dinitro-o-cresol 34661 8U 64. entachioro henol 39U65 8U 58. 4-nitro phenol 3465U I 16U A - Not analyzed.J - Estimated value. 6/- Ch rys ene and/or 1,2-benznn[brace -- 3,4-benzofluoranthene and/or O- Actual value is known to be less than value given. 11,12-benzofluoranthene. Actual ue is kno� to r Chan value given. Claterialawas analyzed for 6but rnot edetected. The number is the Minimum Detection Llmit. ^-•�- - //- Tentative identification. and/mr azoben=ene. - (OttF.R1 107 FISH - 2 �'AO'FCT N.C. Dept. of Natural Resources CURNLST E. W. Loy, Jr. R7C'D.10-16-8000:!P!.'!).2-26 •:•:_--q:.:ae_t.::<:.�.nw:�:.�.>7fc:?-._;:vis .. - Raleigh, N.C. SAD NO. 81C 0076 ----- Pigeon River 01 - .-SOURCE L STATION (Redbreast) DATF/TL:LE Compounds on NRDC Lisa of Pri.•ricy Concentration Concentration Concentrati, Pollutants m;,ik r.,e/k mg/kg -„�.c,.U,..v..:i::- ?%++w^v.,:,••c-,:-:..'ni 17. bis(chloromeah l) echer 14171 lU 61. N-ni[rosodimethvlamine 34442 111. 25. 1 2-dichlorobenzene 34540 1U - 26. 1 3-dichlorobenzene 34570 1U - 27. 1,4-dichlorobenzene 34575 lU 18. bis(2-chloroerhvi) ether 34277 it: 12. hexachloroechane. 34400 lU 42. bis(2-chloroisooro;rvl) ether 34287 lU 6J. N-nitrosodi-n-nrooylamire 344't+ U 56. nicrobem.cne 34451. lU 52. hexachlorobutadiece 34395 lU 8. 1,2 4-trichlorobenzene 14555 lU 55. naoh:halene 34445 1}: 63. bis(2-chloroathoxv) methane 3/.132 lu 54. ' fso➢_-,one 34.',I 3U 53. hexaa lorec:ciooentadice 'j43^U i lU 20, 2-ch Lurona l:thalene 14585 lU 77. acenaphchvlene r, 111 1_ acenaohthene V209 III ' 71. dimethvl h[],a late 34345 1L' I 35. 2 4-dinitrotoluene t;15 'lU -_ 36. 2 6-dinitrotoluene 34630 lU A. s"�=t�"r "�""a•'- ?t"++-a TO. 4-chloro ben. 1 henvl ec::er 464 lU - 80. fluorene 4185 lU _ 70. diethyl hthnlate 34340 lU _ -"'0 37. 1 2-di hen lhvdrazine _ 34350 lU 62. N-nitrosodinhenylamine_ 34437 lU --9. hexachlorobenzene 34688 III ' 41. •4-bromo henvi phenvI ether "' 34640 ID 81, , 34465 ' -' 78. anthracene_/ 34224 - 68. di-n-but 1 phthalatc 34683 1 lU ' 39. fluoranthene 34380 lU -_ 84,_ Dvrene _ - 67. butyl benz 1 ph,.halate 3429(. 1L' _ S_" benzidine 34241 3U - • 66. bis(2_ethvlhe':vl) phthalace 390" 'lU . .:. . . .. 76, chr ;:one D . . '343'24 . . 12. 1 2-benzanchraccne' .21 34530 lU - 26. 3 3'-dichlorobenzidine 34 3`, lu - - 69, di-n-octvl phthalate 34UCIGlti" . 74_ 3 4-benzo Eluoran there _ . . . .. . .. 75. 11 12-benzofluoran ticenq_ 4246 73. 3 4-benzo2yrenc 34251 lU 83- indeno (1 2 3-cd) ovrene 34407 ' ' ' lU 82, 1 2 5,6-dibenzanthrncene 34560 lU ' _ 19- 1,12-benzonerylene 34525 LU ' 2-c110ro henol 34590 8U 57. 7-nitrophenol 34595 811 65a, '.cool (CC/I1S) 34468 AU - _:_ •. - 34. 2,4-dimet5rylphen,I 34610 EL' - _ 31. 2,4-dir, oro henoL 34 G0: gU - - 21, 2,4,E-tri cl,lwrophenol _ 34625 BU • 22, parachlorom,-cn cresol 3445E SU 5967 /� ,_dinitronhnapl 34620 ; 64U 60. 4,6-dini[ro-o-cresol 3466J. g0 64, pentachlaro henol 3906U BU • 58. 4-nitroph,nol 34G50 16U A - Not analyzed. 5/- Chrysene and/or 1,2-benzanchrar I - Estimated value. 6/ 3,4-benzoflunran chcne and/or .. - • _ - E - Actual value is known to be less than value given. 11,12-benzof luoranthene. . - L - Actual value is known to be greater than value given. •'. � •-` Yam, " ' ' Y� Material was -,analyzed for but not detected. The number is the Minimun. Detection Limic. Tentative identification. ` - and/-r azobenzen=.. �•:air`�,?ie�iR:.`.,�'.ucan...ra.,a�.,�:,a.a_[w J/ � .. - � ._ (OVER) 108 . ..: . ,. - FISH , pgO„EO-,N.C. Dept. Of Natural Resources CUGiI(ST E. W. Loy, Jr. REC'D. 30-16-80J`:Pt.'02-26-81' - Raleigh, N.C. SAD S0. 81C 0077 Pigeon River 02 SOURCE 4 STATION (Redbreast) DATE/TINE Compounds on NRDC List of Priority. Concentration Concentration Concentration Pollutants kc me/kg mg/kg ,,, ,w:;c�F ru.{•n .-r'.,.•-�x•_bw .;-m+-x 17. bis chlorame.th•1 ocher14272 lU 61. N-hitrosodineth lamina 34442 lU . 25. 1 2-diehlorobenzcne 34540 lU '- - 26. 1,3-dichlorobenzene 34570 lU 27. 1 4-dichlorobnnzene 34575 1U l8- bis(2-chloroeth 1) ether 34277 lU 12. hexachlora,thane 34400 lU 42. bis(2-chloroisonronvl) ether 34287 lU 63. N-nitrosodi-n-proo lamine 34,431 2U - ., 56. nittobenzena 3445L lU 52. hexachlorobutadicne 34395 lU 2,L-rticlllnrohenzene 34555 lU 55. naoht`:_lene 34446 lK 43. bis(2-chloroethaxv) methane 34281 lU 54. isonhorone 34412 211 - 53. hexachlorocvclooentadiene 3,190 1 111 20. 2-chlorona lithalene 34585 1 lU . - 77. arenaohthylene ar. n4 lU 1. acenaohthene 34209 lU 71. dimethvl phthalate ' 34345 lU 35. 2 4-dinitrotoluene 14615 lU 36. 2 6-din.tzotoluene 34630 lU ' 1''•t ' ,.�_.-,,, "'3.. 40. 4-chloro hen 1 Phenvl ether 14645U - - 80. fluorene 34385 1U 70. diethyl phthalate '34340 lU .- " ' • " ' 37. 1,2-di hen lh:2razine _ 34350 lU -- 62. N-ni.trosodiohenYlanine_ 34437 1U -" 9. 'hexaehlorobeazene 34688 lU 41. •4-brom2 hen tphenyl ether 34640 1U 81. 34465 - 16. an[hracen.4 34224 '1K - -' 68. di-n-but 1 phthalate 34683 lU ' - 39. fluoranthene 34380 1L' ' . . - 64:. nvrcna 3 473 lU ' 67, but ). benz 1 hthalate 34296 lU - 5..• benzidine 34241 211 66. bis(2-eth lhez l) Dhthalace" "390914 ' 1U. 76. chrYsepe _ 324 ' _ 72. '1 2-benzanthracene _ 34530 lU - -T ^'•' 28. 3,3'-dichlorobenzidine 34635 lU .^ 69. di=n-oct 1 hthalntc 6U 'lU 74. 3,4-benzofluoranthene 75. 11 12-benzofluoranthene 4246 ID 73. 3 4-bcnzo yren;, ' 34251 ` lU . '.•. . . ' . `� -"^' �• '�' 83. indeno (1,2,3-cd) nvrene ' ' 341,07 ' ' lU - 82. 1,2,5,6-dibenzanthrac,:ne 34560 lU 79. 1.12-benzonerylc 5 ol ne _ 3� 25 ` lU 24. 2-chlorophen 34590 i 6U 57. 2-ni[zpnbanol 34595 U 65a. phenol (GC/l15) 34468 6U 34. 2,4-dimerhylni•..... l 34610 6U " 31- 2 4-dichlorn hen01 34605 1 6U _ _ 21. 2,4,6-trichloropheno). ' 34625 6U ' 22. arachloromen cresol. 3445,0 6U . . 59. 2 4_dinitrophennl 54620 48U W. 4,6-rlinitro-o-cresol 341,61. bu +.- G' nr•n•nth loronlmnol 39U60 ou 58. 4-mrrnninnol 3465U 12U A - O:o❑ analyzed. 5/- Chrysene and/or 1,2-benzanthrac J - Estimated value., �/- 3,4-benzofluoranthene and/or K - Actual value is known to be less Lhan value givua• 11,12-benzofluoranthene. L - Actual value is known to he greater than value given. U - Material was analyzed for but not detected. The number is the Iunimun Decoction Limit. Tentative identifieatic.'. lO9 x _` 1 j,-.and/or azobenzene- .. - ._ (OVER) - FISH - + I`R03f.CT N.C. Dept. of Na[ureal Resources CGFMIST E. V. Loy, Jr. .. C'0. 10-16-8dr)i!P1.'U 2-26- Raleigh, N.C. - SAD W. B1C 0078 Pigeon River 6*3 _SOURCE L STATION (Hogsuckers) DATE/Ti:IE _ Coa0onndr on NRCC Lis[ of Priority Ummen czacion Cuuc cacra tion Curecnccat i; Pollucdnts .l: nc/kr. m-/kg 17. bis(chlororerh •1) ether •+. + lU -- 61. N-nitrosodir..cthvlamine 34_:,2 25. 1,2-dichlorobanzune 34.a:n LU 26. 1.J-dichlorobenzene 3457U lU _ 27. 1,4-dish locobenzeoe 34575 lU Id. bis(2-chloroethvl) ether 34277 lL 12 he::achioroe thane 34400 l0 42. b__(2-chloroisopro2vl) ether 34287 lU 63- F-ni trosodi-n-nronvlanine 14:.49 2U _ 56. -nitrobenzene 34451_ lU 52. hexachiarobutadiene 347'IS lU 8. 1 2 4-trichlarobenzene 34555 1L' 55. -aohchalene 3444F l7: 4J, his(2-chloroechoxv) methane 34n82 LU 54. isonhorone 34412_ 2U 53• hexachloroe clooeccadir_ne 14 O lU 20. 2-chloronaohthalene 34585 lU 77. acenaohthvlene a4 4 10 1. acenaohthene 34?09 iG 71. dinethv_ l lchalate 31.345 lU 35. 2.4-dinitrocoluera vats i IU _ 36, 2 6-dinitrorclu^•• - 3G630 LU 40. 4-ehloroohenyl uh_avl ether;4f.G4 lU 80. Fluorene 3,18+ 1 lU 70. diothyl phthalace 343411 i lU 62.N-nitresodinhec;iamine 34437 I lU ' 9• h•-xaachlorohor-ene 34688 lU _ 41. -4-bromo h2 en•:1 nhenv' echec 346C0 lu 81n>,�,-1,•. �// 34465 Id. anchraccne4/ 14224 lU - -' 6B. di-n-butyl plith3lace, 34683 lu 39. fluoranthene 34390 lU 84:nvrcne10 =- 67, butyl benr. 1 htha la to 34-L96 lU �' ' 5." benzidine 34241 2U 66, bis(2-ethylhexel) phthalate J9U99 lU ' _ .. 76. chrv::-na _It 3+32.4 2-banzaithracene _ 34530 lU - _ 26. 3,3'-dichloroberzidine 34635 lu ' 69- di-n-octyl phthal:,ce b U lu 74. 3,4-b::nzofluoranthene _ 41 + 75_ 11 12-benzofluoranthene.). 246 lU _ 73. 3 4-henzon rene ' 3425 lU " "0p"w°°'"Y�'• ''a•'t'i 83. indeno (1 7. 3-cd I rene "34407 ' lU 82_ 1 2 5 enzo_, nzap ch rnccne 34560 lU I ' 79__1.12-bnzoer lea: 34535 1 it, - - - 24 2-chloionbcnol __ 34590 oU -� --- Die 2-n itro�nhe.not 34595 6L 65a_ r!mnol. _ 34610T. 2.4-dimerhvlph�nnl 3461U 6L 31. 2:%.-dirh]u•'o_.hcrnl 3460',21, 2,6,6-trichinronhnnol _ 34625 6U 22.__pl rarh to romp ca cu'esol 341,56 6L 59. 7,4-n initrayL•rnol _ 34620 48U 60. 4,6-diniCrn_: crrrnl 3466I 6U T G4, �1 6 nentnrhlomY and 3YU: U i 58, 4-nd tranhunnl ---- 3a,• d_� 12 L'�- -]-- ��: A - rot anal•zed. 5/ �;V Y G/- Chrysene and/or 1,2-hcnzanchr,: 3 - Estimated value. - 3r�-hen ruflwr.tn Chcnu andJuz jt K - Actual value is known to be less than value ivan. :•- g 11,12-bcntofl4e[.anth_!:e. :a L - Actual value is known to be grencer than value given. :Lacerial an auly ed for but not deeececd. 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Dept. of Natural Resources CHEMIST E. W. Loy, Jr. ?..C,D.10-16-8OCrgo+ •D2_26- _-_ - . . Raleigh, N.C. SAD NO. 81C 0080 Pigeon River at _SOURCE 5 STATION Tenn. (Red breast S Hogsuckers) DATEM:1' _ Compounds on NROC List of Priority Concentration Concentration Com:entracic Pollutants kz mg/kg mg/kg •••Y�r. 2•:^^;.-�_= -C;, 17. bis(chlornme[hvl) ocher + lU 61. N-nitrosod 44 imethv la mine 342 lU . 25. 1 2-dichlprnbencpne 34540 lU - 26" 1,3-dichlorobenzulie 34570 lU 27. 1,4-dichlorobenzene 34575 lU 18. bis(2-chloroechvl) ether 34277 1L' 12. hexachloroechn,e 344UO lU 42. bis(2-chlorois02r02vl) ather 342..87 lU 63. N-nitrosodi-n-proovlamin- 344;? 2U ' 56" nitrobencene 3445L lU 1 52. hexachlorobuczdicne 34395 lU - 8. 1 2 4-[rich Lorobenzene 34555 lU • 55. naohchalz e 34446 lU 1 43. bis(2-chloroathoxv) me than•- _ 34281 lU 54. ' isrn,:+arane 34412 I 53. hexachlorocvclopencadiene 3 1,:0 1G 20. 2-chloronanhthalene 34555 77. acenaoSchvlene 7tn n4 lU 1. acenaahchene 342,19 ill 71. dimethvl phthalate 343A5 1U I 35. 2,4-dinitroto Luene 1AA1S lU _ _ - 36. 2,6-dinitrotoluens 34630 1U I '"'--a`""`""'^"2J"^^""`^+-'=`-"•'=^'R' ';+ U. 4-chloroahen 1 phenyl ether - 4 45 1 lU 80. fluorene 343R5 IU 70. diethyl phthalate 34340 lU __- -- - 37. 1 2-di henvlh drazire _ 34350 1 lU 62_N-nitrosodinhen-lamire_ 34437 lU ' 9. hesachlorobenzene - 3468'3 lU 41. 4-bromo henv.L henvl ether 34640 lU 81- _ 34465 ' 78. anthracene_ 34221, 68" :-n-but-1 hthalate 34683 lU - 39. fluotan[hone 34380 lU 84,_ vrent a34 lU 67. butvl benzvi phthalate 2:15. ' benzidine 2U . bis(2-eth lhexvl) hthalate76. chrynene _ - 72_ 1,2-benzanthracene _ 3453U - -. 28. 3,3'-dichlorohenzidine 311635 lU 69. di-,+-pctvl ph[halar.e ' 3,bU • TO - 74. 3,4=benzofluoranthene _ t• 75- 11 12-benzofluorantl+e.,-: 4246 lU 73. 3,4-benzopvrene '34251 lU °''l•' �k"�` N'-�'"�=' ' -5°v� 83. ind:-no (1,2 3-cd) rcne " 34407 lU ' 82. 1 2 5 6-d:benzanthrncene 34560 lU 79. 1.12-benzonert•lene 34525 1.0 -' 24" 2-chloronhenol_ 34590 SU '- 57. 2-ni.trophenol - 34595 DU 65a. r nnol (CC/:1S) 34468 - SO ' 34: 2'.4-dinc[h1�+henpl %510 SU • 31. 2,4-6irhlor.,-,henol 34605 5U - 21. 2,4.6-tri.chlororhenol 34625 5U_ - 22. ratnchiorometa ca:sol 34456 SU 59. 2,4-di:•:[ro hen,___ 3462U _ 400 G0. 4•G-din itro-o-cr,•_snl 34G61 5U G4. :an carh to rop1, l 39u u SU -- 58_4-nitr,::,henol 3465U IOU A - Not analyzed. 5/- Chrysenc and/or 1,2-1,enzan•hrac - J - Estimated value. L,+/- 3.1.-benzoElunrmt[hm:a an:1/or . - K - Actual value is known to be less Lhan value given. 11,12-benzoEluoran thane. L - Actual value is known to be greater than value given. - Material was analyzed for bnt not daccctcd. The number is Lhe Minimum Detection Lie:t. :ue�+�",.•t '_ F'" s>_�;, iR � Y;� �-.Tentative identification. - llz •-,,;�. . - and/or azobenzane.....y�!%:•'W'+a+.asti k' �:F°'.': 5.-f :: ,4"� 3/ .. (OVER) - DATA REPORTING SHEET FISH EFA-LS3-S,iD-_ 63 RO]EC_ NC Dept. Nat'l Resources C;rMi52 3. McDaniel REC D 10-16-80 CnSPL`D 4-30-81 Raleigh NC 'f.0]ECf NUMBER 81-13 )AD NO. SIC 0075 1 81C 0076 81C 0077 BIC 0078 ;OURCE S STATION Pigeon River JL Pigeon River U1 Pigeon River 1=2 Pigeon River d= (Hogsucker) (Redbreast) (Redbreast) (Hogsucker) )ATEIME: :LE:_.::T (,. +/k ) ;iiver* 34474 1K IK 1K 1K lrsenic* 01004 2K 3K 39 2K loron 81657 Sari= 81638 4 5 2 2 3ervlliu* 34252 1K IK 1K I 1K Cadmi=* 71940 1 1K IK 1K Cobalt 81659 IK 1K 1K 1K Chromium* 71939 C000er* 71937 0.8 1K 1 _ :401 bdenu•a 81662 1K IK IK IK • Nickel* 01069 IK 2K 2K IK Lead* 71936 1K 2K 3K IK Antinonv* 01099 IK 1K 2K I 1K Selenium* 01149 1K 2K 3K IK Tin 81663 4 6K 6K Strontiva 81930 13 35 11 7 - Tellurium 1K 2K 2K 1K Titanium 81664 }• Thallium* 01073 4K 6R 6K 4K tj :� .�" Vanadium 81665 IK 1K IK IK 1 sJ1R'6i'lY.i.nl:��:S'::Y�:e-t!::i�.✓"J.�( 1K Yttrium 1K 1K IK 74 >, Zinc* 71938 19 23 37 21 a . 3 Zirconium Mercury* 71930 0.09 0.09 0.02K 0.04 Calciu_-) 81655 3490 10950 11450 6950 Magnesium 81656 335 450 480 400 t - CO:iTINUED ON BACK - � K - Actual value is known to be less than value given. Nt L - Actual value is known to be greater than value given. * - Priority Pollutant. 9 �y .. • 113 CONTINCATIUN EPA-SAD-LSB- 13U DATA RLPORTING .ZKEET FISH 10JECT YC Deo[. Nat'l Resources CHEMIST B. YcDanr.el REC'D 10-16-80 CO:'.YL'J 4-30-81 Raleigh NC RO.IECI NUMBER 81-13 AD "0. 81C 0075 81C 0076 81C 007 B1C OOi OURCE S STATION Pigeon River 41 Pigeon River J1 Pigeon River Pigeon Riv¢ (Hogsucker) (Redbreast) (Redbreast) (Hogsucker) ATE/TI:_ .LE:L'.NT (ro kg) . 1uminu 816a6 72 :10 ^"' 34 ron 81660 92 1:0 70 54 Ian anese 81741 7 35EO 3110 7 iedi= 938 1030 1500 1050 : anide-(Net Weight)34326 'ercent Moisture (Z)70320 lsbestos * 34229 NA NA NA NA ANALYSES ON HET WEIGHT. N - Actual value is known to be less than value given. L - Actual value is known to be greater than value given. • - Priority Pollutant. 114 DATA REPORTING SHEET FISH EPA-LSe-SAD-4/80 RO3EC: NC Dept. of Nat'l Resources CHE�IIST B. McDaniel FI:C'D 10-16-80 CO+1Rr •0 4-30-81 R,1„+g,b� YC ROJECI RUaBLF. 81-13 -AD NO. SIC 0079 81C 0080 :OUP.CE 6 STATION Pigeon River #4 Pigeon River at (Redbreast) Tennessee; (Redbreast and Hogsucker). )ATE/TIME MEMEN'T (m /k ) :ilver* 34474 1K 1K lrsenic* 01004 1K 3K Boron 81657 larium 81658 1 3 lervlliva* 34252 1K 1K :admiva* 71940 1K 1K -obalt 81659 1K lK :hromiu 71939 :000er* 71937 0.7 1 iol bdenum 81662 1K 1K • lickel% 01069 1K 2K Lead* 71936 1K 3K Antimony* 01099 1K 2K Selenium* 01149 1K 3K Tin 81663 2K Strontium 81950 3 19 Telluri= 1K 2K Titanium 81664 Thallium* 01073 2K 6K Vanadium 81665 1K 1K Yttrium IK 1K Zinc* 71938 13 27 Zirconium Mercury* 71930 0.03 0.06 Calcium 81655 5780 26150 Ha nesium 81656 360 770 - CONTINUED ON BACK - K - Actual value is known to be less than value given. L - Actual value is known to be greater than value given. * - Priority Pollutant. 115 CONTINUATION - E?:.-SAD-LSS--. . DAIA i,cPJRi I::G SHEET FISH ;LJJEC NC Dept. of Nat'l Resources CHE`IISI B. McDaniel REC'D 10-16-80 COY?L'D 4-30-81 Raleigh, NC ROJECI NUMBER 81-13 AD C:O. 81C 0079 81C 0090 Pigeon River W4 Pigeon River at OURCE L STATION (Redbreast) Tennessee; (Redbreast and Hogsucker). 1AT-c/i4tE :LE:LlIT .luuin= 3.666 J0 20 :ron b1650 I 30 30 tan anese 81741 9 17 :odi= 1210 1730 snide--(Net Weight)3-326 'ercent Moisture (2)70320 lsbestos 34229 NA NA NA NA ANALYSIS ON NET WEIGHT. K - Actual value is kno�m to be less than value given. L - ActuaL value is known to be greater than value given. • - Priority Pollutant. 116 6/23/81 PREPARATION PROCEDURE FOR THE ANALYSIS OF FISH FOR METALS [Thole fish are ground using a large commercial meat grinder and freezing. A five-gm subsample is weighed into a 125-ml erlynmeyer flask with a screw cap and teflon liner. Add 5 mis concentrated high-purity nitric acid and autoclave for two hours at 15 psi. Transfer flasks to hood/hot plate and remove caps. Reflux gently on hot plate until volume is reduced to near dryness or until residue begins to turn brown (do not char)- Remove flask from hot plate and add two mis of 30% hydrogen peroxide. Return to hot plate to warm mixture until effervescence subsides. Carefully add 2 mis of concentrated nitric acid and again reflux until brown. Repeat peroxide nitric acid additions as before until digestion is complete but no more than. 10 mis of each or five additions. After 5th addition, carefully bring mixture to dryness (do not bake) and add 1 ml cone nitric acid and 1 ml cone hydrochloric acid. Return to a warm hot plate until residue is in solution. Quantitatively transfer to a 100-ml volumetric flask and make up to volume with distilled deionized water. The sample is now ready for plasma analyses. 117 Method PPB 10/80 U.S Environmental Protection Agency S&A Division, Region IV Laboratory Services Branch Athens, Georgia Extraction and Analysis of Priority Pollutants in Biological Tissue 1. Scope and Application 1.1 This method covers the determination of priority pollutants in biological tissue. 1.2 The limit of detection for this method is usually dependent upon the level of interferences rather than instrumental ' limitations. Where interferences are not a problem, the limit of detection for most compounds analyzed by GC/MS is 2 mg/kg (wet weight basis) . 1.3 This method is recommended for use only by experienced residue analysts or under the close supervision of such qualified persons. 2. Summary of Method ; Two 10 gm samples of homogenized fish are mixed with 40 gm of sodium sulfate, dried, and extracted — one for pesticide and the other for base/neutral and acid compounds. The pestici '. are extracted with petroleum ether and base/neutral/acids are e.,xracted with methylene chloride using an ultrasonic probe. The samples are filtered, concentrated to 10 mis or less, cleaned up with acatonitrile partitioning, and concentrated to 1 ml. The extract is analyzed with a gas chromatograph equipped with appropriate detectors. 3. Interferences 3.1 See the summary for General Interferences. (Appendix- No. 1) ; 3.2 Fish oil is eliminated by acetonitrile partitioning. 3.3 The ultrasonic probe must be scrupulously cleaned between samples. The procedure is: 1) Rinse the probe with solvent into the sample. 2) Remove residue on the probe with a wet kimwipe. 118 3) Rinse the probe with methylene chloride. 4) Sonicate with hexane for 3-4 minutes on 50% pulse. 4. Apparatus and Materials 4.1 Beakers - 400-ml. 4.2 Buchner funnels - 9 cm. 4.3 Filter paper - Whatman 41, ashless. 4.4 Vacuum filtration apparatus (Fisher 9-788) or 500 ml suction � filtration flasks. i f i 4.5' Filter vacs. �• 4.6 Kuderna-Danish (K-D) Apparatus. I' 4.6.1 Concentrator tube - 10 mil, graduated (Kontes K-570050- 1025 or equivalent) . ! 4.6.2 Evaporative flask (Kontes K-570001-500 or equivalent) . 4.6.3 Snyder Column - three-ball macro (Kontes K-503000- 121 or equivalent) . 4.6.4 Boiling chips __ Beryl saddles (Fisher, 91915) crushed. 4.7 Separatory Funnels - 120 ml and 2L. 4.8 Vater bath - Heated, with concentric ring cover, capable f temperature control (+20C) . The bath should be , n a 4.9 Drying Columns - 25 mm x 200 mm packed with 4 cm of glass wool. 4.10 Florisil Columns - Pyrex, 400 mm x 25 mm OD with Teflon stop cock, but without glass frit. i 4.11 Vials - Varian 2 ml. 4.12 Sonicator - cell disruptor - Model W-375 with the high gain 3/4 in. probe from heat Systems - Ultrasonics, Inc. or equivalent. 4.13 Food Processor - (Hobart food processor - 8181D ,or equivalent) . - 119 5. Gas Chromatograph 5.1 Gas Chromatograph - Analytical system complete with gas chromatograph suitable for on-column injection and all required accessories including flame ionization detector and electron capture detector, column supplies, recorders, gases, and syringes. 5.2 Base/neutral column and analytical conditions - Chromosorb W (100/120 mesh) , coated with 3% OV-17 packed in a 6' X 2mm ID pyrex glass column. Use ultra pure nitrogen at a flow rate of 30 ml/min. Column temperature is held at 800C for 2 min. , programmed to 290 at 8°/min. , and held at 2900C for 16 min. 5.3 Acid column and analytical conditions - Supelcoport (100/120 mesh) , coated with 1% SP-1240 DA, packed in a 4' X 2mm ID pyrex glass column. Use ultra pure nitrogen carrier gas at a flow rate of 30 ml/min. Column temperature held at 800C for 2 min. programmed to 2900C at 80C/min. , and held 'at 2900C for 16 min. 5.4 Pesticide column and analytical conditions. Supelcoport (100/120 mesh) coated with 1.5% SP-2250, 1.95% SP-2401, packed in a 6-ft. X 4mm ID pyrex glass column. Use Argon 95%/methane 5%, carrier gas at a flow rate of 60 ml/min. Column temperature, isothermal at 2000C. 5.5 Gas Chromatograph/Mass Spectrometer, Finnigan 3200 & INCOS 2300 Data System. 5.5.1 Piirge-and-Trap - Chemical Data System - 310 or equivalent. 5.6 VOA column and analytical conditions - Carbopack E (60/80 mesh) coated with 1% SP-1000 packed in a 10 ft. X 2 mm ID pyrex glass column. Use ultra pure helium carrier gas at a flow rate of 30 ml/min. Column temperature is held at 500C per j 4 min. programmed to 2100C and held for 11 min. 5.7 Gas Chromatograph/Mass Spectrometer, Finnigan 4000 and INCOS I 2300 Data System. Scanned from 33-450 a m u with a scan time of 3 m sec./a in u. Operated in the electron ionization mode. 5.8 GC columns _ Same as listed in 4..17.1 and. 4.17.2. 6. Reagents 6.1 Sodium Sulfate, anhydrous, reagent grade - heated 2 hours at 500°C, colled in a desiccator for 4 hours, and stored in a glass bottle. i 120 i 6.2 Petroleum ether - Burdick & Jackson pesticide quality, distilled in glass or equivalent. 6.3 Methylene Chloride - Burdick & Jackson or equivalent. ' 6.4 Hexane - Burdick & Jackson or equivalent. 6.5 Ethyl ether — preserved with 2% ethenol, Burdick & Jackson or equivalent. 6.5.1 Must be free of peroxide as indicated by M Quant Test Stripes (test stripes are available from EM Laboratories, Inc. , 500 Executive Blvd. , Elmsford, New York 10523) . 6.6 Florisil - (See appendix 11) . 7. Quality Control 7.1 See Section 8 page 2 of the Laboratory Services Branch Operations and Quality Control Manual. 8. Sample Extraction j 8.1 For volatile organic analysis the fish must be ground in area free of volatile organic compounds. I 8.2 . The preferred procedure is to use a blender and blend equal -_ amounts of Dry Ice with the fish. 8.3 If the sample is very large a food processor or meat grinder j is used. 8.4 Immediately-after making the fish homogenious, weigh 1 gm into a screw cap tube lined with aluminum foil. Store in a freezer until analyzed on GC/MS for volatile organic compounds. 8.5 Weigh 10 gm of homogenious sample into a 400 ml beaker and mix with 40 gms of sodium sulfate. Dry thoroughly. ' Label- Pesticide. 8.6 Repeat 8.5 and label Base/Neutral/Acid. 8.7 ' Extract the pesticide sample with 100 ml of petroleum using an ultra sonic probe. Sonicate at 50% pulse for 3 minutes. 8.8 Decant solvent through a Buchner funnel filtration system. 8.9 Repeat 8.7 - 8.8 twice. The last time pour the entire sample into the Buchner funnel. i 121 i 8.10 Repeat 8.7 - 8.9 for base/neutral/acid using 100 ml of methylene chloride. (NOTE: Clean probe between sample) . 8.11 Quantitatively transfer the extract to a K-D flask equipped with a 10 ml concentrator tube. 8.12 . Add a boiling chip-to the flask and attach a three-ball Snyder column. Place the K-D apparatus on the water bath and concentrate to 10 mis. 8.13 Acetonitrile Partioning for Pesticides This procedure is used to isolate fats and oils from the sample extracts. Zt should be noted that not all pesticides are quantitatively recovered by this procedure. The analyst must be aware of this and demonstrate the efficiency of the partitioning for specific pesticides. j 8.13.1 Quantitatively transfer the previously concept;ated extract to a 125-ml separatory funnel with enough hexane to bring the final volume to 15 ml. Extract i the sample four times by shaking vigorously for one minute with 30 ml portions of hexane-saturate acetonitrile. 8.13.2 Combine and transfer the acetonitrile phases to a one liter separatory funnel and add 650 ml of distilled water and 40 ml of saturated sodium chloride solution. i Mix thoroughly for 30-45 seconds. Extract with two 100-ml portions of hexane by vigorously shaking about 15 seconds. i 8.13. 3 Combine the hexane extracts in a one-liter separatory funnel and wash with two 100-ml portions of distilled water. Discard the water layer and pour the hexane layer through a 3-4 inch glass-wool drying column into a 500-ml K-D flask equipped on"th-.a-.lO0-hI..ampf1I. Rinse the reparatory funnel and column with three 10-m1 portions of hexane. 8.13.4 Concentrate the extracts to 6-10 ml in the K-D evaporator in a hot water bath. 8.13.5 Use nitrogen blow down to concentrate the extract to 1 m1. t 8.13.6 Transfer to GC vial. The extracts are ready for analysis. ' I 122 - r 8.14 Acetonitrile Partitioning, for Base/Neutral/Acid 8.14.1 Repeat 8.13.1. 8.14.2 Repeat 8.13.2, make the aqueous layer basic (pH 12) . 8.14.3 Repeat 8.13.3 - 8.13.6. 8.13.4 Make the aqueous layer acidic (pH 2) . Repeat 8.14.2 - 8.14.6 substituting methylene chloride for hexane. 9. Analysis by Gas Chromatography 9.1 Gas Chromatogra h/Flame Ionizatfon Screening of B/N and A Extracts 9.1.1 The B/N and A extracts are screened on GC/FID using the appropriate column to determine if GC/MS analyses are necessary. 9.1.2 Calculate the FID response of 50 ng of hexachlorobenzene (HCB) for B/N compounds and 100 ng of pentachlorophenol (PCP) for A compounds. (The GC/PIS requires about 50 ng I HCB and 100 ng PCP to give a complete mass spectra.) 9.1.2.1. If any peaks are present that are > the response calculated in 9.1.2, calculate the concentration of the largest peak. 9.1.2.1.1 If concentration is >2mg/kg (wet I weight basis) , analyze by GC/MS. 9.1.2.1.2 If concentration is <2mg/kg, report as <2mg/kg. } i 9.1.2.2 If all peaks are < the -responses required in 9.1.2, record the minimum detection limit in the master log. 9.1.3 Analyze all blanks and spikes and record precision- and-accuracy data in the QC log book. 9.2 Gas Chromatograph/Electron Capture Analysis of Pesticide Extracts 9.2.1 A 50X dilution of most samples will provide adequate I minimum detection limits for most samples such as PIDSD, ' EGD, and waste-site samples. 9.2.2 Analyze all blanks and spikes and record precision- and-accuracy data in the QC book. 1 123 i 10. Volatile Organic Analysis 10.1 Add 5-ml of organic-free water already spiked with the surrogate spike to the VOA tube. Replace the cap and shake the contents until the solids are dispersed throughout the water. 10.2 Immediately place the tube on the purge-and-trap apparatus and i heat at 550C for 12 minutes while purging. 10.3 The volatiles are trapped on a 24" tenax trap and backflushed ` onto the CC column at 180oC for 4 min. while the column is - held at room temperature (500C) . The CC is then programmed to 2100C at 8oC/min. and held for 11 minutes. 10.4 The volatile compounds are identified and quantified by the 11S computer system. i 1 I I �I j 124 Appendix II Level III Data Pigeon River & Palmer Creek May 1980 # Collected/Station Palmer Pigeon River Creek 4 6 8A 9 10 Oligochaeta Limnodrilus spp. (immature) 1 128 L. hoffineisteri 20 Lumbriculidae 4 1 7 2 82 Opisthopora 1 1 Nais spp. 1 99 1 9 7 Ophidonais serpentina 1 4 1 Hirudinea Mooreobdella melanostoma 1 Ephemeroptera Baetis spp. 20 65 4 178* 245 Pseudocloeon sp. 30 256 8 51* 42, Paraleptophlebia sp. 12 Isonychia sp. 23 19 Ephemerella lata 10 6 9 25 E. cornutella 69 8 2 E. tuberculata 23 7 2 2 E. wayah 9 E. walkeri 1 15 6 E. simplex 2 3 1 E. temporalis 1 1 E. catawba gr. 16 1150 23 35 317 E. invaria 16 8 4 13 1 E. rossi 15 E. hispida 16 E. berneri 2 E. deficiens 1 1 9 Cinygmula subaequalis 124 36 2 1 Heptagenia spp. 3 Epeorus sp. 1 gr. 97 6 4 2 E sp. 2 4 1 Rhithrogenia sp. 17 13 Stenonema annexum 25 15 1 S. rubromaculatum 6 30 1 18 125 Palmer Pigeon River Odanata Creek 4 6 8A 9 10 Argia sp: 1 Plecoptera Allocapnia sp. 1 Leuctra sp. 7 1 Amphinemoura sp. 8 1 Peltoperla sp. 2 Pteronarcys sp. 8 2 Acroneuria abnormis 6 2 3 3 A. georgiana 4 47 6 46 Paragnetina immarginata 1 Perlesta placida 6 13 Isoperla transmarina 46 3 I. orata 5 Isogenus decicus 3 Alloperla sp. 1 Sweltsa gr. 15 Trichoptera Micrasema sp. 38 41 Glossosoma nigrior 2 2 1 20 Lepidostoma sp. 1 4 Stactobiella sp. 1 Cheumatopsyche sp. 84 45 1 Diplectrona modesta 2 2 Hydropsyche venularis 80 7 11 5 Symphitopsyche bronta 1 S. morosa 3 3 S. slossonae 16 S. sparna 28 1 1 6 2 Doliphilodes sp 67 25 1 10 1 Lype diversa 1 1 Polycentropus sp. 2 2 Nyctiophylax celta 1 Rhyacophila carolina 7 1 R. fuscala 8 R. melita 1 R. vuphiphes 3 1 Coleoptera Promoresia elegans 114 1 11 Optioservus ovalis? 2 1 Psephenus herricki 1 126 Palmer Pigeon River Creek 4 6 8A 9 10 Megaloptera Corydalus cornutus Nigronia serricornis 2 1 Misc. Diptera Palpomyia (complex) 2 Blepharicera sp. 24 2 1 Atherix lantha 6 Protoplasa fitchii 4 Antocha sp. 18 1 1 3 Dicranota sp. 5 Tipula sp. 1 Hexatoma sp. 2 Simulium vittatum gr, 60 75 13 2 37 S. (Phosterodoros) sp• 3 1516 141 9 Prosimulium mixtum (?) 1 Empididae 11 4 5 Diptera: Chironomidae Microtendipes sp. 2 1 Polypedilum aviceps 37 1 2 2 P. convictum 92 2 P. fallax 1 1 P. angulum 1 4 Micropsectra sp. 12 Rheotanytarsus sp. 2 8 2 41 Tanytarsus sp. 4 1 Conchapelopia gr. 1 1 6 1 2 1 Diamesa sp. 7 Sympotthastia sp. 10 Brillia sp. 4 Cardiocladius sp. 1 3 10 19 Cricotopus/Orthocladius gr (C/0) C/O sp. 1: Cricotopus (C.) bicinctus 28 5 16 C/O sp. 5: C. (C.) c.f. infuscatus 44 9 C/O sp. 6: C. (C.) sp 3 1 C/O sp. 46: C. (C.) sp 4 2 10 C/O sp. 7 : Orthocladius (0.) nr. dorenus 6 4 15 C/O sp. 10: 0. (0.) c.f. obumbratus 1 2 20 2 2 C/O sp. 54: 0. (0.) nr. clarkei 7 1 12 C/O sp. 35: 0. (0.) sp. 4 1 4 C/O sp. 36: 0. (0.) sp. 5 52 4 C/O.sp. 13: 0. (Euorthocladius) sp. 1 (Type III) 10 148 52 14 2 127 Palmer Pigeon River Creek 4 6 8A 9 10 C/0 sp. 61: 0. (E.) nr. rivulorum (Type II) 2 C/O sp. 2: 0. (E.) sp. 3 2 2 C/O sp. 20: 0. (E.) sp. 4 1 2 89 92 Eukiefferiella bavarica gr. 3 8 4 2 E. devonica gr. 16 32 24 E. discoloripes gr. 3 8 3 E. claripennis gr. 1 2 1 E. potthasti gr. 10 E. brehmi gr. 3 1 4 1 Paraphaenocladius sp. 1 2 Rheocricotopus c.f. robacki 1 R, sp. 3 2 Gastropoda Goniobasis sp. 2 Hydracarina 2 128 Appendix III Level III Data - Pigeon River and Tributaries August 1980 Pigeon River Creeks 1 2 3 4 Richland Crabtree Fines EPHEMEROPTERA Stenonema annexum 126 - - - 3 - 10 S. ithaca 4 - - - + 28 8 Heptagenia sp. - - - - - + - Epeorus sp. 1 2 - - - - 1 1 Caenis sp. 4 - - - - 1 2 Tricorythodes sp. 2 - - - - - - Ephemera blanda + - - - - - - Isonychia sp. + - - - - + - Baetis nr. intercalaris 39 - - - - + 71 B. flavistriga 19 4 B. pluto (?) + - - - - 1 14 Pseudocloeon sp. 15 - - - 4 4 21 Cloeon sp. + - - - - + - Ephemerella deficiens + - - + - 1 2 E. serrata + - - - - - - E. serratoides + - - - - -E. bicolor - - - - - + - PLECOPTERA Acroneuria abnormis 7 - 4 + - 2 - Paragnetina immarginata 1 - - 1 - + 13 Leuctra sp. 2 - - - - + - Allonarcys sp. - - - - - 1 - TRICHOPTERA Cheumatopsyche sp. 71 1 - 1 141 29 29 Hydropsyche bronta 8 - - - - 9 9 H. morosa 22 1 - 20 - 1 87 H. sparna 16 - 11 11 2 14 114 H. venularis 3 1 18 172 3 - - H. incommoda + 1 5 11H. phalerata H. betteni - Oecetis sp. - Glossosoma nigrior 2 - - - Goera sp. - 1 - Hydroptila sp. 69 - - Leucotrichia pictipes - - - 1 18 - 5 Brachycentrus sp. + - - - Micrasema charonis + - + - Polycentropus sp. - - - 1 129 Phi• n Iti v r Crueks 1 2 } 4 Richland Crabtree Fines COLEOPTERA Jptioservus sp. 1 4 1 1 Oulimnius latiusculus - - - Promoresia elegans + - 1 - Stenelmis sp. - 2 + - Psephenus herricki - - + - - 1 1 Dineutes sp. + - - - Helichus sp. - - + ODONATA Larthus parvulus - - - + Gomphus sp. + - - - Macromia sp. + - - - + - - HENMIPTERA Sigara sp. - - + ,IEGALOPTERA Corydalus cornutus 20 10 1 3 1 7 14 Nigronia fasciatus - - - + DIPTERA: Misc Empididae 5 - 3 26 83 3 - Antocha sp. 18 - - 46 - - 54 simulium (Phosterodoros)sp. 3 - - 1 S. vittatum gr. 1 5 6 Protoplasa fitchii 1 Atherix lantha 4 - - 1 - 1 - Palpcmyia (complex) - - - 1 Atrichopogon sp. - - + - 1 + DIPTERA: Chironomidae Chironomus sp. - + - - + - + Cryptochironoinus fulvus - - + - + - - Microtendipes sp. - Polypedilum convictum - 8 4 P. i1li.noense - + + P. halterale - 1 - Phaenopsectra sp. + - - Stenochironomus sp. - - - Rheotanytarsus sp. 142 - 5 56 1264 48 287 Micropsectra sp. - 1 - Conchapelopia gr. - - 33 42 Cricotcpus/Orthocladius C/0 sp. 1:Cricotopus biciactus 1 - - 117 28 - 19 C/O sp. 5: :ricotopus nr. infus- - - - 1 8 - 36 catus C/0 sp. 6:C. tremulus gr. sp. 2 2 - - 20 8 - 8 — C/0 sp. 14:C. c.f. cylindraceu.s - - 4 130 Pigeon River Creeks 1 2 3 4 Richland Crabtree Fines C/0 sp. 54:Orthocladius (0) nr. - - 4 clarkei C/O sp. 3:Orthocladius - - - 4 - - 3 (F.uorthocladius)sp. Cardiocladius sp. 2 - - 79 45 1 27 Nanocladius sp. - 4 1 - Rheocricotopus c.f. robacki 4 - + Thienemaniella sp. - + 11 Eukiefferiella bavarica at. - 1 E. discoloripes gr. 4 - - - - 2 E. brehmi gr. MOLLUSCA Physa sp. - 593 99 8 1 - - Ferrissia sp. - 3 34 + - - 3 Gyraulus sp. Goniobasis sp. + - - - - + - HIRUDINEA Mooreobdella melanostoma - 1 10 1 OLIGOCHAETA Nais spp. - 959 - 4 36 - 5 Dero sp. - 6 - - Pristina sp. - 31 - - Limnodrilus spp. (immature) - 310 32 11 L. hoffineisteri - 123 80 1 Lumbriculidae - 1 - - 17 6 - Enchytraeidae - - - 4 MISC. Prostoma graecens 1 - - - 14 - 2 Hydracarina 2 - - - Nematoda - + - 131 EXHIBIT 1 CANTON MILL HISTORY YEAR FOR EVENT 1908 MILL CONSTRUCTION COMPLETED -_ NO. 16 & 17 PAPERBOARD MACHINES NO. 18 PULP DRYING MACHINE 1918 NO. 15 PAPERBOARD MACHINE RELOCATED FROM OHIO 1922 NO. 14 PAPER MACHINE 1925 NO. 13 PAPER.MACHINE 1932 NO. 12 PAPER MACHINE 1947 NO. 11 PAPER MACHINE THORNE BLEACH PLANT 1952 'D' HARDWOOD BLEACH PLANT 1958 'C' PINE BLEACH PLANT 1950 NO. 20 PAPER MACHINE 1980 WASTE TREATMENT PLANT PRIMARY CLARIFIER AND DOW PAC TRICKLING TOWER lees NO. 19 PAPERBOARD MACHINE NO. 15 6 16-MACHINES RETIRED NO. 17 MACHINE CONVERTED TO PULP DRYER NO. 10 RECOVERY BOILER 1973 NO. 11 RECOVERY BOILER NO. 6 A 9 RECOVERY BOILERS RETIRED NO. 7 & 8 BOILERS CONVERTED TO OIL - 1974 'A' PINE BLEACH PLANT L THORNE BLEACH RETIRED 1985 CHIP HANDLING SYSTEM COAL FIRED BOILER UNDER CONSTRUCTION LOW DENSITY BLEACH PLANT RETIRED _ NO. 7 A 8 BOILERS RETIRED ROUNDWOOD CHIPPERS RETIRED EXHIBIT 2 1 . -i FACTS ABOUT CANTON MILL L: PRODUCES 1500 tons of pulp per day. 1600 tons of paper and food board Paper is manufactured for the envelope and business paper market Food board supplies approximately 35% �." of the milk and juice cartons in the United States EMPLOYEES 2400 SALARIED AND HOURLY EMPLOYEES j = PURCHASES Approximately 2500 cords of wood per day About 1/2 is purchased from private wood haulers,wood yards, and save mills in Western North Carolina e EXHIBIT 8 ECONOMIC IMPACT OF THE CANTON OPERATIONS IN NORTH CAROLINA N 1985 PAYROLL $73,000,000 in 1985 RETIRED EMPLOYEES' PENSIONS $3,965,280 PURCHASED $35.000,000 Goods and Services in Western North Carolina PAID $2,235,870 state and local taxes PAID $10,000,000 to contractors in mill .site PAID $6,034,293 for medical benefits for the employees and families to area doctors and hospitals L PAID $12,291 ,447 for purchased power to Carolina Power and Light Company _ PAID $17,700,000 to wood haulers and local saw mills The total area economic contribution in 1985 was$160,226,390 7 EXHIBIT 4 ENVIRONMENTAL CAPITAL EXPENDITURES CHAMPION INTERNATIONAL CANTON_ NC MILL AIR EMISSION CONTROL 1973 Combination Bark—Coal Burning ; 1,748,000 Boller Silo—Mechanical S Water Scrubbers 1973 No. 11 Recovery Unit — Oxidizers ; 9,584,000 and Electrostatic Precipitators 1973 Coal Fired Boilers — Three ; 3,591,936 -- Electrostatic Precipitators 1976-77 Lime IQIns — Installed ; 900,000 Wet Scrubbers 77 1977 Heat Exchangers — Odor Control ; 1,014,218 1979-80 No. 10 Recovery Unit — Install Three ; 3,709.000 New Electrostatic Precipitators 1980-82 Odor Pollution Control Project ; 6.378,000 T 1983 Opacity Monitors, Odor Abatement, ; 180,288 a.` Dust Collectors, Stack Broaching, TRS Monitors, Miscellaneous 1981-85 Causticlzing Modification for i 12.841,000 Odor Control 1984 Odor Abatement, TRS Monitoring, ; 536.865 Precipitators, Ducts, Ambient Air Monitoring, Miscellaneous 1984-86 Pollution Control Equipment (esL) ; 6,600,000 New Coal Boller, Under Construction 1985 Odor Reduction, Black Liquor Oxid. $ 300,255 1985 H2S Monitor, Bark Boller Scrubbers, ; 127,303 • NCG System Rebuild TOTAL ; 47,510,864 �- EXHIBIT 5 ENVIRONMENTAL CAPITAL EXPENDITURES CHAMPION INTERNATIONAL rr CANTON. NC MILL -- STREAM IMPROVEMENT AND LANDFILL = 1966 Two 200 FL Primary Clertflers, Screens, Pumps $ 2,187294 1960 One 125 FL Primary Clarifier and Equipment $ 483,874 and No. 4 Sewer 1970 Secondary Wastewater Treatment Plant $4.610.869 l 1976-76 Sludge Dewatering System — Passavant Presses $ 2.264.099 1977 Water Treatment Moderrdzallon — Sludge Removal $ 1.480,336 1977 One 160 FL Secondary Clu ffier and Equipment $ 1,390.626 1979-80 Sludge Removal — Taft—Andrtlz Belt Presses $ 3,530.503 1973—80 LandfIlls $ 1.732.282 1986—82 Miscellaneous Additions, Electrical, Pumps. Piping. $ 2,469.426 Motors, Landnll Equipment, Etc. 1983 Landfill Property, Dissolved Oxygen Monitoring System, $ 428,764 Computer, Sewer Monitoring System. and Misc. 1984 Waste Treatment Electrical ModMeatlons. Front End $ 645.498 Loader, and Misc. .i 1985 Storm Water Collection — New Chip System $ 284,606 - r Oxygen Enrichment System $ 1,469,365 Waste Treatment Plant Improvements $ 316.422 Sludge Trucks $ 206,925 TOTAL $23,421,136 {{( EXHIBIT 6 C CANTON COLOR REMOVAL PROJECT PROJECT MISSION I Demonstrate that ultrafiltration technology, when operated at commercial levels on pine caustic extraction stage bleachery effluent, would remove 75% of the total color in the present mill effluent EXHIBIT 7 CANTON COLOR REMOVAL PROJECT KEY ASSUMPTIONS r a 7096 of total mill color is in the Pine Caustic Extraction t Filtrate (CEF) • Ultrafiltration (UF) can remove 90% of Pine CEF color ® 75% of the mill's total color to the river can be reduced utilizing OF on Pine CEF • Concentrate from OF can be disposed of in an environmentally safe manner L a OF will be technically and economically feasible C L IF. EXHIBrr $ I_ I� CANTON COLOR REMOVAL PROJECT PROJECT TASKS • Verify in—mill color balances r • Construct and operate a 100,000 gallon per day OF demonstration facility to show 90% color removal on Pine CEF and technical feasibility • Determine that treating 2 million gallons per day (MGD) of Pine CEF would accomplish the 75% color reduction target • Determine concentrate disposal and permeate reuse possibilities 17 • Prepare cost and engineering estimates EXHIBIT 9 r, lr l CANTON COLOR REMOVAL PROJECT PROJECT FINDINGS • Pine CEF is 56% of total color . . . . . . _ . _ _ Not 70% Hardwood CEF is 7% of total color Combined CEF is 63% of total color • Full scale color removal requires 4 MGD . _ _ Not 2 MGD ® The optimized demonstration facility removes 72% of Pine CEF color . . . . . . . . . Not lt0% Ell • Thus OF will rernove 45% of total mill color _ _ Not 75% Eii • Dispose of concentrate by evaporation and incineration . . . . . . . . . . . . . . . . . . . . . . Risky F.3 I� EXHIBIT 10 is CMEEON COLOR REMOVAL PROJECT l - PROJECT FINDINGS (continued) a Engineering Estimate ` — Equipment to deliver 4 MG D — Pretreatment — OF System eight parallel lines = 304 modules 4 MGD heat exchanger {{ 473 control valves 1' 106 pumps 9 computers six story building membrane cleaning system t$nk farm permeate return system permeate cooling tower 7. — Concentrate Disposal 77 evaporators - - rotary kiln housing Capital Cost$46.5 million EXHIBrr 11 CANTON COLOR REMOVAL PROJECT PROJECT FINDINGS is (continued) a Operating Cost L_ maintenance mernbrane replacement steam for heat exchanger steam for evaporator fuel utilities depreciation ' Cost per Year — $1 O million • t EXHIBrr 12 CANTON COLOR REMOVAL PROJECT SUMMARY • Not as much color in the Pine Bleachery as - we thought 56% not 70% ar Not as much color removed as we thought 72% not 90% • Larger full—scale color plant required than anticipated — 75,000 gpd n capacity not 100,Uo0 gpd - - 4 mgd required instead of 2 mgd r EXHIBIT 13 CANTON COLOR REMOVAL PROJECT CAPITAL AND OPERATING COST REVIEW • DEMONSTRATION FACILITY 1 .0 Million • CONSTRUCT FULL—SCALE FACILITY $46.5 Million ANNUAL OPERATING COSTS $10.0 Million C CANTON MILL PERCENT RETURN ON SALES 20 18 18 14 ROS 12 H Z W � 10 W a- 8 8 4 2 „ S ' R 0 1966 1970 1975 1980 1985 YEARS CANTON MILL ENVIRONMENTAL OPERATING COST BUREAU OF CENSUS REPORT - MA 200 30 25 i I d� 20 W Of OPERATING COST O15 0 z 0 ZI to 5 I 0 76 77 78 79 80 _ 81 82 83 84 85 YEARS r' r. TT CANTON MILL PERCENT RETURN ON CAPITAL EMPLOYED 30 25 ROCE , 20 z w 15 W fl 10 5 I I 1 0 1966 1970 1975 1980 1985 YEARS r— CEXHIBIT 17 f' i CANTON COLOR REMOVAL PROJECT ECONOMIC FEASIBILITY REVIEW • OPERATING COSTS . . . . . . . . . . . . . . . . . . . . $10.0 Million • % ROS declines from 4.9% to 3.5% • 53% Increase In operating costs for environmental control • CAPITAL REQUIRED . . . . . . . . . . . . . . . . . . $46.5 Million • 2-3 X annual mill capital program • % ROCE declines from 11.2% to 6.1% • ENGINEERING /TECHNICAL/ ENVIRONMENTAL ISSUES • Evaporation and Incineration technology Is unproven • COST ESCALATION FOR REMOVING HIGHER PERCENTAGES OF COLOR - • Evaluate alternate color removal technologies Abstract The paper compares the effluent characteristics from laboratory bleaching of softwood and hardwood kraft and softwood sulfite pulps by conventional se- quences.CEHDED and CEH,respectively,with those from oxygen bleaching se- qunces OCEDED. OCED, COO. CODED, and DICOD. respectively. Data are Or rented comparing color, chloride concentration. BOD. COD• alkalinity, acidity, total•volatile,and fixed solids.Reductions ranged from 30 to 90%for most of the Keywords _ analytes.The reductions observeo were noted to depend on Choice of s u n Oxygen bleaching' initial pulp kappa number, and chemical charge. Information ace, Biological treatment bleaching conditions employed is detailed includin tam on laboratory Color consistency, chemical charge oxygen 9 temperature. time, pulp BOD r, Data on final pulp brightness and kan pressure, and volume of wash water. Chemical oxygen demand studies on simulated effluents from b eaching numbers sequ nces presented. ED.rCEH Chlorides CODED• D/COD.CO. OCEOED, and OCED subjected to aerated stabilization Kraft pulps basin treatment are described, Showingreductions in BOD of Sulfite pulps days' aeration time. 90 with a Effluents i Characteristics of effluents from conventional and oxygen bleaching sequences W. L. Carpenter, W. T. MCKean, H. F. Berger, and I. Gellman Replacement of the fist and/or Second RESULTS AND DISCUSSION concentration, and total, volatile, and bleaching stage by an alkali—oxygen de- lignification stage appears as apossibil• fixed solids. The data assume total re- ity for reduction of bleach Plant effluent Effluent CharaeteNstics During covery of the soak liquor and oxygen loads. With these factors in mind, a Simulated Softwood kraft Bleaching stage wash water when using the study was initiate on the impatt':of a Process water was collected foe each 0 d EDED sequence. If the soak liquor d xygen Stage are not recovered.the change from conventional to oxygen individual bleaching stage and used to BODand COD oftheTBEwllbehigher bleaching on bleach plant effluent make up simulated total bleach plant because of greater extraction of or. characteristics and loadings. This re- effluents based on a proportional Vol. ganics by the oxygen stage than Occurs port covers only the major findings of time from each individual stage. The during chlorination- these extensive investigations of cur- TBE (total bleach effluents) were The results are summarized and pre- rent pulping and bleaching technology analyzed for color, BOD,COD,chloride sented in Table I. Reductions in color, and the impact of the resultant effluents on receiving waters. The complete re- Table I, Comparison port of this study is presented elsewhere lu Simulated Softwood Kraft Total Bleach (1) and includes 12 pulp sources. Of each Plant Effluents Using Long Sequence these, there are five Western, three Effluent load. o Northeastern, two North Central, and fpulp bleached two Southern species.There were seven Chlor• Total Total Total softwood and four hardwood'kraft pulps, Bleaching Sequence Color BOD COD ide solids volatile and one softwood sulfite pulp, flied solids solids CEHDED' 370 35 110 224 570 312 257 OCEDEDb 240 48 164 142 814 436 OCEDED (0 stage 378 recycled) 56 24 43 134 387 233 Effluent load re- 153 duction over CEHDED sequence 85% 31% 61% 409° 329r 25% CODEDb 400e W o Air St and N.F.pr vemenerger.National Coen• CODED(O stage 273 47 167 143 727 376 350 CAI for Air and Stream Improvement.Inc..$outhem Regional Center.P.O.Box 14483.Gainesville.Fla. recycled) 233 25 108 134 580 311 2;7 32604: W.T.McKee",Dept. of wood and Paper Effluent load re- Suenee.North Carolina State Umvers.ty,Raleign, duction over N C.27607: and I.Gellman. National Council for CEHDED sequence 3 7;° o Am and Stream Improvement. Inc.,260 Madison a ° 29° 40° 0 0.37 3.97. Ave.New York.N.Y. 10016. Five pulp sample%averaged. orhree pulp samples averated, Tappi ! November 1976 Vol. 59. Nn f t + Table III. Comparison of Effluent Loadings From Individual Bleaching Stages reBardtn8 water usage mthesestudies. Effluent load for each st fluents was assumed,therebyeaching stage ef- B(eaehing sequence age, Ib/ton of pulp bleached in maximum extraction of the a allt'ng Stage Stage • Stage Stage Sta a St Because rec elfinnot Ytes. 1• 2 3 g ago Stage water usage was20,000 ga employed 4 5 8 7 Bal/stagefton. CEDED Softwood kraft Therefore, the results presented in these studies should reflect the max. Color do 92 17 70 11 2 imum loading one would anticipate BOD •49 269 5 9 13_ ... .Exam individual stage and total •11 7 5 3 plant effluents. In actual bleach sL/OCEDED 3 3 3 1 •.. practice, Chloride a •-- water usage with recycling may reduce Color lla 110 104 67 17 4 4 total volumes to a range from 3000 to 8 BOD 15 49 1 4000 gal/stage/ton of pulp bleached. 5° 27 20 8 C/SL/ODED 5 2 2 1 Chloride gp 24a Color 18 16 Magnesium Content 35 339a 45 4 4 BOD 8 3 3 7 .'• D/C/SL/OD 7a 23 3 2 1 .•. Magnesium ions have been shown(5) Chloride 54 6a •.. to inhibit cellulose depolymerization b Color 16 14 ,.- a formation of complexes with certain BOD 99 + 700 50 2 2 24 5 ._ ::: units of the oxyeellulose. Because of C/SL/O ... this, the soak liquor and oxygen bleach Chloride 98 15a 15 stage effluents were analy zed.Yzed, along BOD 46 153a 78 :� '•• ••• ... with the original pulp,to determine the 14 54 2 .•• ... •_ magnesium content of the pulp as well j " •-• ... as an indication of the extent of mag- CEH Hardwood kraft nesium adsorption(added lulose de to inhibit cel- Chloride 69 gradation) onto the un- Color 13 74 .•. dergoing oxygen bleaching. Pulp at 11 92 g. These data BOD 11 4 •.. summarued here showchattheari SL/OCED 6 4 ••• .- ... ... Pulp magnesium content ran �� Chloride Is to 20 lb/ton. MagnesiumBed from 5 Color 6 10 110 42 15 •„ ••. added at a rate of lb/tons The alts were soak BOD g. 27 10 13 3 .• liquors Contained 0.1 to 3.5 fib of C;SLlOD 17 6 2 .. magnesium/ton,while the oxygen stage ChloriColor de 77 46a 18 14 ••• effluents contained 1.1 to 5.5 lb/ton of HOD 14 606 34 6 ... „• Pulp bleached. These results indicate 19 4° 30 2 ... that most of the magnesium salts are D;C/SL/OD -•• ... adsorbed onto the pulp. Chloride Color 57 4a 10 11 _, f 16 25 BOD 5• 0.34 11 4 ... --- °Soak liquor. 4 ... Effect of Chemical Charge... •_. Load 9 on Color Table IV. Effect of Recycling Soak Liquor and OxygenSelected data developed Stage Effluent 16•e in this study Sodium Losses in Total Bleach plant Effluents of on re examined to determine the effect of chemical charge on overall effluent �� color loading. High color loads were Sodium content, [b/ton noted with higher applied chemical R(.•ethi --Total bleach TBE (SL and o '�•i�.rnce effluent stage Table V. recycled) % recovery Comparison of possible Or:F.DED 188-190 Chemical Recover Or' 65 -75 Y of Sodium on Ot.F. 135-170 5.3- 6.6 60-66 Recycling of Pulp Soaking Liquor p(• D 161 43 95-97 and Oxygen Stage Effluents 131-146 g g_ 7 0 73 95-97 OC£DED hq"''r and oxygen stage effluents to (SL and Sodium Chen„cal recovery. Recovery of sodium proximately 3.5 to S.S�rr, thus Pulp CEHDED O stage recovered, at 11',9 ing the observations of Jamieson and no. sequence recycled) lb/ton 'e point could eliminate makeup Smedman 13). In a similar manner, Yi menu entirely and su lement 1S 96 67 29 0 ts i the digester.PP the sodium content for the Oxygen stage 6S 97 If,ne�ass umesnthat the alkali in the filtrates revealed that recovery of these 65 32.0 ��quor will be derived from inter- filtrates will recapture 70 to 100 lb of an 0 SL naI�,;ources(white liquor),and LL;nt a salt cake per ton of pulp, and parallels and e b B results reported by Engstrom et a(, (ql, CEH stage bl„ N� value it 2600 ), 3800 16 of sequence recycled) quor solids per ton of pulp going 12S y4 u� f'""very, the data for the oxygen Summa a.9 78.1 :hey+fltrates will show that the load to H 7S Summary of Total Water Use l7H 7.0 56.0 IIH 6 6.3 71.7 °ro`•ery boiler will be increa-ed ap- Certain assumptions have been made 8SU 72 4.6 62.1 November 1976 Vol. 4'6 67.a 0 59, No. 11 • - •'•' ki FULP BLEACHIMG charge and higher 'initial pulp kappa oxygen and conventional bleach se- each stage the pulp was dewatered ' number.The color loads at initial kappa quences,showing that they can be effec- vacuum filtration on a Buchner funr numbers of 30-35 and 19-24 averaged tively treated biologically. and washed in three stages by applyi 327 and 1901b/ton,respectively.Higher distilled water to the pulp mat. T chemical charge was applied with ratio of wash water to bleached lilt higher pulp kappa number,thereby ex- SUMMARY volume was precalculated from tvpi( tracting more color. mill bleach consistency and was 1.0 When comparing the data in these A comparative study of effluent 1.5. Combined wash and displac studies, one must consider the differ- characteristics from conventional and bleach water from each stage w( ences related to chemical charge and alkali-oxygen bleaching sequences on stored in closed containers at 30C kappa number.The variations in them- softwood and hardwood kraft and soft. subsequent analysis. ical charge were regulated in these wood sulfite pulps typical of wood For oxygen bleach stages, the p studies to coincide with individual mill species throughout the United States was soaked with precalculated amou practices during conventional bleach- indicate that major reductions in ef. of alkali at 3% consistency for 30 it ing, and subsequently it was desired to fluent color, BOD, COD, and chloride then dewatered to 207f consistency; bleach all the pulp samples by conven- concentration can be realized by the 3% alkali(1.59c hardwood)on pulp.', tional and oxygen sequences to the selectionof bleaching sequences includ- pressed-out soaking liquor was sto same final brightness without regard to ing recycling of an alkali-oxygen 3-tage for analysis. Pulp was fluffed int initial kappa number. The color loads for chemical recovery. The reductions stainless steel autoclave,evacuated; r generated here axe therefore somewhat obtained ranged from 60 to 90% for the pressurized to 120 psig with oxyg dependent on the preconditions used analytes using several different alkali- Bleaching time was about 10 mir here, so comparisons can be made at oxygen bleach sequences, some of 110°C in a heated apparatus that equal final brightness values.This pre- which have not been investigated pre- equipped to rotate the autoclave: i condition is,reflected in all the data viously.The comparisons show that re- about 4 rpm. Pulp was washed as herein. duction of analytes are dependent on scribed above. choice of sequence, initial pulp kappa The initial kappa number and f number, and chemical charge required brightness attained following bleacl, Effect of Biological Treatment on BOO to produce a highly bleached pulp.The for each pulp ranged from 13 to 36 overall reductions for some of the ana- 82 to 89%, respectively, regardles! A series of simulated effluents rep- lytes measured in the effluents paral- number of bleach stages employee resentative of all the pulp samples and leled earlier data reported in'the literati choice of sequence used in these sii bleaching sequences employed in this Lure for laboratory,pilot plant,and full- lated bleaching studies.For the purl phase of these investigations were sub- scale operation employing oxygen of data comparison,chemical charg( jectedto biological treatment byasimu- bleaching. Only modest differences in all the tests was adjusted to yield lated aerated stabilization basin(ASB) loads were noted regarding regional above brightness range. process following dechlorination.PH ad- pulp source: i.e., South vs. West Coast justment, and nutrient addition. Since differences ranged from 5 to 15% above ASB sludge was not available, each or telow the average. LITERATURE CITED sample was seeded with waste activated 1. Carpenter, W. L., McKean, W sewage sludge from a,single source con- + Berger, H.F., and Gellman. L.-Inv tinuously mixed to contain approxi- EXPERIMENTAL gation of Effluent Characteristics I mately 1200 mg/liter of mixed liquor Conventional and Oxygen Bleaching suspended solids. The results of the Cne pulp of each species was fully quences — Results of Laborau study are presented in Table Vic These bleached by conventional bleaching se- Studies." National Council for Air data parallel earlier studies (6) using quences as a reference. The bleaching Stream Improvement Technical Bul simulated ASB with BOD removal av- con litions were aligned with mill rac- C pence g P 2. Carpenter, W.L., McKean, W.T., eraging above 70% or higher on twb, tices. Standard laboratory techniques ger,H.F.,and Gellman,L."A Com day;aeration. These data cover a vari- wete used for chlorination.alkaline ex- son of Effluent Characteristics ety of simulated effluents from alkali- traction,and hypochlorite stages.After Conventional and Oxygen Bleachin quences--Results of a laboratory Sri Proceedings of the 1973 Inter:i t Table VI. BOD of Biologically Treated Conventional and Pulp Bleaching Conference, June Alkali-Oxygen Bleaching Effluents 1973,Vancouver,B.C.,Canada,p. 3. Jamieson. A- and Smedman, L.. 7 BOD, mg/liter after 1-10 days'aeration time 56(5): 107 (1973). Bleaching sequence 1 2 4 5 10 4. Engstrom H-E., lvnas, L., and Pei g 4 son,B..Tappi 54(11): 1899(1971). and pulp sample 0 day days days days days days 5. Croon, L. and Andrews, D.H.. 7 CEHDED, 9S 42 16 6 6 2 2 2 54t11): 1893 0971). CEH, 11H 31 16 11 9 4 3 2 6. Carpenter.W. L..Vainvakias,J.G. CEH, 8SU 55 16 10 9 2 3 q Gellman. I., J. Water Pollution Ca OCEDED, 6S 52 37 35 19 13 9 q Federation 40: 733 (1968). CODED,6S 42 23 12 10 3 2 2 D/COD, 11H 56 19 7 5 2 1 1 ®s r"L°t� vas conducted at the Sch Forest Resourc ."torch Carolina State L niv D/COD, 1S 98 40 20 15 10 9 9 and the NCASI Southern Regional Center.( OC, 8SU 116 27 20 11 10 9 9 ful appreciation is e,netided to Mr.Ed Dre, CO,8SU 125 86 26 23 12 3 2 conducted the work at NCSU and to Dr. Ho Chang. Assistant Professor of Forest Rena A verage% removal NCSU,for hia assistance to the cooperative t in planning the laboratory bleaching progra Conventional related attdim sequences ... 60 77 80 90 93 94 Received an Match 3.19"6 for preprinting ui Oxygen papers of the 1976 International Pulp Blea sequences ... 51 72 81 89 92 94 Conference held in Chicago. nl.,May 2-6. Accepted for publication in Tappi May 24. 1 + - Canton Mill • Box C-10 Canton,North Carolina 28716 V Champion Champion International Corporation April 21, 1992 Mr. Forrest Westall Regional Water Quality Supervisor NCDEHNR - Water Quality Section Asheville Regional Office 59 Woodfin Place Asheville, North Carolina 28801 Dear Mr. Westall: On July 13 , 1988, the North Carolina Environmental Management Commission, through the NPDES Committee, issued Champion International Corporation's Canton Mill a variance to water color criteria for the Pigeon River. The variance requires Champion to continue to study and evaluate color reduction technologies and annually report its findings to the Division of Environmental Management. Champion is pleased to submit the attached report in accordance with the variance requirement. If you have any questions, please call me at (7043 646-2318. Sincerely, Derric Brown Environmental Supervisor DB/spm Attachment RECEIVED Water Quality S-tion MAY - 4 1992 Asheville Regional Ohtistl Asheville, Horth Carotliv Champion International Corporation Mr. Forrest Westall April 21, 1992 Page 2 Copy: Mr. Richard Diforio Vice President - Environment, Health and Safety Champion International Corporation One Champion Plaza Stamford, Connecticut 06921 Mr. George Everett Director - North Carolina Department of Environment, Health and Natural Resources 512 North Salisbury Street Raleigh, North Carolina 27604 Mr. J. Ross Kilpatrick Vice President - Operations Manager Champion International Corporation PO Box C-10 Canton, North Carolina 28716 Mr. Steve Tedder, Chief Water Quality Section North Carolina Department of Environment, Health and Natural Resources Raleigh, North Carolina 27604 ` Champion International Corporation Champion International Corporation Effluent Color Control Technology Investigation Canton Mill April 1992 This report is the fourth annual report of color control technology investigations conducted by Champion International Corporation for the Canton Mill. The report is provided in accordance with the requirements detailed in a North Carolina variance for the Canton Mill. The report is divided into four sections. The first section is a review of color control technologies currently in practice or planned. The second section is an update on color control technology investigations being conducted by Champion. The third section discusses those technology evaluations which were concluded during the past year and the fourth section is a summary. Current Color Control Strategies Through March 1992, construction of the Canton Modernization Project (CMP) is approximately 42% complete. Engineering is approximately 85% complete. d° ' ¢° tOCD This project represents a three year commitment of some laqi $290 million in new equipment and technology for the Contnui r+�•�4 mill. The major focus of the CMP is to improve the .cam.«.-� LSurvl quality of treated mill effluent. err iSa nn Process changes include the installation of oxygen delignification and upgrading the black liquor systems. Permanent shut-down of existing process equipment includes the C & D brownstock washing and bleach plants and the east set of black liquor evaporators. Each of these improvements are aimed at removing and subsequently recovering lignin prior to bleaching. The reclaimed lignin will be returned to the mill's recovery system and burned. Planned changes in the bleaching area include 100% chlorine dioxide substitution and caustic extraction with an oxygen supplement. These approaches minimize the amount of color generated during pulp bleaching. Installation of these color control measures is expected to reduce treated effluent color to achieve compliance with the NPDES permit conditions now in effect. Color Control Technology Investigation Update Color control technologies are divisible into two groups; those that reduce color at the source (i.e. in-mill process changes) and those that treat color through end- of-pipe approaches. As discussed in the 1991 report and previously in this report, process changes which are considered feasible for color reduction at Canton are incorporated in the Canton Modernization Project. Champion International Corporation Champion International Corporation, Canton Mill Effluent Color Control Technology Investigation April 1992 Page 2 Color Control Technology Investigation Update - continued However, Champion continues to examine new and emer inq technologies to prevent the formation of materials that produce color in bleach plant effluent. Champion is also evaluating available technologies to recycle and internally destroy these materials. Extended delignification is a method of reducing the lignin content of the pulp prior to entering the bleach plant. Extended delignification requires a sequenced addition of pulping chemicals and the removal of solubilized lignin during the cook. However, extended delgnification offers only a marginal reduction in effluent color loads from a modernized Canton Mill with oxygen delignification. Champion continued evaluating ozone and other elemental chlorine-free bleaching technologies in the laboratory and through literature review. Reduced levels of u(1O- chloride in bleach plant effluent may ultimately allow recycle of this effluent to the black liquor recovery system. Our investigations in this area will continue. Enzymes have been developed for application in pre- bleaching following oxygen delignification. Enzymes have �s the potential to marginally reduce color by degrading ` hemicellulose which allows pulp to be more readily delignified. Color reduction can be achieved if the enzyme filtrates can be recycled to the recovery process. Champion has participated in a trial of this process at our Cariboo Mill in British Columbia. To assess the technical and economic feasibility, future trials using enzyme are being considered at our Pensacola Mill. Champion is currently investigating end-of-pipe color control alternatives. The technologies include S� `aq chemical/oxidation reactions which destroy color a- constituents in the wastewater; and separation processes which produce an additional sludge residue. During 1991 Champion continued to conduct pilot-scale studies of various oxidation technologies including the use of ozone. The advantage of the oxidation approach is the elimination of a by-product sludge. We found that specific ozonation conditions have a significant impact on the quantity of ozone required to achieve a given decolorization level. These investigations continue but require significant further development to determine whether they will be practicable as full scale treatment Champion International Corporation Champion International Corporation, Canton Mill Effluent Color Control Technology Investigation April 1991 z Page 3 Color Control Technology Investigation Update - continued processes. Although advanced oxidation processes are being applied to a number of industrial systems, the volume and light absorbance of bleach plant effluents result in a qualitatively different application from the other industrial cases. Champion is continuing the evaluation of full scale use of polyamines for coagulating and separating lignin during primary clarification. We continue to study the effects of polyamines on the dewatering characteristics of polyamine generated sludge. Kemiron and Champion conducted a full scale trial of total mill effluent using Kemiron's proprietary grade of ferric sulfate in a proprietary process at the Pensacola Mill. A short "mini" trial was also conducted at the Canton Mill using one primary clarifier. "Poly" ferric J�u sulfate is low in free acidity and therefore adds little �nC or no conductivity to the treated effluent. However, effluent iron concentrations were elevated as a result of the "Poly" ferric sulfate treatment which may adversely affect effluent chronic toxicity. During the Canton Mill trial the color solids settled poorly in the primary clarifier and produced a sludge with poor dewatering properties. Both the large quantity of sludge generated and the poor sludge dewatering characteristics remain a major obstacle with precipitative color treatment technologies. Technology Evaluations Concluded Five technology evaluations are concluded in this report. FMC and Champion conducted pilot studies of peracetic acid and persulfuric acid oxidation of bleach plant effluent. Color oxidation performance of the pilot study indicated that this technology was unable to achieve color removal levels achievable with other technologies. Rolls Incorporated conducted an evaluation of bacteria and enzymes for the bio-degradation of lignin as discussed in the 1989 Report. No definitive results were received from this evaluation. Champion continues to follow the academic developments for the bio-degradation of color; however, it appears the most promising application is in pre-bleaching as described above. Champion International Corporation Champion International Corporation, Canton Mill Effluent Color Control Technology Investigation April 19911 Page 4 Technology Evaluations Concluded - continued The Stone Process consists of post-secondary mill effluent treatment with a polyamine coagulant and a polacrylamide flocculant in a dissolved air flotation clarifier. The Stone Process is practiced at several unbleached or partially bleached mills around the country. Champion is not able to support any advantage of the Stone Process over polyamine effluent treatment. Champion evaluated the use of UV light with peroxide in small-scale pilot tests at our Pensacola Mill. Although the technology appeared to perform as claimed on conventional mill (without oxygen delignification) effluents, performance on Pensacola Mill (with oxygen delignification) effluent was degraded to a level not economically feasible. Champion and Radiation Disposal Services (RDS) evaluated the use of ozone in combination with ultraviolet light (UV) as a decolorizing agent. The evaluations showed that UV had no effect on the degree of decolorization achieved by ozone alone. However, Champion continues to follow developments for the potential application of ozone treatment of mill effluent. SUMMARY The Canton Modernization Project includes process and equipment changes which are expected to meet the recently approved NPDES permit color requirements. Color technology evaluations continue, from literature reviews to full scale trials. Champion continues to develop experience in alternative color control methods. CHAMPION INTERNATIONAL CORPORATION COLOR TECHNOLOGIES AND ECONOMICS UPDATE TO THE NPDES COMMITTEE OF THE NORTH CAROLINA ENVIRONMENTAL MANAGEMENT COMMISSION August 10, 1992 r Jointly Prepared by Champion International Corporation and SEC Donohue (formerly Sirrine Environmental Consultants) - '-r TABLE OF CONTENTS SECTION A PAGE EXECUTIVE SUMMARY . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . A-1 TABLE A-1 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . A-4 TABLE A-2 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . A-6 SECTION B I. ANALYSIS OF SELECTED TECHNOLOGIES . . . . . . . . . . . . . . . . . B-1 A. INTRODUCTION . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . B-1 B. CONCLUSIONS . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . B-2 TABLE B-1 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . B-4 H. ASSUMPTIONS AND ISSUES . . . . . . . . . . . . . . . . . . . . . . . . . . . . . B-5 III. TREATMENT TECHNOLOGIES . . . . . . . . . . . . . . . . . . . . . . . . . . . . B-7 A. LIME COLOR REDUCTION SYSTEM . . . . . . . . . . . . . . . . . . . . B-7 B. ALUM COLOR REDUCTION SYSTEM . . . . . . . . . . . . . . . . . . . B-11 C. POLYAMINE COLOR REDUCTION SYSTEM . . . . . . . . . . . . . . . B-15 D. CARBON ADSORPTION COLOR REDUCTION SYSTEM . . . . . . . B-18 E. ULTRAFILTRATION COLOR REDUCTION SYSTEM . . . . . . . . . . B-20 F. STORED AND TIMED RELEASE SYSTEM . . . . . . . . . . . . . . . . B-23 SECTION C CURTAILED PULP PRODUCTION . . . . . . . . . . . . . . . . . . . . . . . . . . . C-1 TABLE C-1 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . C-2 POTENTIAL COLOR REMOVAL TECHNOLOGIES . . . . . . . . . . . . . . . . C-3 IN MILL PROCESS CHANGES . . . . . . . . . . . . . . . . . . . . . . . . . . . . . C-3 END-OF-PIPE TREATMENT . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . C-4 SECTION D GROSS MARGIN TEST . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . D-1 TABLE D-1 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . D-3 TABLE D-2 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . D-4 APPENDIX A DESIGN BASIS - GENERAL APPENDIX B DESIGN COST BASIS APPENDIX C STORED AND TIMED RELEASE CALCULATIONS APPENDIX D ANNUAL REPORTS TO NCDEM 1989 -> 1992 APPENDIX E PROCESS FLOW DIAGRAMS CHAMPION INTERNATIONAL CORPORATION COLOR TECHNOLOGIES AND ECONOMICS UPDATE TO THE NPDES COMMITTEE OF THE NORTH CAROLINA ENVIRONMENTAL MANAGEMENT COMMISSION August 10, 1992 Jointly Prepared by Champion International Corporation and SEC Donohue (formerly Sirrine Environmental Consultants) SECTION A EXECUTIVE SUMMARY SECTION A EXECUTIVE SUMMARY At the request of Mr. Steve Tedder by letter to Mr. David Craft, dated March 16, 1992, Champion International Corporation is providing an update of the information submitted to the USEPA and NCEMC in 1987 and 1988 respectively which supports the granting by EMC of a variance from USEPA's interpretation of North Carolina's narrative water quality standard for color in the Pigeon River. This information also supported the issuance of an NPDES permit to champion's Canton Mill by USEPA on September 25 , 1989, which became final and non-appealable on March 12 , 1992 . The information presented here is divided into four sections: Section A. this Executive Summary, Section B. an updated review of the technologies selected by USEPA as the most feasible for color treatment in 1987 prepared by SEC Donohue (formerly Sirrine Environmental Consultants) , Section C. a review of pulp production curtailment and additional technologies investigated by Champion and submitted in the annual reports to the NPDES committee of the EMC, and Section D. an updated analysis of the economics of applying the six identified technologies (assuming their feasibility) pursuant to USEPA's Gross Margin Test. Since issuance of the variance in July of 1988 , and prior to finalization in March of 1992 of the NPDES permit, Champion has undertaken an aggressive and extensive Mill modernization project with an emphasis on pollution prevention including the reduction of color generated in the pulping process. A brief description of the status of this project is appropriate. This project represents a three year commitment of $300 million in new equipment and technology for the Mill. The major focus of the Canton Modernization Project (CMP) is to improve the quality of the treated mill effluent. Process changes include the installation of oxygen delignification and upgrading the black liquor reclamation systems. Permanent shut down of existing process equipment includes the C & D brownstock washing and bleach plants and the east set of black liquor evaporators. These improvements are aimed at removing and subsequently recovering lignin prior to bleaching. The reclaimed lignin will be returned to the mill's recovery system and burned. Section A 1 Changes in the bleaching area include the elimination of molecular chlorine by using 100% chlorine dioxide substitution in addition to caustic extraction with an oxygen supplement. Champion believes �= the Canton Mill will be the first bleached kraft mill to completely eliminate the use of molecular chlorine. These approaches minimize the amount of color generated during pulp bleaching. In the oxygen delignification system, washed unbleached pulp from the digesters is mixed with caustic soda and oxygen at elevated temperatures and pressures. The delignification method does not use chlorine as an agent for delignification allowing the colored filtrate's to be recycled to the recovery boiler. The lignin is burned for energy and the recovered chemicals are reused in the pulping process. The pine and hardwood fiberlines include systems to collect colored losses and return them to the recovery process. In addition, major rebuilds are complete for two of Canton's black liquor evaporator sets. These rebuilds were required to increase the capability to reclaim process losses. Modifications are also planned for improved control of process losses and increased storage. Systems are also provided to contain and recover process losses in the evaporator area. These color control measures are expected to reduce final effluent color to achieve compliance with the NPDES permit conditions now in effect. Presently, engineering on the modernization project is 95% complete while overall construction is 55% complete. Work on the black liquor recovery boilers, the evaporators, the non-condensible gas system, and the new mill water system are essentially complete. The CMP will reduce effluent color by at least 50%. However, as reflected in the EMC's Final Decision, the treated effluent color will not meet the USEPA interpretation of the water quality standard of 50 ppm color units in the Pigeon River at the point of discharge. Since, in periods of low flow, the flow in the Pigeon River immediately below the Canton Mill is 100% Mill effluent, any determination of whether or not the color standard can be met must be based on effluent quality "at the end of the pipe. " Once this modernization project is completed, the impact of the project on the Pigeon River and the western North Carolina economy can be fully analyzed. Until such time, and while the CMP is ongoing, it would be inappropriate to modify the requirements of the variance. It is anticipated that the CMP will reliably reduce color effluent from the Mill, and result in compliance with the provisions of the NPDES permit at the North Carolina/Tennessee state line, a condition slightly more stringent than the 85 color unit standard established by the variance. Section A 2 In the course of issuing the variance, the EMC and the DEM reviewed the feasibility of applying six technologies for end-of-pipe treatment and curtailment of Mill pulp production. As concluded in Section B of this report, and as determined by EMC in 1988, none of those technologies would enable the Canton Mill to meet USEPA's interpretation of the North Carolina narrative water quality standard for color at the point of mill discharge. The findings from SEC Donohue are summarized in Table A-1. While curtailing pulp production is a possible alternative to utilization of the other color removal technologies, pulp production would have to be reduced by approximately 80% from current levels in order to achieve the desired color reduction. Since it would not be economical to operate the pulp mill only 20% of the time, such curtailment would result in closure of the pulp mill and reliance on purchased pulp. Pulp mill closure would result in a capital expenditure of $51,113 ,000 and an annual cost increase of $108,783 ,000 to enable the Canton Mill to purchase 100% of its pulp. Over and above the extensive increases in costs associated with this operational change, the purchase of pulp from outside the western Carolina timberlands market would virtually destroy that market and result is losses of approximately $60,000,000 per year in chip purchases from the western Carolina region. It must be concluded that curtailment of pulp production at the Canton Mill, although technically feasible, is an unacceptable socioeconomic alternative. In addition to the detailed analysis of the six previously selected technologies, Champion has undertaken annual reviews of new technologies for color reduction/removal. A brief summary of these annual reports is found in Section C along with copies of the annual reports submitted for the past 4 years. In the course of those reviews, Champion has spent in excess of $5,000 ,000 evaluating technologies, representing a corporate commitment in excess of 25 man years. As shown in Section C, none of the reviewed technologies have been successfully demonstrated on a commercial scale. Therefore, it is impossible to assess their long- term feasibility and their potential when applied to effluent from the Canton mill. As required by paragraph 4 of the final order of the EMC (page 23 of the Final Decision) , Champion will continue to submit annual reports to the EMC staff updating these analyses. Section A 3 1 Champion Internation Corporation Color Technologies and Economic Update to NCEMC Section A- Executive Summary TABLE A-1: SUMMARY OF 1992 ASSESSMENT OF COLOR REMOVAL TECHNOLOGIES Issues/Technology Limo Color Alum Cofer Polyamine Color Ultraflltretlon Carbon Adsorp0on Stored&Timed Removal Removal Removal Color Removal Release Color Reduction Achieve 50 ppm at No No No No' No' No point of discharge? Total Capital Coats" $67,282,000 $55,937,000 $24,400.000 $288,887.880 $142.891,000 Not determined Total Annual Costs" $28,362,000 $23,990,000 $20,571,600 $69,380,800 $47,304,000 Not determined Influent Color Load 344,300 344,300 345,000 344,300 344,300 344,300 Problems a. Downstream site required a. Downstream site required a. Downstream she required d a. Downstream site required a. Downstream site required a.Technically impossible at amem due to inadequate space on site. due to inadequate space on she. tertiary application is used due to inadequate apace on she. due to inadequate space on she. mill loads b.Failure in earlier application Is. No testing done to rule out color b. Incineratorneeessary b. Would result in doubling miles b. incinerator necessary b. Requires installation of some because A wlorreversion reversion in receiving stream surtem electrical requirement. other color removal technology nnisrequired c New air peanhsrequired first to be lessible. c. High efguera total dissolved c. High off lwnttotal dssolved c. Newairpe c. Indneatornewssary solids(DS)likely. solids IDS)likely. d. Uncertainty m sebr removal d. No prior experience for c. Requires large lard area for d. May require add on process d. May require add on process less across Wrle. d. New Airpermhsrequired lecilrology,at this scale, ponds which is unavailable nearby. for DS removal at additional seal for DS removal at additional cost e. New air permhsmquired e. indreatornecessay f. New air permharequred ' Technology may be theoretically capable of achieving 50 ppm color at the point of discharge by adding more modules. However,the cost of installing additional modules would be prohibitively expensive. "For a system designed to achieve 50 ppm at the state line 8/7/92 Section A- Page 4 To determine their affordability the six color control technologies were evaluated economically using USEPA's Gross Margin Test and are summarized in Section D, Table D-1. That test was developed by _= USEPA as set forth in 40 CFR 131.10(g) (6) and is described in USEPA's "Guidance Manual for Estimating the Economic Effects of Pollution Control Costs" (1983) . In 1987 the Gross Margin Test compared the cost of applying various technologies on the impact to the cost of goods sold and revenues for the Canton mill. In 1988 it was concluded by USEPA that the Canton Mill failed the test by a factor of 6 to 1, using the least expensive technology irrespective of feasibility. Table A-2 presents the application of the Gross Margin Test to 1991 data. The Canton Mill currently fails the gross margin test by a factor of 4-1/2 to 1, using the least expensive technology and assuming its feasibility for application at the plant. As reported in Finding 38 on page 11 of the EMC final decision, In 1988, Champion also presented a report prepared by National Economic Research Associates, Inc. (NERA) . That economic analysis reported the impacts of color reduction scenarios comparing their relative costs and benefits. That report concluded that costs to Champion, and ultimately the western North Carolina economy, were far in excess of any benefits to be derived from requiring installation of the identified technologies. Since the updated review reflects an increase in those costs, a new NERA study has not been undertaken since it is believed there would be no change in NERA's calculation of benefits until after the CMP has been completed and river impacts analyzed. Recognizing that the mill modernization project is currently on schedule and that there have been no significant changes in the bases for the granting of variance in 1988, Champion suggests that there is no basis at this time for modifying the terms of the variance or the goals of the mill modernization project. Section A 5 TABLE A-2 GROSS MARGIN TEST ANALYSIS FOR THE VARIOUS EVALUATED COLOR REDUCTION SYSTEMS COLOR GROSS TOT.ANNUAL COST LOW REDUCTION MARGIN OF POLLUT.CONT. (EBT/ SYSTEM (GM) (TACPC) GMI) FOR TACPC/ INDST* GM LIME $38, 380,000 $ 28,362,000 0.118 0.739 ALUM $38,380,000 $ 23 ,990,000 0. 118 0.625 POLYAMINE $38,380,000 $ 20,572,000 0.118 0.536 ULTRAFILTRATION $38, 380,000 $ 69,391,000 0.118 1.808 CARBON ABSORPTION $38,380,000 $ 47,304,000 0.118 1.233 CURTAILED PRODUCTION $38,380,000 $108,783,000 0.118 2.834 TACPC/GM > LOW EBT/GMI FOR THE PULP AND PAPER INDUSTRY =___> THE CANTON MILL SHOULD NOT BE ABLE TO AFFORD ADDITIONAL COSTS INCURRED BY THE IMPLEMENTATION OF COLOR REDUCTION ALTERNATIVES EPT = EARNINGS BEFORE TAX FOR THE PULP AND PAPER INDUSTRY GMI = GROSS MARGIN FOR THE PULP AND PAPER INDUSTRY * BASED ON THE 1991 ROBERT MORRIS ASSOCIATES' ANNUAL STATEMENT STUDIES Section A 6 COLOR TREATMENT TECHNOLOGY ASSESSMENT CHAMPION INTERNATIONAL CORPORATION CANTON MILL CANTON, NORTH CAROLINA SEC DONOHUE JOB NO. G-2920 AUGUST 1992 SEC DONOHUE INC. GREENVILLE, SOUTH CAROLINA SECTION B ANALYSIS OF SELECTED TECHNOLOGIES ASSUMPTIONS AND ISSUES TREATMENT TECHNOLOGIES 1. ANALYSIS OF SELECTED TECHNOLOGIES A. INTRODUCTION As part of the North Carolina Environmental Management Commission's (EMC) Triennial Review of water quality standards and their review of Champion International Corporation's color variance that was granted in 1988, an updated economic analysis of the costs of implementing specified color removal technologies must be submitted to the Division of Environmental Management (DEM). The EMC granted a variance from United States Environmental Protection Agency's (EPA's) interpretation of North Carolina's narrative color limitation of 50 parts per million (ppm) at the Canton Mill. SEC Donohue was retained by Champion to perform this evaluation and produce a report for submittal to DEM. SEC Donohue, formerly Sirrine Environmental Consultants, produced the original cost analyses and technical reports for five color removal technologies applied at the Canton Mill that were submitted to the EMC and EPA in 1987 and 1988, respectively. In addition to the studies of color reduction treatment technologies conducted for Champion, SEC Donohue has carried out similar studies for other pulp and paper clients since 1987. This experience has resulted in an indepth working knowledge of current available technologies for color removal in pulp and paper mill effluents. Based on SEC Donohue's experience and knowledge, it is concluded that since 1987 no new technologies have been developed for color removal that can be effectively applied to the Canton Mill's effluent other than those reported in 1987/1988. The analysis of color removal technologies at the Canton Mill in 1987 was based on achieving a color concentration of 50 ppm in the Pigeon River at the North Carolina-Tennessee border. Based on historical color loads and wastewater flowrates, this translated to a required reduction in color of 80% just prior to discharge to the Pigeon River, i.e., at the end-of-pipe. SECTION B 1 The treatment technologies evaluated in 1987 and reevaluated in this report are as follows: Lime Treatment Alum Treatment Polyamine Treatment Carbon Adsorption Ultrafiltration Stored and Timed Release B. CONCLUSIONS SEC Donohue evaluated both the technical and economic feasibility of each of the technologies listed above. Table 1 summarizes the result of this analysis. Technically, none of these systems is capable of removing color in the mill's effluent to a concentration of 50 ppm at the end-of- pipe- The technical, but not economic, evaluation of color removal technologies which follows is based upon achieving EPA's interpreted color concentration of 50 ppm in the Pigeon River at the end of the mill's mixing zone. This color concentration is the limit from which the mill has been granted a variance. At 7Q10 flow conditions in the Pigeon River at the mill, which is defined by the lowest 7-day average flowrates for the past 10 years, however, the mill's water usage and subsequent discharge equal the entire river flowrate. Under these conditions, there is no dilution of color by the river between the discharge and the end of the mixing zone. Therefore, the technical evaluation of the color treatment technologies is based on achieving a color concentration of 50 ppm at the end-of-pipe. Four of these systems - lime, alum, polyamine, and stored and timed release - are not capable of achieving a concentration of 50 ppm at the end-of-pipe. It is theoretically possible that two of the technologies - ultrafiltration and carbon adsorption - may be able to meet the color standard at the end-of-pipe if more treatment modules were to be added. However, these technologies have never been demonstrated at this level and the additional costs would make the economic evaluation of these technologies even more out of the SECTION B 2 realm of economic feasibility. Also, to our knowledge, no commercial systems of this size and complexity have ever been operated. Since no system modifications will allow the technologies to meet the EPA's interpreted color limits at the end-of-pipe, the economic evaluation was based on updating the cost estimates from the previous report in 1987/1988 based on current design conditions and costs. These estimates reflect cost of achieving compliance at the North Carolina/Tennessee state line. SECTION B 3 Table 1 Summary of Color Reduction Technology Assessment Issuesrrachnology Llme Treatment Alum Treatment Polyamine Treatment UltraitRratlon Carbon Adsorptlon Stored&Timed Release 1987 1992 1987 1992 19137 1992 1987 1992 1987 1992 1987 1992 Commercially Demonstrated Technology Capable of Achieving No No No No No No No No No No No No Discharge Limit(1) Total Capital Costs(4) $55.500.000 $67,282,000 $43,900.000 $55,937.000 $24,700,000 $24,400.000 $204.000.000 $288,887,800 $117,000,000 $142,891-.000 $94.405,000(5) — Total Annual Costs(4) $23,177.000 $28,362,000 $17,939,000 $23,990.000 $21,936,000 $20.571,600 $64.726,000 $69,380,800 $42,574.000 $47,304,000 $20,718,000(5) — Influent Color Load,LBSIDay $357,000 $344,300 $357,000 $344,300 $357,000 $344,300 $357.000 $344,000 $357,000 $344,000 357.000(5) $344,000 (1)50 ppm at mixing zone (2)Technology Is theoretically capable of achieving discharge limits by addlton of modular units:system cost would be prohlbldvely expens". (3)For the anent mill color loads,this technology will not work (4)System designed to achieve 50 porn at state line (5)The economic evaluation for 1987 was based on a 50%color reduction prior to application of SUR. II. ASSUMPTIONS AND ISSUES Several general assumptions were made in the design of the various color removal systems. These assumptions were made due to: 1) the systems are presented only as conceptual designs, 2) significant time and costs would be required to validate or disclaim the assumptions, and 3) testing or technology are not presently sufficient to verify. If any of the assumptions are incorrect, each has the potential of precluding implementation of any of the color removal systems. The assumptions which are common to most or all of the color removal technologies are as follows: • Most of the process designs are based on laboratory and bench scale testing. Although some pilot testing has been performed in the pulp and paper industry for polyamine, lime, alum, and ultrafiltration, actual full scale application has been utilized for only polyamine and lime. Only polyamine is presently being used in the pulp and paper industry for a limited degree of color reduction. • The five color removal technologies each include the operation of a dryer or incinerator. Dryers and incinerators will result in emissions to the atmosphere of particulates, hydrocarbons, SO,, and NO,. Issuance of an air permit will probably be either difficult or impossible due to growing concerns with major new sources emitting into the Smoky Mountain National Park area. • Each of the color removal systems has the potential of being a source of odor. Odor could occur from the sludges or color concentrate produced as well as burning of hydrocarbons for drying or incineration. • The only mill property currently available within reasonable proximity to the mill is located at Fibreville, approximately one mile downstream from the mill. All of the systems, except polyamine, would be located at Fibreville. • Major construction in Fibreville may impact the flood zone along the Pigeon River, which may not be acceptable under federal guidelines. SECTION B 5 • The assumption has been made that a right-of-way can be obtained to construct and maintain one 84-inch diameter and one 60-inch diameter underground pipeline. The right-of-way between the mill site and Fibreville would require approval to route pipelines through a residential neighborhood, city streets, and a state road. • All of the systems would require site work and excavation. The cost estimates include site work and excavation, but not in areas of rock or hardpan. If these materials are encountered, which is highly likely in this area, the estimated cost will increase. Subsurface exploration and testing have not been conducted. • It is assumed that relocation of public utilities would not be required. It is also assumed that temporary closing of streets and a highway would be allowable. • All of the color reduction systems incorporate some means of reducing solid waste, therefore, minimizing additional landfill requirements. Should air permits not be granted, solid waste would then require additional landfill space. Although acquiring a permit for a new landfill may be currently possible, as with air permits, landfill permits will become more difficult or impossible to obtain in the future. SECTION B 6 III. TREATMENT TECHNOLOGIES A. LIME COLOR REDUCTION SYSTEM SEC Donohue has prepared a conceptual design for a lime system for color reduction in the Canton Mill effluent. The lime system would be designed for an influent color load averaging 344,300 pounds per day and design peak of 370,600 pounds per day (based on 1991 data). Bench scale testing has resulted in 86% reduction of effluent color, whereas full scale systems have been reported to achieve 80-90% effluent color reduction in pulp and paper mill effluents. The design configuration of the lime system is the same as the one used in 1987. Experience with color reduction systems in the pulp and paper industry has shown that color reversion could occur if decolorized wastewater is held for long periods or subjected to biological treatment. This problem was the reason that full-scale lime treatment systems have been abandoned. Testing to confirm that color reversion would not occur in the receiving stream has not been conducted. The addition of lime and other chemicals to the wastewater would cause large increases in the total dissolved solids concentration in the discharge. This is likely to cause violations of discharge or water quality limits, including toxicity. Removal of dissolved solids would require treatment by an ion exchange or reverse osmosis process. Costs for such a system, if proven feasible, could be of the same magnitude as the cost of the lime color reduction system itself, but have not been included herein. Effluent from the existing wastewater treatment plant would flow by gravity to the lime treatment system through an 84-inch diameter underground reinforced concrete cylinder pipe. Normal flowrate through the pipe should be 46 mgd, and maximum flowrate would be 52 mgd. The site is approximately one mile downstream from the mill on the Pigeon River and immediately north of Fibreville. SECTION B 7 The wastewater would flow into a reaction basin sized for 15 minutes retention time at 52 mgd. The basin would be a concrete structure, 110 feet x 60 feet x 15 feet deep and would be —_ equipped with baffles and eight mechanical agitators. Lime slurry would be fed into the reaction basin to be mixed with the incoming wastewater. The wastewater would then flow by gravity to dual flocculating clarifiers, each sized for 60% of the normal flowrate, where the floc produced as a result of the lime reacting with color compounds -in the wastewater would be allowed to settle. The clarifiers would be concrete structures 200 feet in diameter and 15 feet sidewall depth. They would be designed for an upflow rate of 900 gpd/ft' and a 3-hour retention time at a flowrate of 46 mgd. Each clarifier would be furnished with a flocculation well where the wastewater would enter. It would flow through the well to the clarification section of the unit where solids would be allowed to settle. Rake arms would be provided to continually move the settled solids inward to the sludge removal zone where it would be removed through desludge piping. The rake arms would be driven by a constant speed drive. Due to the dense nature of the lime sludge, the mechanism would have a torque rating of 2 x 106 ft-lbs. The wastewater would then leave each unit through an effluent launder. A carbonation basin would be provided to adjust the pH of the wastewater to 10.5 and to convert calcium hydroxide to calcium carbonate prior to final settling in the carbonator clarifier. The carbonation basin is a concrete structure that provides 2 minutes of retention at 46 mgd wastewater flow. The basin is provided with a sparging system constructed of type 316 stainless steel piping and nozzles and with a mechanical agitator to achieve complete mixing of carbon dioxide with wastewater. Purchased carbon dioxide would be used for the carbonation system. A carbon dioxide storage and feed system would be provided complete with a liquid CO,storage tank, vaporizers, control valves and piping. SECTION B 8 The carbonation clarifiers would be conventional type clarifiers without the center flocculation zone and would be 200 feet in diameter by 15 feet deep each. They would be used to settle the calcium carbonate sludge formed in the carbonation process and would be equipped with center drive units and rake mechanisms similar to the color clarifiers. The pH of the wastewater would be adjusted to approximately 7.0 in a pH adjustment basin that would provide 2 minutes retention time for reaction of wastewater with 66 a Baume sulfuric acid that would be pumped from a carbon steel storage tank by diaphragm-type metering pumps. The sulfuric acid storage tank would have a capacity of 32,000 gallons which would be a three-day supply. The two metering pumps would each have a capacity of 8 gpm. Following pH adjustment, the wastewater would be pumped back to the existing outfall at the mill wastewater treatment plant to be discharged to the Pigeon River. The lift pumps would be sized for the design flowrate of 52 mgd. Three pumps would be provided, each with a capacity of 20,000 gpm which is 50% of the maximum flowrate. The wastewater would be returned through a 60-inch diameter underground reinforced concrete cylinder pipe. Sludge from each clarifier at 10-15% solids would be pumped to a common sludge blend tank with a one hour retention time. Dual 100% capacity pumps would be provided for each clarifier. The sludge blend tank would be an open-topped carbon steel tank with baffles and a top-mounted agitator. Sludge would be pumped from the sludge blend tank to three vacuum precoat filters where it would be dewatered and concentrated to a consistency of about 45% solids. Each filter would be sized for 50% of the sludge flow. The precoat would be a 25% calcium carbonate slurry that would be prepared in the precoat mix tank from bagged calcium carbonate and mill water. Filtrate from the vacuum filters would be pumped back to the reaction tank to be mixed with the incoming wastewater. The vacuum filters would be designed to dewater approximately 2,300 tons/day of sludge (at 45% solids). The. sludge handling and dewatering equipment would be housed in a prefabricated metal building. SECTION B 9 The dewatered sludge would discharge from the vacuum filters to a screw conveyor that would route it to the lime kiln where the sludge would be burned and the lime recovered. The lime kiln would have a capacity of 700 tons/day and would be fired with No. 6 fuel oil. A storage tank with a three-day capacity of fuel oil would be provided as well as a pump and heater set for pumping fuel oil to the lime kiln. Combustion gases from the lime kiln would pass through a venturi scrubber where particulate matter would be removed by scrubbing with mill water. The scrubber waste would go to the reaction basin to be treated. The combustion gases would then go to a stack. All materials of construction in contact with the flue gas would be corrosion resistant. Reburned lime from the lime kiln would be transported by a drag line conveyor and bucket elevator to a lime storage silo with a two-day storage capacity. Volume of the silo would be 55,420 cubic feet, and it would be provided with a dust collection system and bin vibrators. A pneumatic unloading system for truck shipments of lime would be provided with a capacity of 80 tons/hour and for makeup lime as a backup when the lime kiln is out of service. Dual lime feeders of 100% capacity each would feed lime to two 50% capacity lime slakers. The slakers would use mill water heated to 120`F with 30 psi steam from the mill to produce a 10% lime slurry. A dregs washing and handling system would be provided for the slakers. Dual 100% capacity lime slurry transfer pumps would pump the lime slurry to a storage tank with a 2-hour capacity. An agitator would be provided to keep the slurry in suspension. Dual 100% capacity feed pumps would feed the lime slurry to the reaction basin to mix with incoming wastewater. The feed rate would be proportional to the wastewater flowrate. The pumps would be equipped with variable speed drives that would be controlled by a flow controller in the wastewater line. A building would be included to house the central control room, laboratory facilities, lunch area, and restrooms. SECTION B 10 The designed lime color reduction system would not meet the end of pipe color discharge limit. However, it would be capable of meeting 50 standard color units at the state line. The total capital cost of the lime color reduction system is estimated at$67,282,000. The total annual cost of the system is estimated at $28,362,000. B. ALUM COLOR REDUCTION SYSTEM SEC Donohue has prepared a conceptual design for an alum system for color reduction in the Canton Mill effluent. The alum system would be designed for an influent color load averaging 344,300 pounds per day and design peak of 370,600 pounds per day (based on 1991 data). Although bench scale testing has resulted in a 92% reduction of effluent color, no mills are known to be currently utilizing alum color removal on a full scale operation in the pulp and paper industry. The design configuration of the alum system is the same as the one used in 1987. Experience with color reduction systems in the pulp and paper industry has shown that color reversion could occur if decolorized wastewater is held for long periods or subjected to biological treatment. This problem was the reason that full-scale alum treatment systems have been abandoned. Testing to confirm that color reversion would not occur in the receiving stream has not been conducted. The addition of alum and other chemicals to the wastewater would cause large increases in the total dissolved solids concentration in the discharge. This is likely to cause violations of discharge or water quality limits, including toxicity. Removal of dissolved solids would require treatment by an ion exchange or reverse osmosis process. Costs for such a system, if proven feasible, could be of the same magnitude as the cost of the alum color reduction system itself, but has not been included herein. SECTION B 11 Effluent from the existing wastewater treatment plant would flow by gravity to the alum treatment system through an 84-inch diameter underground reinforced concrete cylinder pipe. Normal flowrate through the pipe would be 46 MGD, and maximum flowrate would be 52 MGD. The site is approximately one mile downstream from the mill on the Pigeon River, and immediately north of Fibreville. The wastewater would flow into a pH adjustment basin sized for 2 minutes retention time at 52 MGD. The basin would be a concrete structure, 30 ft x 30 ft x 12 ft deep and would be equipped with baffles and four mechanical agitators. Into this basin would be fed concentrated sulfuric acid to adjust the pH to 5.5 and alum at a dosage of 1800 mg/L. The alum would be a mixture of regenerated alum mud and makeup (50%) liquid alum. Makeup requirements are assumed to constitute about 5% of total alum requirements. In addition to alum and sulfuric acid, the basin would receive flue gas scrubber water from the incinerator and filtrate from the dregs screen separator in the alum recovery system to be recycled through the treatment plant. The wastewater would then flow by gravity to dual reactor clarifiers operating in parallel where the floc, produced as a result of the alum reacting with color compounds in the wastewater, would be allowed to settle. The clarifiers would be concrete structures 200 feet in diameter and 15 feet sidewall depth. Each clarifier is sized to treat 60% of the normal flowrate of 42 MGD at an upflow rate of 430 GPD/fe and a 3-hour retention time. Each clarifier would be furnished with a conical-shaped reaction well where wastewater would enter. It would flow through the well to the clarification section of the unit where solids would be allowed to settle. Rake arms would be provided to continually move the settled solids inward to the sludge removal zone where it would be removed through desludge piping. The rake arms would be driven by a constant speed drive. The wastewater would then leave the unit through an effluent launder. The concrete clarifier basins and the steel mechanisms in contact with wastewater would be protected by acid-resistant coatings to prevent against attack by low pH wastewater. SECTION B 12 Following the clarifiers, the pH of the wastewater would be adjusted to approximately 7.0 by in-line addition of 50% caustic. A carbon steel storage tank, heated and insulated, would provide 3 days storage capacity for the caustic. Dual 100% capacity metering pumps, controlled by an in-line pH controller, would feed the caustic into the wastewater. Following pH adjustment, the wastewater would be pumped back to the existing outfall at the mill wastewater treatment plan to be discharged to the Pigeon River. The lift pumps would be sized for the design flowrate of 52 MGD. Three pumps would be provided, each with a capacity of 20,000 GPM, which is 50% of the maximum flowrate. The wastewater would be returned through a 60-inch diameter underground reinforced concrete cylinder pipe. Approximately 91 tons/day of dry solids at a consistency of about 1/2% solids would be pumped from the clarifiers to a dissolved air floatation thickener where it would be dewatered and concentrated to a consistency of about 5% solids. The thickener is a concrete structure 60 ft in diameter and includes a thickener mechanism, air pressurization system, and recycle pump. Air is dissolved in the recycle portion of the thickener effluent and mixed with the sludge. The fine air bubbles rise to the surface of the thickener, and, as they do, suspended solids attach to the rising gases and a floating sludge layer is formed on the surface. This layer is mechanically skimmed off. The sludge that is skimmed off as well as any settled sludge flows by gravity to a sludge blend tank sized for thirty minutes storage capacity. The tank would be open-topped carbon steel with baffles and a top-mounted agitator, and it would be coated with an epoxy type acid-resistant coating. Sludge would be pumped from the sludge blend tank to a screw press that would dewater the sludge to a consistency of about 25% solids. A level controller in the feed well to the screw press would control the feed rate of sludge into the screw press. Filtrate from the screw press would be recycled to the influent pH adjustment basin, because it would contain suspended solids. The dewatered sludge would be conveyed by a screw conveyor to a flash drying system and a fluidized bed incinerator for alum recovery. A concrete pad storage area, sufficiently sized for 24 hours of storage time would be provided in the event the incinerator is out of service. Alum sludge would be landfilled when the incinerator is out of service. The thixotropic nature of sludge could result in operational problems under these conditions. SECTION B 13 The incinerator system would include a flash drying system that would mix the incoming wet sludge with a portion of the hot alum ash and flue gas. The sludge would be dried and ground in a cage mill prior to being fed into the incinerator where it would be burned at approximately 1000017. Air would be injected to keep the bed in a fluid state. Combustion gases from the incinerator would pass through a high energy cyclone separator where particulate matter would be removed. Residual particulate materials would be removed by scrubbing with mill water. The scrubber water would go to the influent pH adjustment basin for treatment. The combustion gases would then go out of the stack. All materials of construction in contact with the flue gas would be of Type 316 stainless steel construction. The alum ash that settles in the incinerator would be carried by screw conveyor and bucket elevator to a storage silo with one day storage capacity. The volume of the silo would be 3,500 cubic feet, and would be furnished with a dust collection system and bin vibrators. A screw conveyor would feed alum ash into a the and acid brick-lined batch reactor where it would be mixed with sulfuric acid, water and steam to make alum mud. The reactor is sized to make one batch of alum mud per 8-hour shift. It is equipped with a side-entry agitator to keep the slurry in suspension. After a reaction time of 4 to 5 hours, the alum mud would be pumped to dual alum storage tanks, that provide 3 days storage capacity for the color removal process. The tanks are of type 316 stainless steel construction. They would also be provided with unloading facilities for truck delivery of 50% liquid makeup alum. Approximately 26 tons/day of 50% liquid alum would be required for makeup. Dual 100% capacity alum feed pumps would be provided to feed an alum dosage of 1800 mg/l to the wastewater. The feed rate would be controlled by a flow controller in the wastewater line that would control variable speed drives on the pumps. SECTION B 14 Dregs that settle out in the batch reactor would flow to a washing tank where they would be washed with mill water prior to being separated in a stationary screen separator and hauled to the landfill. The tank would be a tile-lined steel structure with a side mounted agitator similar to the batch reactor. Pumps would be provided to transfer the washed dregs slurry to the screen separator. A sulfuric acid storage tank would provide 3 days capacity of 660 Baume sulfuric acid for pH adjustment of the incoming wastewater and for the alum regeneration process. Dual 100% capacity metering pumps controlled by pH would feed acid to the pH adjustment basin. Dual 100% capacity centrifugal pumps, manually-controlled, would feed the batch reactor. A dry polymer dilution and feed system would be provided to add a coagulant aid to the wastewater prior to clarification to assist in solids settling. The system would consist of a dry polymer hopper for receiving bagged polymer, an auger feeder, mixing tank with agitator, transfer pump, storage tank, and feed pump. A building would be included to house the central control room, laboratory facilities, lunch area, and restrooms. The designed alum color reduction system would not meet the end of pipe color discharge limit. However, it would be capable of meeting 50 standard color units at the state line. The total capital cost of the alum color reduction system is estimated at $55,937,000. The total annual cost of the system is estimated at $23,990,000. C. POLYAMINE COLOR REDUCTION SYSTEM SEC Donohue has prepared a conceptual design for a polyamine system for color reduction of the Canton Mill effluent. Unlike the other color reduction systems, the polyamine system is operated in conjunction with primary effluent treatment. Therefore, the system is designed for an influent color load averaging 345,000 pounds per day and a peak of 501,000 pounds per day (based on 1991 data). SECTION B 15 Champion is presently operating a polyamine system in conjunction with primary effluent treatment at the Pensacola Mill. The Pensacola system adds polyamine into a pre-existing settling basin. Sludge is continuously dredged from the settling basin and pumped into decant ponds for dewatering, excavation, and landfill disposal. Operation of this polyamine system has resulted in approximately 65% color removal efficiency. The settling basin and decant ponds encompass an area of approximately 25 acres. The polyamine system conceptual design for Canton varies from the system at Pensacola. Canton design utilizes: 1) primary clarifiers with a 4-hour retention time instead of a settling basin for settling, 2) sludge presses instead of decant basins for dewatering, and 3) an incinerator instead of a landfill for disposal. Due to these differences in design, it is questionable as to the applicability of the Pensacola system to the Canton Mill design. Polyamine addition in the primary treatment system has been shown to result in a significant waste of polyamine. At this point, it is not clear whether it is better to add polyamine to the primary system or in a tertiary treatment system. If tertiary treatment were proven to be the better choice for polyamine treatment, additional clarifiers and associated equipment would be required. These would be located at Fibreville with a resultant increase in cost since sufficient property does not exist at the mill site. The current Canton Mill polyamine system design has been changed since the 1987 design. The 1987 design utilized: 1) belt presses capable of 20% solids discharge, 2) a sludge dryer capable of 45% solids discharge, and 3) a landfill specifically for sludge disposal. The current design utilizes: 1) screw presses capable of 45% solids discharge, 2) a sludge incinerator for reduction of sludge to ash, and 3) no additional landfill since disposal quantity has been minimized. The design changes were prompted by improvements in screw press dewatering capabilities and an effort to minimize solid waste. Also, the four existing belt presses incorporated into the 1987 design are aging and would soon need to be replaced. SECTION B 16 Equipment required for the polyamine system would be located in the area of the existing primary clarifiers and sludge handling facilities. New liquid polyamine storage and feed equipment and sludge dewatering equipment would be included to handle the color sludge that would be added to the primary sludge volume. A new dewatering building is included to house the dewatering equipment. A sludge incinerator is included to dry and burn the sludge. Ash would be hauled to an existing landfill. The designed polyamine color reduction system would not meet the end-of-pipe color discharge limit. However, it would be capable of meeting 50 standard color units at the state line. The total capital cost of the polyamine color reduction system is estimated at$24,000,000. The total annual cost is estimated at $20,571,600. SECTION B 17 D. CARBON ADSORPTION COLOR REDUCTION SYSTEM —= SEC Donohue has prepared a conceptual design for a carbon adsorption system for color reduction in the Canton Mill effluent. The carbon adsorption system is designed for an influent color load averaging 344,300 pounds per day and a peak of 370,600 pounds per day (based on 1991 data). Although bench scale testing has resulted in more than 90% reduction of color for the carbon absorption system under consideration, further reduction in effluent color could be achieved by the addition of modular carbon absorption units to the designed ones. Effluent from the existing wastewater treatment plant would flow by gravity to the site of the color removal facilities through a new 84-inch diameter buried pipeline. This site is approximately one mile downstream from the mill on the Pigeon River, and immediately north of Fibreville. Wastewater would flow into a pH adjustment tank sized to provide a five minute retention of the average flow. The tank would be a below grade concrete structure 38 feet x 38 feet x 16 feet deep with a mechanical agitator and baffles. Sulfuric acid would be metered from an 18,000 gallon storage tank into the pH adjustment tank. A pH monitor and controller would maintain the pH of the wastewater at approximately 5.5. Following pH adjustment, the wastewater would be pumped to sand filters for removal of suspended solids. Three pumps, each rated at 20,000 gpm, would be provided. Total pumping capacity would be 150% of the maximum flow rate. The sand filters would be of the gravity type with automatic backwash. Filtration rate would be 4 gpm per square foot of surface area at the average flow (It is assumed that this filtration rate would reduce TSS to less than 5 mg/L). Total filter area requirement is 8,800 square feet. Twenty-two cells at 400 square feet each have been provided. This would allow one cell to be out of service for backwash at all times. Filters would be in a concrete, above-grade structure, and arranged in two rows of 11 cells. Overall dimensions would be 233 feet long and 43 feet wide. Filtered water would drain into a 725,000 gallon clearwell directly beneath the filter structure which would be below-grade. Two backwash pumps, each rated at 7,000 gpm, would be provided. SECTION B 18 Three pumps, each rated at 20,000 gpm, would pump filtered water from the clearwell to the carbon adsorption columns. Six columns have been provided. Each has a volume of 49,000 cubic feet and would be 40 feet in diameter and 40 feet high. These would be constructed of carbon steel. Each column would also provide 30 minutes retention of the average flow. Each column would be filled with granular activated carbon. The columns would be separated into three parallel trains of two columns each. Flow would be equally divided between each parallel train. Effluent in each train would pass in series through the two columns. When breakthrough is about to occur in the first column, the flow would be diverted to enter the second column in series, while the first column is emptied and recharged with fresh carbon. Color bodies in the wastewater would be adsorbed on the carbon and retained. Decolorized effluent would flow into a final pH adjustment tank. The final pH adjustment tank would be identical to the influent pH adjustment tank. Sodium hydroxide would be added to increase the pH to approximately 7.0. Three tertiary effluent pumps, each rated at 20,000 gpm, would pump the wastewater back to the mill area through new 60-inch diameter piping. Wastewater would be discharged in the existing outfall. Economics of the system operation favor on-site regeneration and reactivation of the carbon. These facilities would be provided. Periodically, much of the color could be washed from the carbon by a caustic wash solution. A 350,000 gallon 50% caustic storage tank would be used to store a two-week supply of caustic. The caustic would be transferred to a solution make-up tank where it would be diluted and stored until needed. The regenerant solution would then be pumped through the carbon column not in use. Wash water would then be pumped through the column. This regenerant solution, containing the color bodies, would flow under pressure to an evaporator. The evaporator would be sized for an inlet flow of 2,000 gpm. Evaporator bottoms would contain the color in a flow of 70 gpm. This stream would be at 8.9% solids. The evaporator would utilize combustion gases from the incinerator for heat. Evaporator bottoms would be pumped to one of two available rotary incinerators. Each incinerator would be sized for 100% of the color load. The incinerators would be fired with No. 6 fuel oil. Combustion gases would pass through a secondary combustion chamber to insure complete destruction of organics. Flue gases would be directed through a scrubber before discharge to the atmosphere. Approximately 22 cubic yards per day of ash would be produced and hauled to a landfill. SECTION B 19 After several cycles, the carbon would be thermally reactivated. Carbon from the column which is out of service would be pumped in slurry form to the spent carbon storage tank. This tank —= would have sufficient volume to contain the entire carbon load for one column. Spent carbon from the tank would be pumped in slurry form to a dewatering screw conveyor which would feed the thermal regeneration unit. Natural gas would be used to raise the temperature of the carbon to the point where organic compounds are driven off and oxidized. Reactivated carbon would be discharged to a quench tank where it would be re-slurried and pumped to the fresh carbon storage tank-to await reuse. This storage tank would also be 40 feet in diameter and 40 feet high with a conical bottom. Pumps would be available to recharge the carbon adsorption columns. The designed carbon adsorption system for color reduction would not meet the end of pipe color discharge limit. It would, however, be capable of meeting 50 standard color units at the state line. The total capital cost of the carbon adsorption system is estimated at $142,891,000. The total annual cost of the system is estimated at $47,304,000. E. ULTRAFILTRATION COLOR REDUCTION SYSTEM SEC Donohue has prepared a conceptual design for an ultrafiltration (UF) system for color reduction of the Canton Mill effluent. The OF system is designed to operate as a tertiary system. Laboratory scale testing with Canton's secondary effluent and pilot testing on the CE bleaching stages effluent have shown this to be a technically effective method for removing color. However, from a practical and an operational standpoint, there are serious doubts as to the viability of this process to treat a flow of 46 MGD. The OF system design specifies an additional 60,000 Hp of energy requirements. This equates to about 45 megawatts of electricity, which would double the current mill power consumption. It is assumed, but highly questionable, that this amount of energy would be available. The OF design is based on an 80% color reduction which was the basis for the 1987 study. OF is theoretically capable of removing all of the color if additional membranes are added to the system. An 80% color reduction creates enormous capital and operating costs. Therefore, it was deemed inappropriate to estimate costs which would probably increase exponentially. SECTION B 20 Space does not exist in the present mill area for the new equipment required. Therefore, property owned by Champion approximately one mile downstream and north of Fibreville would be utilized. Treated secondary effluent would flow through new piping to the treatment area. The effluent would pass through sand filters for suspended solids removal before being pumped to the OF system. Permeate from the OF system would be sent to a cooling tower to lower the temperature to within discharge limits and then pumped back to the existing outfall for discharge. Concentrate from the OF system would be concentrated further in a multiple-effect evaporator and then incinerated. The incinerator would include an afterburner, waste heat boiler, and ionizing wet scrubber. Sand filter backwash, evaporator condensate, and incinerator blowdown would be pumped back to the primary clarifier of the existing wastewater treatment plant. Wastewater would be collected and pumped to sand filters for removal of suspended solids. Three pumps, each rated at 20,000 GPM would be provided. Total pumping capacity would be 150% of the maximum flow rate. The sand filters would be the gravity type with automatic backwash. Filtration rate would be 4 GPM per square foot of surface area at the average flow. Total filter area requirement would be 8,040 square feet. Twenty-two cells at 400 square feet each, 8,800 square feet total, would be provided. This would allow two cells to he out of service for backwash at all times. Filters would be in a concrete, above-grade structure, and arranged in two rows of 11 cells. Overall dimensions would be 232 feet long and 43 feet wide. Filtered water would drain into a 960,000 gallon clearwell directly beneath the filter structure which would be below-grade. The clearwell provides 30 minutes of hydraulic residence time at the design flow rate. Three backwash pumps, rated at 5,000 GPM each, would be provided. Backwash would be pumped back to the primary clarifiers of the existing wastewater treatment plant. It is assumed that a sand filtration rate of 4 GPM/FT' would reduce TSS to less than 5 mg/1. SECTION B 21 Three pumps, each rated at 20,000 GPM, would pump filtered water from the clearwell to the OF units. Seventy OF modules, each rated at 750,000 GPD, would be enclosed in a 385,000 ft' ventilated building. Each module contains 11 OF membrane/recycle pump units. A forty- fold concentration in color would be achieved by each module. Five percent solutions of detergent, caustic and citric acid would be generated inside the building for cleaning the membranes. The cleaning cycle lasts one hour and each module would be cleaned every three days. An external 50,000 gallon steam-jacketed tank would provide 160'17 rinse water. Cleaning solutions and rinse water would be supplied to the membranes at 100 psig. Permeate from the OF system would be at 1150F which is above the allowable discharge limit. A three cell 35,000 GPM cooling tower with three 150 HP fans would lower the permeate temperature 25OF. Cooled permeate would be collected in a 140,000 gallon basin beneath the tower and pumped to the existing outfall for discharge. Three pumps, rated at 20,000 GPM each, would be provided. Concentrate from the OF system would be sent to a storage tank without additional pumping. From here, the concentrate would be pumped at 650 GPM to a six-stage falling film evaporator. The evaporator would reduce the flow to 70 GPM and increase the solids to 50 percent. Vapor from the last stage would be condensed by 5,000 GPM of cooled permeate taken from the cooling tower basin. All condensate from the evaporator would be collected and pumped to the primary clarifiers of the existing wastewater treatment plant. Reductions in pressure throughout the evaporator stages would be accomplished by a 700 HP vacuum pump. The concentrated product from the evaporator would be pumped to a 18" by 120", 3/4" tube stainless steel heat exchanger and brought to 220OF to prevent polymerization. Rating of the heat exchanger is 2,500,000 Btu/HR. Heat would be provided by 35 psig steam. From the heat exchanger, waste would be sent to an incinerator. A double-door ram feeder would force the waste into a refractory-lined rotary kiln. The kiln would be 12 feet in diameter and 80 feet long. An afterburner, operating at 1,800'F to destroy residual organics would follow the kiln. Supplemental heat of 28,000,000 Btu/HR would be supplied with No. 6 fuel oil. Total heat release of the incinerator is estimated to be 93,000,000 Btu/HR. SECTION B 22 Due to the nature of the material to be incinerated, operational or maintenance problems could require dual 100% capacity incinerators. This redundancy is not included in the cost estimate. A waste heat boiler would follow the afterburner. A prescrubber would follow the waste heat boiler and further cool the exhaust gases. Recycle waste would be pumped at 150 GPM and fresh waste would be applied at 70 GPM. Blowdown from the prescrubber would be sent to the primary clarifiers of the existing wastewater treatment facility. A wet electrostatic precipitator would reduce particulate emissions below 0.08 grains per SCF. Halogen removal would be 99% and SO, removal would be 95%. An induced draft fan would send the treated exhaust gases through a 300 foot stack for final release. The designed OF system for color reduction would not meet the end-of-pipe color discharge limit. It would, however, be capable of meeting 50 standard color units at the state line. The total capital cost of the OF system is estimated at $288,887,800. The total annual cost of the system is estimated at $69,380,800. F. STORED AND TIMED RELEASE SYSTEM This system is based upon the premise that color laden effluent could be stored as necessary in a holding basin until such time that the assimilative capacity of the Pigeon River allows metered effluent discharge. This system would not reduce the effluent color, but would allow discharges during higher river flows. The Pigeon River has an average flow of 206 MGD at the millsite, based on data from 1929 through 1991. The background color averages 13 ppm of true color. Water quality standards allow a total maximum of 50 ppm true color. Therefore, the average assimilative capacity of the river is 52,300 pounds of color per day (see calculations in Appendix C). Since the mill effluent contains 344,300 pounds of color per day, it would be impossible for stored and timed release system to function. Effluent inventory in a holding basin would continually be increasing, year after year, requiring an unlimited volume holding basin. SECTION B 23 The 1987 stored and timed release system estimated a holding basin based on a reduced color effluent discharge. In order to use stored and timed release, it would require use of another color reduction technology upstream. Since the color reduction technologies have exorbitant prices, addition of a stored and timed release system would only add to already prohibitive costs. Therefore, this technique was not estimated for a reduced color effluent discharge. SECTION B 24 SaIDOUONHoas aaHIO QNY SNaxaIYS2ino NOISOnUOUd d'Ind Jo SISAWKv o moiloaS (squegTnsuoo TequamuoaTAua OUTaaiS ATa9maO3) engouoa oas pue uorgeaodaoo TeuOigeuaaqul uotdmeuo �q peaedead ATguTOr Z66T 'oT gsnbny NOISSINxOO INUMDVNYN 'IV&NMMOUTANa YNI'IO2 vo MHON alu ao aaJZIxxOJ SaQdN am OS asYadn s3imoxooa cw sal9mom mas xOyloo NOI;LVHOCIHOo 'IYNOILvmaamI xoldNYHo Section C Analysis of Pulp Production Curtailment and Other Technologies Curtailed Pulp Production Based on the long term average Pigeon River flow of 206 million gallons per day (MGD) and the 1991 annual average color load, Champion predicts that approximately 80% of the time effluent color will be in excess of the USEPA interpreted standard of 50 ppm color at the end of the discharge pipe. Based on these assumptions. Champion estimates a long term average color load of 52 ,500 pounds per day of color is required to meet the USEPA 50 ppm color standard. This information was used to estimate the pulp production curtailment required at the Mill to meet the USEPA interpretation of the North Carolina narrative standard at the point of discharge. Pulp production curtailment was calculated to be 388, 370 tons per year. The greatest tonnage reductions were taken on the pine side because this created the least financial penalty to the mill. These reduced pulp production rates would create numerous shutdown and restarts of major process operations in the pulp mill, thereby causing significant upsets in the ability to control product quality, process operations and environmental emissions. Rather than operate the pulp mill under changing conditions, the pulp mill would be shut down and dry furnish (dried bleached pulp or "market pulp") would be purchased to meet 100% of the Mill's pulp needs. Since there are no dry furnish suppliers in the western Carolina region, all purchases would be from outside this economic region. The net financial loss associated with purchasing replacement pulp at market prices is $108,783 ,000 per year. The figure excludes: 1. losses associated with decreased area timberlands activity, 2. the financial impact of market share losses associated with turpentine and tall oil sales, 3. extra labor requirements or market premiums associated with buying and handling large quantities of market pulp and 4. the extensive writeoff of the capital investment in the pulp mill and demobilization costs. Consequently, the pulp replacement cost is a conservative estimate of the anticipated financial penalty. Approximately 1,886 ,000 tons of chips would no longer be purchased from North Carolina and neighboring states, with a resultant annual loss of $60 ,000,000 to the local economy. In order to maintain the mill's sales of paper and paperboard products, as well as cover the shortfall of pulp production, it would be necessary to spend $51,113,000 to install equipment for handling market pulp. The equipment is used commercially throughout the pulp and paper industry. The capital cost detail for this equipment is listed in Table C-1. Section C 1 TABLE C-1 CAPITAL COST SUMMARY CURTAILED PULP PRODUCTION Champion International Corporation Canton Mill Canton, North Carolina Purchased Pulp Handling System Building "Revisions, including Ramp $ 857,000 Ventilation (Bleach Pulper & Chest) 545,000 Dewiring Line and Bale Handling 6 , 389,000 Pumps 623,000 Agitators 623 ,000 Hypo and Sodium Thiosulfate Tanks 390 ,000 Pipe Fittings and Valves 1, 870,000 Motors 390,000 Electrical 662,000 Instrumentation 468,000 Relocate Pulper for Colored Broke (expense) - Convert two (2) Pulpers to Volkes Rotor 3 ,428,000 Twenty six (26) Pulpers with Volkes Rotors (continuous) 23 ,376,000 Subtotal $ 39,621,000 Engineering (12%) 4,755,000 Sales Tax (2%) 793 ,000 Contingency (15%) 5,944, 000 TOTAL CAPITAL COST $ 51,113,900 Section C 2 Potential Color Removal Technologies Champion has annually submitted a report to the NPDES Committee -- updating its review of alternative color control technologies. These annual reports are attached in Appendix D. Color control technologies are divisible into two types; those that reduce color at the source (i.e. in-mill process changes resulting in pollution prevention) and those that treat color through end-of- pipe approaches. As provided to the Division of Environmental Management in the annual reports, those process changes which are considered feasible for color reduction at Canton are already incorporated in the CMP. In Mill Process Chances Champion continues to examine new and emerging technologies to prevent the formation of materials that produce color in in-mill processes, as well as technologies to recycle and internally destroy these materials. It should be understood that based on Champion's research, it has been concluded that effects of various technologies are not directly additive, i.e. , adding one color removal technology to another does not yield an overall color reduction equal to the sum of that obtained by separate technologies. Each color control technology is evaluated independently to determine the impact to effluent color. A brief discussion of technologies which continue to be investigated follows. Extended delignification may be performed using chemical catalysts or by modifying the Kraft pulping process by installing new process technology. Also, enzymes have been developed for application in prebleaching. Whereas, both of these technologies reduce the lignin content of the pulp prior to entering the bleach plant, they are not actually color reduction techniques. Rather, they are designed to reduce the amount of bleaching chemicals. Less bleaching chemical is required when a reduced lignin content pulp enters the bleach plant. (With less lignin to be removed, somewhat fewer color bodies are generated in the bleach plant effluent. ) For the current mill, the color load would be reduced by an estimated 10% with either extended delignification or enzymes. The treated effluent obviously would not meet the stream standard of 50 ppm color in the Pigeon River at the point of discharge. Champion is evaluating ozone bleaching technologies in the laboratory and through literature review. Ozone bleaching is not currently being performed at any kraft pulp mills. Ozone bleaching is in the developmental phase and the successful operation of a full scale system is questionable. Although a system to replace one of two pulp bleaching lines at a U.S. mill is scheduled to ' Section C 3 start operating later this year, currently, ozone bleaching is not a demonstrated technically feasible technology. Furthermore, Champion believes that the process improvements being installed as part of the CMP will provide benefits equivalent to ozone bleaching, and represent technologies posing a greater chance of success. End-of-Pipe Treatment Pilot scale studies are being conducted on mill effluent for various oxidation technologies, including ozone. To date, Champion has spent in excess of $900, 000 evaluating oxidation technologies. An advantage of the oxidation approach is the reduction or elimination of a by-product sludge. Although advanced oxidation processes are being applied to a number of industrial systems, the different volume and light absorbance of bleach plant effluents result in a qualitatively different application from the other industrial cases. While ozone oxidation of mill effluent has been touted as a promising technology, it has not been commercially demonstrated and the feasibility of applying it to the effluent stream at Canton cannot be currently determined. Without such commercial demonstrations, similarly, there can be no detailed evaluation of the costs of implementing this technology should it ultimately be determined to be feasible. Champion has evaluated the full scale use of polyamines for coagulating and separating lignin during primary clarification in an activated sludge wastewater treatment plant as well as the effects of polyamine generated sludge. A discussion of a polyamine color removal system and associated costs are detailed in the enclosed Color Treatment Technology Assessment Report by SEC Donohue. As discussed in the report, polyamine color treatment will not meet 50 ppm color in the Pigeon River at the point of discharge. A "mini" trial using polyferric sulfate was conducted at the Canton Mill using one primary clarifier. The trial duration was shortened because of an inability to clarify and thicken the generated color floc. The floc which was generated was impossible to dewater on any of the bench scale press equipment used for the trial. Additionally, trial experience at Champion's Pensacola Mill shows that increased effluent iron concentrations result from the use of this chemical, and may adversely affect effluent chronic toxicity. Based on trial experience polyferric sulfate is not a technically feasible color removal technology. Ongoing research and investigation of color control and removal technologies demonstrate Champion's commitment to determine which technologies might be technically and economically suitable for use at the Canton Mill. Section C 4 CHAMPION INTERNATIONAL CORPORATION COLOR TECHNOLOGIES AND ECONOMICS UPDATE TO THE NPDES COMMITTEE OF THE NORTH CAROLINA ENVIRONMEITPAL NANAGE4ENT COMMISSION August 10, 1992 Jointly Prepared by Champion International Corporation and SEC Donohue (formerly Sirrine Environmental Consultants) SECTION D GROSS MARGIN TEST GROSS MARGIN TEST The Gross Margin Test measures the total annual cost of pollution control as a fraction of Gross Margin (Gross Profit) . If the total annual cost of color removal exceeds a defined range, then the technology may adversely affect the plant's profitability. The range is delimited by the ratio of Earnings before Taxes (EBT) to Gross Margin for a specific industrial sector (defined by SIC code) . The Gross Margin Test was carried out for each of the color reduction options under consideration. The information needed for carrying out that test included: 1. The total revenues for the Canton Mill in 1991. 2. The cost of goods sold by the Canton Mill in 1991. 3 . The total annual cost of each color reduction alternative under consideration. This cost was determined based on an interest rate of lot and a 20-year equipment lifetime. 4.. Income Date for different plant sizes in the Pulp and Paper industry; SIC, # 2621 (Robert Morris Assoc. , 1991) . The data used included Gross Profit (Gross Margin) data and Earnings before Taxes (EBT) for the Pulp and Paper industry (Appendix) . The industry's corresponding ratio of Earnings before Taxes to Gross Margin (EBT/GM) were determined from the listed income data. The Gross Margin Test was performed on the various color reduction alternatives by dividing the annual cost of pollution control for each alternative by the 1991 Gross Margin (Total Revenues - Cost of goods sold) for the Canton Mill and by comparing this ratio to the lowest EBT/GM ratio determined for the Pulp and Paper industry in 1991. Tables 1 and 2 summarize the results of the Gross Margin Test for the different color reduction alternatives. Table 2 indicates that the ratio of the Total Annual Cost of Pollution Control to the Gross Margin for each of the color reduction alternatives evaluated is greater than the lowest EBT/GM ratio for the Pulp and Paper industry (lowest industry EBT/GM = 0.118) . The Canton Mill should; therefore, not be able to afford additional costs that will be incurred by the implementation of any of the color reduction systems evaluated in this study. Section D 1 TABLE 1. SUMMARY OF DATA USED FOR THE GROSS MARGIN TEST CANTON MILL DATA ° REVENUES $379,028,000 COST OF GOODS SOLD $340,648,000 GROSS MARGIN $38,380,000 THRESHOLD VAL INDUSTRY EST/GM RATIOS PLANT SIZE PLANT SIZE PLANT SIZE PLANT SIZE No. 1 No. 2 No. 3 No. 4 IND. EBT 3.0 3.9 4.8 8.6 IND. GROSS MARGIN 25.4 20.9 21.8 19.5 IND. EBT/GROSS MARGIN 0.118 0.187 0.220 0.441 LOW IND. EBT/CROSS MARGIN 0.118 ° 1991 DATA °* BASED ON THE 1991 ROBERT MORRIS ASSOCIATES' ANNUAL STATEMENT STUDIES Table 2. GROSS MARGIN TEST ANALYSIS FOR THE VARIOUS EVALUATED COLOR REDUCTION SYSTEMS GROSS TOT. ANNUAL COST LOW (EBT)/(GMI) TACPC/GM COLOR REDUCTION SYSTEM MARGIN OF POLLUT. CONTROL FOR INDUSTRY ' (GM) (TACPC) , LIME $38,380,000 $28,362,000 0.118 0.739 ALUM $38,380,000 523,990,000 0.118 0.625 POLYAMINE $38,380,000 $20,572,000 0.118 0.536 ULTRAFILTRATION $38,380,000 $69,391,000 0.118 1.808 CARBON ADSORPTION $38,380,000 547,304,000 0.118 1.233 CURTAILED PRODUCTION 538,380,000 5108,783,000 0.118 2.834 IF TACPC/GM > LOW EBT/GMI FOR THE PULP AND PAPER INDUSTRY THEN THE CANTON MILL SHOULD NOT BE ABLE TO AFFORD ADDITIONAL COSTS INCURRED BY THE IMPLEMENTATION OF COLOR REDUCTION ALTERNATIVES EST : EARNINGS BEFORE TAX FOR THE PULP AND PAPER INDUSTRY GMI : GROSS MARGIN FOR THE PULP AND PAPER INDUSTRY • BASED ON THE 1991 ROBERT MORRIS ASSOCIATES' ANNUAL STATEMENT STUDIES APPENDIX A DESIGN BASIS - GENERAL DESIGN BASIS - GENERAL Following are design bases for the conceptual designs and cost estimates for the color removal systems. These values were derived from actual annual mill operating data. It is common practice in engineering design to use average values for determining operating costs and 95% exceedance limits for determining equipment sizes and costs. A skew analysis was applied to each of the parameters to provide values which are most applicable for design purposes. The skew analysis technique was utilized due to the nature of the data being analyzed. Wastewater treatment data typically does not fit a symmetrical "bell curve", but is instead skewed to the right or left. A typical arithmetic analysis does not take the skewness into consideration. With color for example, the arithmetic average, 95% exceedance limit, and maximum values are 306,800, 477,000, and 748,000 pound per day, respectively. Due to the skewness the skew analysis average value is more and the 95% exceedance level is substantially less. It should also be noted that actual maximum values were not used for equipment sizing due to their sporadic behavior. With these values, equipment sizing was based primarily on experience with similar systems and on good engineering judgement. Second= Effluent Design Parameters 199 Average Flow, MGD 46 95% Exceedance Flow, MGD S2 Average Color, pounds per day 344,300 95% Exceedance Color, pounds per day 370,600 Average pH 7.4 pH Range 6.8-8.0 Average TSS, PPM 18 95% Exceedance TSS, PPM 43 APPENDIX A I APPENDIX B DESIGN COST BASIS DESIGN COST BASIS The color removal studies submitted in 1987/1988 were used as the basis for this update of costs. Typically, individual units of equipment were either adjusted by the number of units involved or by a unit size change. If only a unit size change occurred, then the new size was divided by the old size and raised to the 0.6 power. This factor was then applied to the 1987 equipment unit cost. This is a common engineering method for revising the estimated cost of equipment that has changed in size. If the type of equipment specified changed from 1987, the new piece of equipment was estimated based either on equipment vendor quotes or good engineering judgement. Cost adjustments from June 1, 1987 to June 1, 1992 were estimated by utilizing the "Engineering News-Record" construction cost index (CCI). The June 1, 1987 CCI was 4406. The June 1, 1992 CCI was 4965. The 1992 CCI was multiplied by the 1987 cost and divided by the 1987 CCI to obtain a current equipment cost. Costs are presented as June 1, 1992 prices. Further escalation of the total construction cost has not been included. The estimated design/construct time required for this project would be 24 to 30 months. Permitting would add another 6 to 12 months. However, the start date of the project is unknown at this time. The cost for land acquisition for pipelines between the mill and the Fibreville site are included. It is assumed that this land can be purchased from the individual landowners and from the City of Canton. All labor costs are based on merit shop labor with construction forces working a nominal 40-hour week with some occasional overtime. The construction costs are based on historical factors of equipment costs for similar type projects, except the utilities between the proposed site and the present mill, and these were estimated on a takeoff method. APPENDIX B l An allowance for contractors' overhead is included at 1.2 times direct labor. An allowance for owners project administration is included at 8% of total direct cost plus land acquisition cost. Engineering and consultants include costs for design, survey, soil investigation, testing and environmental permits/studies. Permitting costs are omitted. An allowance for contingency is included at 15% of total project costs. Depreciation is based on a 20 year life of total direct costs and interest on 10% of total capital costs. APPENDIX B 2 APPENDIX C STORED AND TIMED RELEASE CALCULATIONS PI®eon River 206 MGD 13 ppm 22330#/Day Color 46 MGD 897 ppm Color 344300 6/Day Color Champion Holding Basin F"=+39.01 MGD Increase/Day Storage F=6.99 MGD 897 ppm Color C'=52300 X/Day Color F=167MGD 50 ppm Color C"=69600#/Day Color C 7-1ONO Block Flow Diagram Ti J Df Stored and Timed a F�Vim=at&Inhaimi Release System Pigeon River Assimilative Color Capacity Basis: Average River Flow Upstream of Mill, MGD 206 Average River Color Upstream of Mill, PPM 13 Maximum River Color Downstream After Mixing, PPM 50 Average Mill Flow to Storage Pond, MGD 46 Average Mill Color to Storage Pond,#/Day 344,300 Calculations: Maximum River Color Increase, PPM 50 - 13 - 37 Average Mill Color, PPM 344300 46 ' 8.34- 897 Average River Flow at Millsite, MGD 206 - 46 - 160 Color Capacity at Millsite,#/Day 160 ' 37 ' 8.34 - 49,400 Metered Mill Discharge Flow, MGD 49400 (897 - 50) 8.34 - 6.99 Metered Mill Discharge Color,#/Day 6.99 ' 897 ' 8.34 - 52,300 River Flowrate After Mixing Zone, MGD 160 + 6.99 - 166.99 Total Downstream Color Capacity,#/Day 167 ' 50 ' 8.34 - 69,600 Daily Pond Storage Increase Requirement, MGD 46 - 6.99 - 39.01 APPENDIX D ANNUAL REPORTS TO NCDEM 1989 -> 1992 Caren Ntill Box C-10 Cantca.Nonr.Carouna 2871 E CChampion Charnmon International Corporation May 1 , 1989 Mr. Forrest Westall Regional Water Quality Supervisor North Carolina Department of Natural Resources and Community Development Asheville Regional Office P.O. Box 370 Asheville, North Carolina 28802 Dear Mr. Westall: On July 13, 1988 the North Carolina Environmental Management Commission through the NPDES Committee issued Champion International Corporation' s Canton Mill a variance to a USEPA Region IV interpretation of North Carolina' s narrative water quality standard for color. The variance requires Champion to continue to study and evaluate color removal technologies and report its findings to the Division of Environmental Management annually on or before April 30 of each Year. Pursuant to this requirement, Champion hereby submits the first annual review of effluent color control technologies. Please contact Paul Wiegand at the Canton Mill if any questions should arise regarding this information. Very truly yours, �(AXXV4X J. R. Kilpatrick Enclosure Copy: Mr. R. Paul Wilms Director, Division of Environmental Management 512 North Salisbury Street Raleigh, North Carolina 27611 Mr. Richard Diforio Vice President - Environmental Affairs Champion International Corporation One Champion Plaza Stamford, Connecticut 06921 EFFLUENT COLOR .CONTROL TECHNOLOGY REVIEW In accordance with requirements detailed in a variance for Champion' s -Canton, North Carolina Mill, this is the first annual report of effluent color control technologies investigated by Champion. This report is divided into three sections. The first section is a review of color control technology research efforts prior to 1988. The second section is a discussion of Canton Mill plans to install color control technology under the terms of an NPDES wastewater discharge permit to be issued by the United States Environmental Protection Agency (USEPA) . The third section details continuing research of color control technology for the Canton Mill. Review of Color Control Efforts Prior to 1988 On May 14, 1985 North Carolina issued the Canton Mill an NPDES wastewater discharge permit. The permit required Champion to investigate the feasibility of installing ultrafiltration color removal technology. The goal of the investigation was to demon- strate, through the use of ultrafiltration, that the mill could achieve a 75% reduction in effluent color. Following a one year demonstration of this technology and concurrent evaluation of in- mill color sources it was determined that ultrafiltration would not be feasible on a full scale level and that 75% effluent color reduction could not be achieved with this technology. Prior to the final determination that ultrafiltration was not a feasible color removal technology at Canton Mill, the USEPA rejected the validity of the North Carolina issued permit and assumed permitting authority. During subsequent deliberations with USEPA Champion was requested to evaluate the cost of employing seven discrete color treatment technologies aimed at achieving an 80% effluent color reduction. A list of these tech- nologies along with the capital and annualized cost of operating the respective systems is provided in Table I. Costs for these seven alternatives are based on mid-1987 costs and would almost certainly be higher than shown if reevaluated today. C Page 1 TABLE I Color Treatment Technologies Suggested by EPA and Cost Estimates for Application at Canton Mill Capital Cost Total Annual Cost Carbon Adsorption $ 117, 000, 000 $ 42, 547, 000 Ultrafiltration 204, 000,000 64, 726, 000 Lime Treatment 55,500, 000 23, 177,000 Polyamine Treatment 24, 700 ,000 21 , 936,000 Alum Treatment 43, 900, 000 17, 939,000 Effluent Storage 94, 405, 000 20, 718,000 Curtailed Production 6, 647,000 24, 257, 000 Evaluation of the costs of applying any of these approaches indicated that all failed USEPA' s Gross Margin Test at the plant level as described in USEPA' s "Workbook for Estimating the Economic Effects of Pollution Control Costs" . In addition several of the technologies had major adverse environmental impacts. Subsequent to the evaluation of the above technologies, Champion submitted a report to EPA and North Carolina entitled "Effluent Color Reduction Project - Technology Review" (February 1988) . This report was a comprehensive review of technologies examined by Champion to reduce effluent color discharged to the Pigeon River and involved literature surveys, laboratory studies, pilot plant trials, contracted research work and visits to pulp and paper mills around the world. The technologies identified were divis- ible into two groups; those that reduced the source of color through in-mill process changes, and those that treated color through end-of-pipe approaches . Each technology was investigated for economic and technical feasibility, as well as environmental impacts . A copy of this report is included as Appendix A. plans for Color Cont7-ol at Canton Mill Prior research (documented in the February 1988 report) served as a basis for selection of realistic color removal technologies which could be employed at the Canton Mill. In February 1987, Champion proposed color control for the Canton Mill which incorporated both in-mill process changes and end-of-pipe treatment to achieve color reduction. This proposal was intended to achieve maximum color reduction while maintaining current Production levels at the mill . Page 2 .. :. -...cia,Ccr^c,- -- - Of the in-mill process changes detailed in the report Champion proposed to install oxygen delignification technology, closed screen room, and filtrate reclamation systems. Each of these technologies is aimed at removing and subsequently reclaiming lignin prior to bleaching. The reclaimed lignin can be returned to mill ' s chemical recovery system and burned. In addition, changes in the bleaching area were proposed including partial chlorine dioxide substitution for chlorine and caustic extraction with oxygen. These approaches minimize the amount of color generated during pulp bleaching. The end-of-pipe treatment technology used chlorine dioxide to de- colorize filtrate from the caustic extraction stage of pulp bleaching. Champion research has shown that chlorine dioxide is suitable as a decolorizing agent and does not produce undesirable by-products. A schematic comparing the current mill pulping operation and the proposed pulping operation is provided in Figure 1 . In December, 1988 the State of Tennessee denied Champion' s request for a variance from Tennessee' s narrative color criteria of 50 color units. The proposal for color reduction made in February 1987 was not capable of a level of color reduction necessary to achieve 50 color units at the North Carolina - Tennessee border. Champion is currently evaluating alternatives, including production curtailment, to meet 50 color units at the border. Continuing Color_Reduction Research Efforts As mentioned earlier, color control technologies are divisible into two groups; those that reduce the source of color through in- mill process changes, and those that treat color through end-of- pipe approaches. With respect to in-mill process changes, Champion continues to study the benefit of increased "chlorine dioxide substitution for chlorine in the first bleaching stage. Research indicates that color is reduced through increased use of chlorine dioxide in the first stage. End-of-pipe color treatment may be sub-divided into two groups; separation technologies and chemical treatment technologies. Separation technologies use either physical or chemical means with which to separate lignin from wastewater. Examples of these types of processes include ultrafiltration and chemical flocculation. All separation processes must include, as a final step, ultimate disposal of separated color material. Discussed below are pro- cesses under evaluation for possible application as color control technologies at the Canton Mill. Champion is either directing or actively following engineering and scientific research of with these processes. Page 3 Hansel Enterprises, partially through a Champion sponsored grant to the University of North Carolina at Asheville, operated a laboratory bench top scale color removal system during 1988 . The process is proprietary and uses common water treatment chemicals to accomplish a precipitation reaction with lignin. Although this process was successful in removing color from Canton Mill waste- water, sludge disposal remained a major obstacle. The pulp and paper industry trade publication TAPPI Journal published an article which detailed a process called the Lignin Removal Process (LRP) . This process is a variation on a well known property of lignin. Lignin is known to form a precipitate at acid pH' s of 1-2 standard units. The LRP reaction uses waste fiber as a location for the precipitate form. Sludge generated can then be separated in conventional clarification equipment. Champion has investigated acid precipitation as a color removal method, but is investigating the LRP method further. The Stone Process for color removal invented by Stone Container' s Charles Ackel is a process which uses polyamine precipitation technology for color removal. In the Stone Process separated color sludge is returned to the recovery boiler in the kraft recovery cycle. Stone Container has not applied this technology to a fully bleached mill. The Stone Process was evaluated in 1987 (see Appendix A) . Champion continues to follow the development of this process. Chemical treatment technologies are methods by which the lignin in wastewater is altered in some way such that it no longer appears colored. These technologies usually involve some type of oxi- dation reaction. Champion is currently researching two such alternatives . Radiation Disposal Services (RDS) is evaluating the use of ozone in combination with ultraviolet light as a decolorizing agent. In addition, RDS is' developing a proprietary electrode for generating ozone. Work to date has focused on decolorizing bleach plant effluents . Champion considers this research to be in the develop- mental stage and it is too early to determine if this technology could be employed at Canton. Rolls Incorporated is evaluating the use of specially developed bacteria and enzymes for bio-degrading lignin. Past evaluations of bio-depredation for color removal have yielded insufficient levels of removal. The largest obstacle to overcome with this technology seems to be the long wastewater retention time (sometimes weeks) necessary to allow bio-depredation to take Place. Rolls claims that their special bacteria may be able to bio-degrade lignin within the retention span of the existing Canton Mill aeration basin. Results of tests with colored effluents are not available. yet. Page 4 Nutek Corporation is evaluating the use of electron beam tech- nology either alone or in combination with oxidants as a color reduction technique. This technology is currently used in varied applications such as wastewater sterilization and food irrad- iation. Use of electron beams as a decolorization technique is new for Nutek and research with wastewater and bleach plant filtrates is continuing. Dr. David 011is from North Carolina State University through his consulting firm Photolytic is evaluating a proprietary process using -ultraviolet light and titanium dioxide as a color reduction technique. No information is available regarding the effect- iveness of this process at this time. EcoTech Systems, Inc. has asked Champion to evaluate a product known as Beta X-12. EcoTech claims both oxidative destruction of organics and encapsulation of inorganics action from the product. Tests have yet to begin with this product. In summary, during 1988 there was no new technological development which would allow the Canton Mill to achieve a greater level of color reduction than is already planned. However, Champion continues to pursue development of color control alternatives and has a program in place to seek out promising new technologies. This program involves not only primary research but also consid- eration of color control technologies brought to our attention by companies, scientists and interested citizens . Page 5 Box C-10 Canton.North Carolina 28716 V Champion Champion International Corporation April 30, 1990 Mr. Forrest Westall Regional Water Quality Supervisor NCDEHNR - Water Quality Section Asheville Regional Office 59 Woodfin Place Asheville, North Carolina 28801 Dear Mr. Westall: On July 13 , 1988, the North Carolina Environmental Management Commission, through the NPDES Committee, issued Champion International Corporation' s Canton Mill a variance to water color criteria for the Pigeon River. The variance requires Champion to continue to study and evaluate color reduction technologies and annually report its findings to the Division of Environmental Management. Champion is pleased to submit the attached report in accordance with the variance requirement. Very truly yours, Paul Wiegand Environmental Supervisor Attachment mm................--.-, Mr. Forrest westall April 30, 1990 Page 2 _ Copy: Mr. J. Ross Kilpatrick Vice President - Operations Manager Champion International Corporation P.O. Box C-10 Canton, North Carolina 28716 Mr. Richard Diforio Vice President - Environment, Health and Safety Champion International Corporation One Champion Plaza Stamford, Connecticut 06921 Mr. George Everett Director - North Carolina Department of Environment, Health and Natural Resources 512 North Salisbury Street Raleigh, North Carolina 27611 *SOS usgq slow dq aoToo quenTJ99 p94e914 aonpaz oq pagoedxa sT saanseaw TOa4uOO 10TOO asag4 90 UOT4eTTe4sui •buTuoeaTq dTnd buTanp pa}ea9u96 iOTOO 90 qunowe aqq azTWTUTw sagOeoadde asags •uabdxo 194TM UOT}Oeagxa OTgsn2D pug SUTaOTgo ao; uoT4n4Tgsqns apTxoTp allTZOTgO TeuoT4Tppe apnTOuT ease buTgOeaTq aqq UT sabuggO pauueTd Pau' anq Pug w94sAs ,CaanoOaa s , TTTw aqq oq pauangaa aq TTTM UTUbTT pawTeTOaa aqs •buTgOeaTq 04 aOTad UTUbTT bUTwTeTOaa ATquenbesgns pug bUTAOwaa }e pawTV ST SarboTougOa} asagq go go2a • swagsAs UOT4eweT3aa 94e24TT9 Pug 'wooa UaaaOs pasOTO 'UOTg2OT9TU5TT8p ua5Axo 30 U014eTT24SUT aqq apnTOuT TTTM saB=40 ssaooad •;uanT339 TTTW paIe814 90 d}TTenb aqq anoadwT 04 paubrsap aq TTTM A5OTOUgOaq sTg} go gOnW •TTTW aqq log ivawdinba Mau UT uOTTTTW OSZ$ awns 90 4u9w4TwwOD agaA ealgq a squaseadea weaboad sTgs •TTTW uO4u2o 8q4 go UOTgezTuaapow g g4TM pagooid oq quaquT s4T peounouue UOTdwegZ) '066T 'gOa2w a}PT u= se •oOT dT84ewrxoadde dq peonpaa uaa q q quanTgja TTTW uo}ugo pageaa} go aOTOO 91q4 'uebaq UOTgn4Tgsqns apTxoTp auTaOTgO aOUTS •UTxOTp 90 UOTgewaog agq TOa4UOO oq sueaw a se pazTUB00aa ST qO buTgOeaTq dTnd aog pasn autaOTgO aeTnoaTow 90 4unow2 eq4 ezTwTurw 04 pa4eT4TUT S2M UOT4eOT9TpOw STgy •abugs buTgOgaTq 4saT3 aqq UT pasn MOu ale apTxoTp aUTaOTgO pug auTaOTgO g4og •abg}S bUTgOeaTq gSaTg aq} UT apTxoTp auTaOTgD 90 asn aqq ageaodaoouT oq eouenbas buT4099N sqT p8T9Tpow TTTW U04u2O aqq '686T 'ATnr uI •abegs buTgOeaTq gsaT3 ag} UT 9UTIOTg0 aq4 90 awos log apTxoTp auTaOTgO buTgngTgsqns dq peonpaa aq u2o aOTOO }eqq sa}eOTpUT goaeasea 'gaodea 686T eqq UT paTTg}ap sV S8T a4ea4g TOa4uo0 aOTOZ) 4u9aan0 •Aaewwns e ST UOT400S g4anog aqq pug aeatt gsed aq} buTanp papnT=00 aaaM gOTgM suOTgenTeea A5OTOugO9q 9sOg4 sassnosrp UOT408s paTgq aqy •uOTdwego dq pagonpuoo buTaq SUOTgebT;SanUT dbOTOUgOaq TOaqu= aOTOO uo agepdn up ST UOT40as puoOas agy u paueTd ao aOT}Oead UT dTquaaanO s8r5OTOugOa4 _TOa4uOO aOT03 90 MaTnaa a ST UOT409S 4saT9 aqs •suoTgoas anog 04UT papTnTp ST gaodea agy •TTTW U04UPO 8q4 log 9=T1en euTT01e0 ggaoK a UT paTTe}ap s}uawaaTnbaa ag} g}TM aOuepaOOOe UT papTnOad ST gaodea aqy •TTTW uOWRO aq} log uOTgeaodaoc) TeuoTgeuaagU= uOTdwego Aq pagonpuoo suOTgebT}sanuT dbOTOUgO94 TOa}uOz aOTOO 90 gaodaa Tenuue puooas aq} ST gaodea sTgs 066T TTadY UOT4e5T4s8nul dbOTOUgOay Toaquoo aoToo quenTgja TTTW UOIUe0 'uOT4eaOdaOO TBUOTg2ua84u= UOTdwegD Color Control Technoloqv Investigation Up-date Color control technologies are divisible into two groups; those that reduce color at the source (i.e. in-mill process changes ) and those that treat color through end-of-pipe approaches. As discussed in the 1989 report and previously in this report, process changes which are considered feasible for color reduction at Canton have been incorporated into the mill modernization program. Champion is currently investigating four end-of-pipe color control alternatives. Two of the technologies are chemical treatments which involve an oxidation reaction to destroy the colored constituents in the wastewater. The other two technologies are separation processes which produce a color based sludge. Champion has purchased a laboratory scale pilot reactor to evaluate the use of ozone in combination with ultraviolet light as a decolorizing technique. Laboratory bench scale evaluations of this technology during the last year have been favorable enough to warrant further investigation. Color reduction work using this pilot reactor will begin in mid or late 1990 . A second oxidation technology under investigation involves the use of hydrogen peroxide in combination with ultraviolet light to decolorize wastewater. This technology is in the developmental stages and laboratory work is expected to continue through most of 1990 . Champion continues to study the Lignin Removal Process (LRP) . This separation process involves an acid precipitation of lignin in the presence of waste pulp fiber. The color sludge produced in the process must be disposed of. Bench scale testing will be the primary focus during 1990 . Champion is also currently evaluating the full scale use of polyamines for coagulating and separating lignin during primary clarification. This work is being conducted at Champion' s mill in Cantonment, Florida (near Pensacola, Florida) . The Cantonment Mill uses a series of lagoons for primary solids clarification, secondary treatment, and sludge management. As such, the wastewater treatment process is quite different than that used in Canton. Should this process prove viable at Cantonment, a similar evaluation will be conducted at Canton. In addition to the above technologies, Champion continues to evaluate the use of bacteria and enzymes capable of degrading lignin. �,uan Wun irnen is a�i mi..�i y�i aiwi i Technology Evaluations Concluded In 1989 Hansel Enterprises operated a laboratory bench scale color separation system during 1988 and 1989 . This work was partially sponsored through a Champion grant to the University of North Carolina at Asheville. The process is proprietary but uses common water treatment chemicals to accomplish a precipitation of lignin. Champion has received a final report of the work conducted by Hansel. Based on this report and prior evaluations of similar process, Champion has concluded that this process is not a feasible color control alternative for the Canton Mill. This conclusion is based largely on economic considerations and the complexity of the precipitation technology itself. Three other technology evaluations were concluded in 1989 . A color destruction technique involving the use of an electron beam, either alone or in combination with oxidants, was evaluated in 1989 . This technology was found to be ineffective when operated using a reasonably economic amount of power. A technology involving the use of ultraviolet light in combination with titanium dioxide was evaluated . After review of laboratory results and other published data, it became clear that the technology was not economically feasible. In 1988 , Ecotech Systems, Inc. asked Champion to evaluate a product known as Beta X-12 . Champion ' s intent to test this product was described in the 1989 report. However, Ecotech Systems elected not to evaluate the product ' s applicability to Canton Mill wastewater. Summary Initiation of chlorine dioxide substitution for chlorine provided an approximate 10% reduction in effluent color during 1989 . Champion has committed to a modernization of the Canton Mill which will reduce effluent color by more than 50% . During 1989 there were no new technological developments which would allow the Canton Mill to achieve a greater level of color reduction than is already planned. Research into alternative color control methods continues . A program is also in place to seek out promising new color control technologies . J - rlli Champion April 30 , 1991 Mr., Forrest Westall Regional Water Quality Supervisor NCDEHNR - Water Quality Section Asheville Regional Office 59 Woodfin Place Asheville, North Carolina 28801 Dear Mr. Westall: On July 13 , 1988 , the North Carolina Environmental Management Commission, through the NPDES Committee, issued Champion International Corporation' s Canton Mill a variance to water color criteria for the Pigeon River. The variance requires Champion to continue to study and evaluate color reduction technologies and annually report its findings to the Division of Environmental Management. Champion is pleased to submit the attached report in accordance with the variance requirement. If you have any questions, please call me. Sincerely, David F. Bonistall Environmental Supervisor Attachment Mr. Forrest Westall April 30 , 1991 Page 2 Copy: Mr. J. Ross Kilpatrick Vice President - Operations Manager Champion International Corporation P.O. Box C-10 Canton, North Carolina 28716 Mr. Richard Diforio Vice President - Environment, Health and Safety Champion International Corporation One Champion Plaza Stamford, Connecticut 06921 Mr. George Everett Director - North Carolina Department of Environment, Health and Natural Resources 512 North Salisbury Street Raleigh, North Carolina 27611 Champion International Corporation, Canton Mill Effluent Color Control Technology Investigation April 1991 This report is the third annual report of color control technology investigations conducted by Champion International Corporation for the Canton Mill. The report is provided in accordance with the requirements detailed in a North Carolina variance for the Canton Mill. The report is divided into four sections. The first section is a review of color control- technologies currently in practice or planned . The second section is an update on color control technology investigations being conducted by Champion. The third section discusses those technology evaluations which were concluded during the past year and the fourth section is a summary. Current Color Control Strategies Construction has started on the Canton Modernization Project with approximately 40% of the engineering completed at this time. This project represents a three year commitment of some $250 million in new equipment and technology for the mill. Much of this technology is designed to improve the quality of treated mill effluent. Process changes will include the installation of oxygen delignification, closing the screen room, and upgrading black liquor reclamation systems. Each of these improvements is aimed at removing and subsequently reclaiming lignin prior to bleaching. The reclaimed lignin will be returned to the mill ' s recovery system and burned. Planned changes in the bleaching area include additional chlorine dioxide substitution, completed in 1990 as part of the Dioxin Control Plan, and caustic extraction with oxygen. These approaches minimize the amount of color generated during pulp bleaching. Installation of these color control measures is expected to reduce treated effluent color to achieve compliance with the proposed NPDES permit. Color Control Technology Investigation UD-date Color control technologies are divisible into two groups; those that reduce color at the source (i .e. in-mill process changes ) and those that treat color through end-of-pipe approaches. As discussed in the 1990 report and previously in this report, process changes which are considered feasible for color reduction at Canton have been incorporated into the Canton Modernization Project. However, investigations Champion International Corporation, Canton Mill Effluent Color Control Technology Investigation April 1991 Page 2 -_-' continue to examine new and emerging technologies to prevent formation or to recycle and internally destroy the materials that produce color in bleach plant waste. Ozone bleaching is one area that is currently being investigated. Ozone is an undemonstrated technology for bleaching without molecular chlorine. As a strong oxidant, ozone can adversely affect pulp quality. Our investigations in this area will continue over the next several years. Champion is currently investigating four end-of-pipe color control alternatives. The technologies include chemical/oxidation reactions to destroy color constituents in the wastewater and separation processes which produce an additional sludge residue. During 1990 Champion conducted several pilot scale studies of various oxidation technologies including UV light in combination with peroxide, peracetic acid, Caro ' s acid and ozone. These investigations continue but require significant further development to determine whether they will be practicable as full scale options . Though advanced oxidation processes are being applied to a number of industrial systems, the volume and light absorbance of bleach plant effluents result in a qualitatively different application from the other industrial cases. Champion is continuing the evaluation of full scale use of polyamines for coagulating and separating lignin during primary clarification. Current investigations include studying the effects of polyamines on effluent toxicity and the dewatering characteristics of polyamine generated sludge. Additional chemical coagulation studies with a polymeric form of ferric sulfate are ongoing. Polyferric sulfate may offer some advantages in reducing color as well as TOC and BOD. However, the potential adverse effect on conductivity and sludge volume is being further investigated . In addition to the above technologies, Champion continues to evaluate the use of bacteria and enzymes capable of degrading lignin. The current state of this technology is still at the academic level. Through discussions with companies in the biotechnology field, enzymatic and biological approaches to delignification have yet to produce a commercial product specific for lignin degradation. Champion International Corporation, Canton Mill Effluent Color Control Technology Investigation April 1991 Page 3 Technology Evaluations Concluded In 1990 One technology evaluation was concluded in 1990. Results from the bench scale study of the Lignin Removal Process, an acid precipitation of lignin in the presence of waste pulp fiber, indicated that this technology was unable to achieve color removal levels achievable with other technologies. Summary The Canton Modernization Project includes process and equipment changes which will be sufficient to meet the proposed NPDES permit color requirements. Technology evaluations continue, from literature reviews to full scale trials . Champion continues to develop experience in alternative color control methods. �uau�Noe3gF suds/g0 aOSinzadnS TPgU9MUOaTnu3 UMOag 0T13aQ 'ATaiaoUTS ' 8TCZ-979 ( VOL ) ge am ZTPo asPaTd ' SUdTgsanb AuP anPq ncA 3I '4Uawa3Tnbaa aoueT3Pn aqg ggTM aouepa000P UT gaodea pagoeggE aqg gTmgns og paseaTd sT UOTdmPT4o •guau[abeuPW Te4u8u[U0aTAUg ;o UOTSTATG aqg 04 SbUTpuT; sgT gaodaa ATTenUua PUP satbOTOugOag UO gonpaa a0T00 agenTPna PUP �Cpngs og anUtgUoo Og UOTdnteg0 sasTnbaa a0UPTaen aqy •zanrg UOabtd aqg aO; PTiagizo a0T00 aageM og aoUeraen P TTTw uoguPo S,U0Tge30d30J TPU0T49Uaa4UI UOTduisgD pa * nSST '99441n00 S3QdN aqg gbnoagg 'UOTSSTMMOD gUamobeUPW TP4uaMU03TnU3 PUTTO.IPo ggsON aqg '886? ' Cl hTnr UO .TTPgsaM 'zN apao T08.8Z euTTOaPo ggsON 'aTTTnagsV aoeTd uT;P00M 65 90T;30 TeUOTbag aTTTnagsV UOT409S jC4TTeno aagPM - 2iNH3QJN aOSTnaadns dgiTenb a94PM TeUOTbaH TTPgsaM gsa-lao3 .-IN Z66T 'TZ TTadY UOl4UJDL— CD -_— .amnion ir.=mnonai wmoraiion Mr. Forrest Westall April 21 , 1992 Page 2 Copy: Mr. Richard Diforio Vice President - Environment, Health and Safety Champion International Corporation One Champion Plaza Stamford, Connecticut 06921 Mr. George Everett Director - North Carolina Department of Environment, Health and Natural Resources 512 North Salisbury Street Raleigh, North Carolina 27604 Mr. J. Ross Kilpatrick Vice President - Operations Manager Champion International Corporation PO Box C-10 Canton, North Carolina 28716 Mr. Steve Tedder, Chief Water Quality Section North Carolina Department of Environment, Health and Natural Resources Raleigh, North Carolina 27604 +.moron vn=rnaaona,k,aoc:ai cr Champion International Corporation Effluent Color Control Technology Investigation Canton Mill April 1992 This report is the fourth annual report of color control technology investigations conducted by Champion International Corporation for the Canton Mill . The report is provided in accordance with the requirements detailed in a North Carolina variance for the Canton Mill . The report is divided into four sections. The first section is a review of color control technologies currently in practice or planned. The second section is an update on color control technology investigations being conducted by Champion. The third section discusses those technology evaluations which were concluded during the past year and the fourth section is a summary. Current Color control Strategies Through March 1992, construction of the Canton Modernization Project (CMP) is approximately 42% complete. Engineering is approximately 85% complete. This project represents a three year commitment of some $290 million in new equipment and technology for the mill . The major focus of the CMP is to improve the quality of treated mill effluent. Process changes include the installation of oxygen delignification and upgrading the black liquor systems. Permanent shut-down of existing process equipment includes the C & D brownstock washing and bleach plants and the east set of black liquor evaporators. Each of these improvements are aimed at removing and subsequently recovering lignin prior to bleaching. The reclaimed lignin will be returned to the mill 's recovery system and burned. Planned changes in the bleaching area include 100% chlorine dioxide substitution and caustic extraction with an oxygen supplement. These approaches minimize the amount of color generated during pulp bleaching. Installation of these color control measures is expected to reduce treated effluent color to achieve compliance With the NPDES permit conditions now in effect. Color Control Technology Investigation U date Color control technologies are divisible into two groups; those that reduce color at the source ( i.e. in-mill Process changes ) and those that treat color through end- of-pipe approaches. As discussed in the 1991 report and previously in this report, process changes which are considered feasible for color reduction at Canton are incorporated in the Canton Modernization Project. _namojon irnemauona: _.;;OOranGr. Champion International Corporation, Canton Mill Effluent Color Control Technology Investigation April 1992 Page 2 Color Control Technology Investigation Update - continued However, Champion continues to examine new and emerging technologies to prevent the formation of materials that produce color in bleach plant effluent. Champion is also evaluating available technologies to recycle and internally destroy these materials. Extended delignification is a method of reducing the lignin content of the pulp prior to entering the bleach plant. Extended delignification requires a sequenced addition of pulping chemicals and the removal of solubilized lignin during the cook. However, extended delgnification offers only a marginal reduction in effluent color loads from a modernized Canton Mill with oxygen delignification. Champion continued evaluating ozone and other elemental chlorine-free bleaching technologies in the laboratory and through literature review. Reduced levels of chloride in bleach plant effluent may ultimately allow recycle of this effluent to the black liquor recovery system. Our investigations in this area will continue. Enzymes have been developed for application in pre- bleaching following oxygen delignification. Enzymes have the potential to marginally reduce color by degrading hemicellulose which allows pulp to be more readily delignified. Color reduction can be achieved if the enzyme filtrates can be recycled to the recovery process. Champion has participated in a trial of this process at our Cariboo Mill in British Columbia. To assess the technical and economic feasibility, future trials using enzyme are being considered at our Pensacola Mill . Champion is currently investigating end-of-pipe color control alternatives. The technologies include chemical/oxidation reactions which destroy color constituents in the wastewater; and separation processes which produce an additional sludge residue. During 1991 Champion continued to conduct pilot-scale studies of various oxidation technologies .including the use of ozone. The advantage of the oxidation approach is the elimination of a by-product sludge. We found that specific ozonation conditions have a significant impact on the quantity of ozone required to achieve a given decolorization level . These investigations continue but require significant further development to determine whether they will be practicable as full scale treatment ':aMMon in•o.nauonai Guocrauon Champion International corporation, Canton Mill Effluent color Control Technology Investigation April 1991 Page 3 Color Control Technolow invest 'aation Update - continued processes. Although advanced oxidation processes are being applied to a number of industrial systems, the volume and light absorbance of bleach plant effluents result in a qualitatively different application from the other industrial cases. Champion is continuing the evaluation of full scale use of polyamines for coagulating and separating lignin during primary clarification. We continue to study the effects of polyamines on the dewatering characteristics of polyamine generated sludge. Kemiron and Champion conducted a full scale trial of total mill effluent using Kemiron's proprietary grade of ferric sulfate in a proprietary process at the Pensacola Mill . A short "mini" trial was also conducted at the Canton Mill using one primary clarifier. "Poly" ferric sulfate is low in free acidity and therefore adds little or no conductivity to the treated effluent. However, effluent iron concentrations were elevated as a result of the "Poly" ferric sulfate treatment which may adversely affect effluent chronic toxicity. During the Canton Mill trial the color solids settled poorly in the primary clarifier and produced a sludge with poor dewatering properties. Both the large quantity of sludge generated and the poor sludge dewatering characteristics remain a major obstacle with precipitative color treatment technologies. Technology Evaluations Con hided Five technology evaluations are concluded in this report. FMC"" and Champion conducted pilot studies of peracetic acid and persulfuric acid oxidation of bleach plant effluent. Color oxidation performance of the pilot study indicated that this technology was unable to achieve color removal levels achievable with other technologies. Rolls Incorporated conducted an evaluation of bacteria and enzymes for the bio-degradation of lignin as discussed in the 1989 Report. No definitive results were received from this evaluation. Champion continues to follow the academic developments for the bio-degradation Of color; however, it appears the most promising application is in pre-bleaching as described above. -namion mrernauonat Corooracoo Champion International Corporation, Canton Mill Effluent Color Control Technology Investigation April 1991 Page 4 Technology Evaluations Concluded - continued The Stone Process consists of post-secondary mill effluent treatment with a polyamine coagulant and a polacrylamide flocculant in a dissolved air flotation clarifier. The Stone Process is practiced at several unbleached or partially bleached mills around the country. Champion is not able to support any advantage of the Stone Process over polyamine effluent treatment. Champion evaluated the use of UV light with peroxide in small-scale pilot tests at our Pensacola Mill . Although the technology appeared to perform as claimed on conventional mill (without oxygen delignification) effluents , performance on Pensacola Mill (with oxygen delignification) effluent was degraded to a level not economically feasible. Champion and Radiation Disposal Services (RDS) evaluated the use of ozone in combination with ultraviolet light (UV) as a decolorizing agent. The evaluations showed that UV had no effect on the degree of decolorization achieved by ozone alone. However, Champion continues to follow developments for the potential application of ozone treatment of mill effluent. SUMMARY The Canton Modernization Project includes process and equipment changes which are expected to meet the recently approved NPDES permit color requirements. Color technology evaluations continue, from literature reviews to full scale trials. Champion continues to develop experience in alternative color control methods. APPENDIX E PROCESS FLOW DIAGRAMS