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HomeMy WebLinkAboutNCD991278540_20010215_Weyerhaeuser Company_FRBCERCLA SAP QAPP_White Catfish Dioxin Data-OCR-• . .; ' UNITED STATES ENVIRONMENTAL PROTECTION AGENCY REGION 4 February 15, 200 I Richard Gay Environmental Manager Weyerhaeuser 810 Whittington Avenue Hot Springs, Arkansas 71901 Dear Mr. Gay: ATLANTA FEDERAL CENTER 61 FORSYTH STREET ATLANTA, GEORGIA 30303-8360 L. EPA received a letter dated November 13, 2001 from RMT. Inc. (RMT) on behalf of Weyerhaeuser. EPA appreciates the time and effort that went into RMT's review of white catfish data collected as part of the Lower Roanoke River Study currently being conducted by EPA. After reviewing RMT' s evaluation of the data, EPA found no evidence of analytical or sampling error related to sample RR436WCC or RR436WCF. However, due to the possible anomalously high levels in the fillet relative to the carcass, an additional investigation to confirm these results should be perfom1ed. The catfish dioxin data will enable characterization of the distribution of dioxin TEQ in exposed catfish in the section of the Roanoke River corresponding with previous sample composite location RR436. The resulting data will be used to replace the previous RR436 data for purposes of human health risk assessment. The sampling and analysis plan provided below provides a potential approach for such a confirmation investigation should Weyerhaeuser wish to conduct such an investigation. Please find attached a detailed dioxin data review by EPA Region 4's Office of Quality Assurance and Data Integration and an assessment by Dr. Russell Plumb. Background White catfish sample RR436WCF, collected in June 2000 in the Roanoke River immediately downstream of the confluence with Welch Creek, was the fillet portion of a composite of five white catfish. This sample contained high concentrations of dioxin (TEQ = 26 ppt) relative to the corresponding carcass portion (TEQ = 5.3 ppt) and other catfish fillet and carcass composites collected upstream and downstream of this location (TEQs ranging up to 4.2 ppt). It is unknown whether the RR436WCF dioxin TEQ concentration is anomalous due to possible analytical or sampling errors or whether the dioxin TEQ concentration in this sample reflects actual biological and physical phenomena related to habitat proximity to Welch Creek, a known source of sediment dioxin contamination. Independent laboratory data quality reviews by Weyerhaeuser and EPA have disagreed on this issue; however. there does not appear to be _any evidence to indicate an analytical problem for this sample. Nevertheless, both parties recognize the unusual result whereby higher dioxin TEQ concentrations are measured in fish fillet tissue relative to the remainder (carcass) of a fish; this is based on the concept that dioxins should tend to accumulate in the more "fatty" carcass tissues. Internet Addruss (URL)• http://www.n~a.gov R~,;yc1tr.:VRecyclable • PrinfGd wilh Vegetable Oil B,1sod Inks on Aecycl,Jd r,apor (Mtn,mum :JD% Postcon~umer) ;1!)! 1•J, :' •h I , iON • • -2- Sampling and Analysis Plan The objective of the investigation, if implemented, would be to confinn dioxin TEQ concentrations in white catfish tissue in the area at and/or near previous sample location RR436. The confinnation results would form a new set of data for characterization of the distributional form of dioxin TEQ and for assessment of human and ecological risk in the area of RR436. In order to provide reasonable coverage of the uncertainty associated with the biological and habitat phenomena related to dioxin bioaccumulation in white catfish, i.e., a statistically sound basis, a new set of multiple tissue samples a!_ multiple locations (corresponding with the proximity of RR436) will need to be collected. This is necessary since it is not possible to resample the "same" RR436 fish composite (i.e., under the same set of biological and physical factors) and simply replace the current RR436WCF observation in the data set with a new RR436WCF observation. We simply do not understand the factors and their interactions well enough to replace the composite observation with another composite observatio_n, and have sufficient confidence that the new observation will be representative of the complex phenomena responsible for dioxin bioaccumulation in catfish. In particular, we do not have sufficient infonnation regarding the type and shape of the distribution of dioxin TEQ in catfish in the area of RR436. Currently, all we have is one observation (a 5-point composite) indicating that the mean dioxin level in white catfish fillets in this area is TEQ = 26 ppt. Since this is a composite. we have no infonnation regarding the dispersion of TEQ about the mean. For example. it could be that all five catfish had TEQ = 26 ppt, or that four of the five had TEQ = 0 ppt and one of the five had TEQ = 130 ppt, or any other combination that produces a mean TEQ = 26 ppt. Therefore, it is impossible to estimate based on normal or lognonnal distribution models how many observations would be necessary to characterize the phenomena. For purposes of this sampling plan it is assumed that at least 15 observations will be necessary to adequately characterize the distribution of dioxin in fish tissue due to exposure in the vicinity of the Roanoke River impacted by Welch Creek. It is also assumed that a minimum of five locations in the Roanoke River will be selected for sample collection. One of these locations should be upstream and four downstream of the confluence with Welch Creek. The five locations should be separated approximately 500, 1,000 or 2,000 feet (see below), and they should be restricted to the south side of the river, i.e., in the shallow water on the same side of the river where Welch Creek flows into the river, since this environment represents the catfish habitat where exposure to dioxin contaminated sediments from Welch Creek are most likely. The required sample locations are as follows: Location ID RR436B1 RR436B2 RR436B3 RR436B4 RR436B5 Location Description (relative to Welch Creek confluence) 0 -500 ft upstream 0 -500 ft downstream 500 -1,000 ft downstream 1,000 -2,000 ft downstream 2,000 -4,000 ft downstream • • -3- From each of the five locations, a minimum of two (2) individual white catfish should be collected, for a total of 2 x 5 = 10 catfish. Compositing of these samples is not desirable. If more than 2 white c·atfish are obtained from an individual location, all will be prepared and sent to the laboratory. The laboratory will randomly select two fish for analysis and archive the remaining samples for later analysis, if required. If less than 2 catfish are collected during an event, additional sampling using either electroshock or line-and-hook methods will be necessary. Each individual sample will be separated into fillet and carcass portions and submitted for separate dioxin analysis following the field and analytical protocols of previous investigations. The minimum number of total dioxin analyses is therefore 2 x 10 = 2Oanalyses. Analysis Requirements Dioxin analysis must follow SW-846 Method 8290. For fish tissue, this method requires a minimum sample size of 20 g (bulk or wet weight). Since even a small catfish is expected to weight about I 00 g, of which about 25 g will be the fillet portion (both left and right fillets combined), there should be no problem with collecting and analyzing individual fish for dioxin, i.e., there is no analytical requirement for compositing the samples to obtain an adequate sample size. Analytical protocols must include the prescribed types and numbers of field quality control/quality assurance samples, including duplicates ( l per 20), decontamination rinsate blanks, and performance evaluation samples. as necessary and appropriate. Please contact me at 404.562.8814 to discuss the letter in more detail. Thank you for your consideration of this matter. Sincerely, /')/·/!_,II I Y.t;;, {~kl Lt e1 ,__, Beth 0 \Vaiden Remedial Project Manager . cc: Tom Augspurger, USDOI Nile Testerman, NCDENR Luann Williams, NCDHHS Stacy McAnulty, RMT • • UNITED STATES ENVIRONMENTAL PROTECTION AGENCY SCIENCE AND ECOSYSTEM SUPPORT DIVISION OFFICE OF QUALITY ASSURANCE REGION IV 980 COLLEGE ST A TION ROAD A THENS, GA 30605 4SESD-OQA MEMORANDUM SUBJECT: Lower Roanoke River White Catfish Dioxin Data Project 00-0589 Weyerhaeuser Company FROM: THRU: TO: Re-examination of Samples RR436WCF and RR436WCC John P. McConney yjtl L, <.::..s. Environmental Scientist Office of Quality Assurance and Data Integration Gary Bennett, Chief J!/zl, Office of Quality Assurance and Data Integration Beth Walden, Remedial Project Manager Waste Management Division ..... On behalf of Weyerhaeuser Company, RMT, Inc. (RMT) conducted a laboratory data quality review of white catfish dioxin analytical data, specifically subject samples RR436WCF and RR436WCC of Project 00-0589. RMT concluded that the analytical results are unreliable due to laboratory QC problems and are likely due to some type of laboratory contamination. Our re-examination of the subject analytical data showed that the data were appropriately qualified and that the laboratory QC problems do not significantly affect the usability of the data. The conclusions reached by RMT will be addressed in the order presented in their memorandum dated November 13, 2001. I. Laboratory Method Blank contamination -While the associated method blank did contain positive results for all 2378-substituted congeners except TCDD, these blank results were used to qualify the results of all of the associated samples including RR436WCF and RR436WCC. Data qualification was performed in accordance with established organic and dioxin data validation procedures and Region 4 SOP; the 5X blank rule was used. The method blank was analyzed immediately after the continuing calibration and two hours prior to the analysis of the associated samples. While it is possible carryover from the calibration analysis affected the method blank, this carryover was not present in the • • system when the subject samples were analyzed, as evidenced by the results of the two samples analyzed between analysis of the method blank and subject samples. It should be noted that the analytical results included by RMT in Table I did not reflect the qualified results as reported by Region 4. See Exhibit # I for blank results, Region 4 reported results, RMT's Table 1, and see Exhibit #2 for Region 4 reported results of the two samples analyzed between the method blank and subject samples. 2. CarryoveF-from the laboratory blank spike -RMT stated that the laboratory blank spike and method blank were analyzed in sequence immediately before the subject samples and that ca!D'over of the spike compounds was therefore IJ.O~sible. Examinat.ion. of the analysis run log shows that in fact the laboratory blank spike was analyzed three hours after the subject samples were analyzed. Carryover of the spike compounds was therefore not possible. Moreover, the sample analyzed immediately prior to the subject samples did not contain reportable amounts of any target compounds and the sample analyzed immediately prior to that sample contained only 2,3,7,8-TCDD in an amount less than the detection limit. Therefore, it is not possible that carryover to the subject samples occurred. See Exhibit #2 for the analysis run log, Region 4 reported results and selected SICPs of the subject samples as well as the samples analyzed immediately before the subject samples. 3. Inconsistency between the subject samples was most likely caused by fugitive contamination -As stated above, while contamination was present in the associated method blank, the reported results of the subject samples were greater than 5 times this contamination. In addition, the samples analyzed immediately before the subject samples did not contain reportable amounts of target compounds that were greater than the detection limit. Therefore, there is no evidence that the analytical system was compromised by fugitive contamination to such an extent as to affect the reported results of the subject samples. 4. The accuracy and precision of the MS/MSD associated with the subject samples was inconsistent and poor -The results of the MS/MSD associated with the subject samples show that the RPO of only two of the seventeen spike compounds exceeded the method QC limits. The method QC limit for the RPO was 20%; the RPO of 1,2,3,7,8,9-HxCOF. was 21 % and 1,2,3,4,7,8,9-HxCOF was 29%. However, it must be noted that neither of the subject samples was used for the MS/MSO sample; the sample used for the MS/MSO was RR449LBF. In accordance with established organic and dioxin data validation procedures and Region 4 SOP, qualification resulting from the results of the MS/MSO are only applied to the sample used for the MS/MSO and not to associated samples. This is due to the variable nature of the matrices analyzed. In addition, subject sample RR436WCC was analyzed as a laboratory duplicate and all of the RPO values were below 10%, which is well below the method QC limit of25%. The internal standards in the original and duplicate analyses of subject sample RR436WCC also showed good agreement. This agreement and the low RPD values indicates that this sample was not subject to the same matrix interference that sample RR449LBF was subject to. Therefore, the MS/MSO results have little if any bearing on the results of the subject samples. See Exhibit #3. • • In summary, based on our re-examination of the raw data associated with the subject samples, we can find no information which supports the theory that dioxin and furan results reported for samples RR4_36WCF and RR436WCC were due to laboratory contamination for the following reasons: ► The method blank contamination which was noted by RMT as a significant problem, was observed by EPA data reviewers and was appropriately handled prior to reporting the data in accordance with EPA data review standard operating procedures. ► There is no evidence of cross contamination ( carryover) of the subject samples by the laboratory blank spike because the spike was analyzed after samples RR436WCF and RR436'WCC in the analytical sequence. ·· • _ ► The samples analyzed immediately before samples RR436WCF and RR436WCC in the analytical sequence do not show elevated levels of dibenzofurans or dibenzodioxins as would be expected if some type of instrumental cross contamination had occurred. Please contact John McConney at 706-355-8555, or Gary Bennett at 706-355-8551 if you have any questions. l.Jlbotaloty lO 039969 EPA ID Melhod blank SOG RR-44~WCC CXlullon F aaor % Moislure ~ WeighlNolume 10.000 FV 20 .,._ Injection Volume 10 ,, . H•tlve Come,ounds JJ71-Ft.nna ion, o, ....... ,.,.,. ...,..,.., R.T . 2.3.7,&-CM-Obenzoflnn JOJ IOII 27:23 ..... ._.,,.,_,,,,JJ ..... 27;24 77324 1.2.J.7 .a-O~Oibenzofinn lll 1517 34:5-4 2616-41 ._.,.., .. ,.. J,11.~ 34:5-4 181905 2.3.4,7,a-ct~~inn u,a,; . · 36:03 290865 --•JS••-••1""11 ,., .... 36:02 183145 1.2.3.4,7.e-o&-Oiberu:ohnn ln.azar 39:42 3162911 --•»•••.a JUll71 39:42 268000 1,2,3.S.7,8-06-0oenzofuran l7l l207 39:49 363449 "-•»U•-llpllltf) ns 1111 39:49 256000 2.3,4.8, 7 .a-o&-Obel'IZofuran 1n l207 40:24 mooo _..,. ... ,, ... »CN(YJ 17S.1171 40:24 3172-47 1.2.3. 7 .8.t-06-0Lbenzofuran 1nmr 41:10 378930 -...■•111o••apllltf) US1171 41:10 32UM6 1.2,3.U.7,a-07-Dlt>eru:~inn 407.1111 42:51 346280 -...■Ud•"-1:Ei «-.n11 42:50 ,...,. 1.2,3,4, 7 .8, 9-07-Dlbenzoti.-n •01.1111 44:21 309000 "-.......... (MT! •011n11 44:21 260000 1.2.3.4.11,7 ,11.9-05-0.bel'IZofuran •.U.1CH 47:39 583164 "-•OZJ•dll(MT} UJ.7lN 47:39 641557 :IJ71-DJa.lns 2,3, 7 .8-CM-Obenzo-p-dl(wn JttllllS ...... R-.,•H.lllllH.lt 121.1131 • 53500 1,2,3,7,1-0S-Oibenzo-p-dioxit\ ....... 36:34 181395 "-••:111o»• J.57.1517 35:33 105000 1.2,3. 4,7 ,8-CJ6.0.beN:o-p-,dlo1dn Ut.t1k 40:33 247537 "-•OOJC11o•.a(MT! ltUUt 40:33 193000 1.2,3,8,7,8-Cl&-OiberU:~ llll Ilk 40:43 198917 ......... "'!, ltl.1117 40:44 164000 1,2.3, 7 .8.9-05-0lbenzo-p-dlcwn Jll11k 40:56 2771!155 ............ Jl1 1121 40:56 21'1711 1,2,3,U,7 .&-Cl7 •CWbenzo-p-dioain •n.nu 43:54 , ..... -..■uu•u• m.mr 43:54 362221 1,2,3,4.1,7 ,8,9-Cl&-O.benZo-p-dioaln 01.nn 47;28 797521 "-.. , .... ,. 01.7~1 47:21!1 .,., .. Philip Analytical Services EPA Method 8290 • {ppt) Sample Receipt Date OOAJ7/21 Exlfactlon Date 00/08113 tnjeclion Dale 00108129 Injection Time 13:53 F~e Natne 29AUG EPA041 CodH EMPC • Estimated Maximum Posslble Concenttallon OPE " Poulble Diptien)'lether lnl_erference (Furans)I NOR = Nol Delected Due lo lncoaect Isotope Ratio ■ RT• Relenllon Time not Wllhan ·1 lo •3 &econd window C • Confirmation Resull ltom OB-'225 column EMCL • &.ceeds Method Cabbralion Limit Rotio SIN Total Amounl NU (wt) Code TEF 0.78 • 1362651 0.78 0.078 .~ .. • 1.44 10 443448 u 0.189 1122-11WJ 10 1.59 12 474010 u 1JM2 (lll-ll'll " 1.18 " ... ,.. '·' 0.449 11•1•:11 " 1.42 IS 619449 ... 0.477 IIOloUll " 1.11 IS 670247 u 0.643 ,, .. ,._ " 1.18 IS 700876 ,., 0.155 11-.u:11 " o ... 20 714735 ... 0.069 ,.. .. ,~ 20 1.19 " 569000 1.0 0.080, 111•1J111 IS 0.91 26 1224721 17 0.017 flll'l-101) 25 .. .. -94159 ,c 0.1 -c0.772 flllWIIII .. 1.73 • 286395 .J.01 1.540 1111-1n1 1 1.28 " 440537 ·~ 0,516 1101-1•:11 12 1.21 10 362917 4.0◄ 0,404 (I Ol-14,JJ 11 120 " 4975611 ,.o 0.498 °:: ,, .. ,.,. " 1.01 " 728793 ••• 0.0!5 .... ,Jill ,. 0.95 ,. 1634279 " 0.024 ior..111Z) ,. 0 -·~-- I I RRF• 1.15 0.85 0.79 1.08 1.00 0.87 0.11 1.07 0.74 1.07 0.08 0.88 0.79 0.03 0.92 1.00 0."7 FIie : (0112SEPA.xt.WJ0399119 EPA molllnk_0813 • 0 c:, '3 .:,.. u, • EPA Method 8290 • (ppt) Sample Recelpl Date OD.(17/21 -U--Ub<ntcwy 10 039969 Extr1iction Dau, 00/08113 EPA ID Method blanll Injection Dale OQ108129 SOG RR-449--'NCC lnjectton rme 13:53 ' F~e Name 29AUG EPA041 Odulion F ■ctor % Moisture .. Cod■-EMPC • Estimated Ma:dnun POSSlble Cencentration · Weighl/Votume 10.000 OPE ■ Possible Oiphenytelher ln!erferenc■ (F~) FV 20 VL NOR ■ Not Detected Due to loco(rect Isotope lnjectionVolume 1.0 VL RT• Retention Twne not wilhln •1 lo +3 5econcl window I I C • Conlitm■llon Result from Ofr-225 column EMCL • Excffds Method Calibr■lion Umll lnlem■I Standards Ions """""" ,.,., Rollo SIN Total Amount %RECOVERY RRF, ,.,, .. MonllO< .. R.T. ""' Mcie<! (pg} • 2.J.7.&-T4COf-13C12 J1Skll 27:20 32966300 0.77 1271 75008000 2500 " 121 JU.l)N 27:20 428-41700 C11H•1 1140 1.2.J,1,&-P5C0f-13C12 ...... 34:52 ◄7700000 1.62 250< 77200000 2500 " 1.28 )5)1170 34:52 20500000 (IJ.1·•1'1 .,. 1.2,3,4.1 .&-H&COF-13C12 ,.,..,. 39;41 52305900 0.53 '"" 150167500 6250 .. 121 •• ,o, 39:41 97561600 , .. w., 4614 1,2,3,◄,l,7.&-H7COF-13C12 4111251 42:50 36321300 0.0 1535 120173200 6250 .. 0.97 41IIZ20 42:50 1131151900 fllll.OUI 2478 Oloxln• 2.l,7 ,&-T4C00-13C12 llt .... 211:34 36025000 0 ... 623 89232300 2500 .. 12e I ""'" 21!1.34 53206500 telH•I 15'4 C 1.2.l,7 ,&-PSC00-13C12 ,., .... 36:32 32123300 1.55 1574 52790600 2500 " 0.72 C *"" 36:32 20667300 11.1,2.111,1 1004 ..... t,2,3.11, 7 .&-H&C00-13C 12. 401.1551 40:37 75050800 12, .. ,. 135353200 6250 " 1.00 403115:,0 ◄0:37 60302400 ,, .. ,o, 2964 .., 1,2.3.4.8.7 .&-tf7C00-13C 12 USIIN 43:53 54676300 1.05 ••◄4 106970900 6250 .. 0.75 0-nr.1uo 43:SJ 52294600 te•' ») ,.., OC00-13C12 Hl.71IO 47:27 80228700 o ... 6719 1730:M400 12500 .. 0.81 01.71)0 ◄7:27 92805700 '°""'121 8926 Recove!Jt: Standards 1,2,l,◄·HCOO 1JC.12 lll .... 28:U 25550200 0.71 473 61754600 1000 • "'"" 28:14 36204400 ,otw•1 1108 1,2.3,7,8,9-H&COO llC-12 '01.ISH ◄0:56 2"03200 125 1724 ,...,... 1000 ..,..,. 40:56 18079700 11 -.1431 '" An•!x•t Comments Philip Analytical Services FIie : l01!129EPA.XLW}039969 EPA mblank_01!113 IIOXINS SAMPLE ANALYSIS EPA -REGION IV SESD, ATHENS, GA Sample 10066 FY 2000 Project: 00-0589 .DIOXIN SCAN Facility: Weyerhaeuser Company Program;_ SFE Plymouth, NC Id/Station: RR436WCC / Media:OTHER BIOTA D No:436WC RESULTS 4.3 4.3J 8.9U 8.9UJ 8.9U 8.9U 8.9U 23UJ 29U 120J 460 4.7 4.9J 8.9U 8.9U 8.9UJ 8.9U 8.9U 8.9U 8.9U 8.9UJ 8.9U 8.9U 8.9UJ 18U 5.3 8.7 UNITS NG/KG NG/KG NG/KG NG/KG NG/KG NG/KG NG/KG NG/KG NG/KG NG/KG NG/KG NG/KG NG/KG NG/KG NG/KG NG/KG NG/KG NG/KG NG/KG NG/KG NG/KG NG/KG NG/KG NG/KG NG/KG NG/KG % ANALYTE 2,3,7,8-TETRACHLORODIBENZODIOXIN TETRACHLORODIBENZODIOXIN (TOTAL) 1,2,3,7,8-PENTACHLORODIBENZODIOXIN PENTACHLORODIBENZODIOXIN·(TOTAL) 1,2,3,4, 7,8-HEXACHLORODIBENZODIOXIN 1,2,3,6, 7,8-HEXACHLORODIBENZODIOXIN 1,2,3, 7,8,9-HEXACHLORODIBENZODIOXIN HEXACHLORODIBENZODIOXIN (TOTAL) 1,2,3.4,6,7,8-HEPTACHLORODIBENZODIOXIN HEPTACHLORODIBENZODIOXIN (TOTAL) OCTACHLORODIBENZODIOXIN 2,3,7,8-TETRACHLORODIBENZOFURAN TETRACHLORODIBENZOFURAN (TOTAL) 1,2,3,7,8-PENTACHLORODIBENZOFURAN 2,3.4,7,8-PENTACHLORODIBENZOFURAN PENTACHLORODIBENZOFURAN (TOTAL) 1,2,3.4,7,8-HEXACHLORODIBENZOFURAN 1,2,3,6,7,8-HEXACHLORODIBENZOFURAN 1,2,3,7,8,9-HEXACHLORODIBENZOFURAN 2,3.4,6,7,8-HEXACHLORODIBENZOFURAN HEXACHLORODIBENZOfURAN (TOTAL) 1,2,3.4,6, 7,8-HEPTACHLORODIBENZOFURAN 1,2,3,4, 7 ,8,9-HEPTACHLORODIBENZOFURAN HEPTACHLORODIBENZOFURAN (TOTAL) OCTACHLORODIBENZOFURAN TEO (TOXIC. EQUIV. VALUE, FROM 1-TEF/89) % LIPIDS SAS Number:DIOX Org Contractor: PAS -average value. NA-not analyzed. NAl-interferences. J-eslimated value. N-presumptive evidence of presence of material. Production Date: 10/18/2000 12:49 Produced by: Mcconney, John Requestor: Project Leader: BLEWIS. Beginning: 06/21/2000 12:00 Ending: I I -actual value is known to be less than value given. L-actual value is known ta be greater than value given. U-material was analyzed for but not detected. the number is the minimum quantitation limit. -qc indicates that data unusable. compound may or may not be present. res"arnpling and rea'nalysis is necessary for verification. Page 1 of 1 • DIOXINS SAMPLE ANALYSIS EPA -REGION IV SESD, ATHENS, GA Sample 10067 FY 2000 Project: 00-0589 DIOXIN SCAN Facility: Weyerhaeuser Company Program:_ SFE Plymouth, NC Id/Station: RR436WCF / Media:OTHER BIOTA D No: 436WC RES UL TS UNITS 4.5 59J 8.5U 41UJ 8.5U 8.5U 8.5U 48UJ 24U 50J 100U 27U 110J 24 20 190J 67 26 8.5U 8.5U 180J 74 12U 97J 31U 26 4.0 NG/KG NG/KG NG/KG NG/KG NG/KG NG/KG NG/KG NG/KG NG/KG NG/KG NG/KG NG/KG NG/KG NG/KG NG/KG NG/KG NG/KG NG/KG NG/KG NG/KG NG/KG NG/KG NG/KG NG/KG NG/KG NG/KG % ANALYTE 2,3, 7 ,8-TETRACHLORODIBENZODIOXIN TETRACHLORODIBENZODIOXIN (TOTAL) 1,2,3, 7 ,8-PENTACHLORODIBENZODIOXIN PENTACHLORODIBENZODIOXIN (TOTAL) 1,2,3,4, 7 ,8-HEXACHLORODIBENZODIOXIN 1,2,3,6, 7,8-HEXACHLORODIBENZODIOXIN 1,2,3, 7,8,9-HEXACHLORODIBENZODIOXIN HEXACHLORODIBENZODIOXIN (TOTAL) 1,2,3,4,6,7,8-HEPT ACHLORODIBENZODIOXIN HEPTACHLORODIBENZODIOXIN (TOTAL) OCTACHLORODIBENZODIOXIN 2,3, 7 ,8-TETRACHLORODIBENZOFURAN TETRACHLOROOIBENZOFURAN (TOTAL) 1,2,3,7,8-PENTACHLORODIBENZOFURAN 2,3,4, 7 ,8-PENTACHLORODIBENZOFURAN PENTACHLORODIBENZOFURAN (TOTAL) 1,2,3,4,7,8-HEXACHLORODIBENZOFURAN 1,2,3,6,7,8-HEXACHLORODIBENZOFURAN 1,2,3,7,8,9-HEXACHLORODIBENZOFURAN 2,3,4,6,7,8-HEXACHLORODIBENZOFURAN HEXACHLORODIBENZOFURAN (TOTAL) 1,2,3,4,6,7,8-HEPTACHLORODIBENZOFURAN 1,2,3,4, 7 ,8,9-HEPTACHLORODIBENZOFURAN HEPTACHLORODIBENZOFURAN (TOTAL) OCTACHLORODIBENZOFURAN TEO (TOXIC. EQUIV. VALUE, FROM I-TEF/89) % LIPIDS SAS Numtier:DIOX Org Contractor: PAS !\-average value. NA-not analyzed. NAl-interferences. J-estimated value. N-presumptive evidence of presence of material. Production Date: 10/18/2000 12:49 Produced by: Mcconney, John Requestor: Project Leader: BLEWIS Beginning: 06/21/2000 12:00 Ending: I I -<-actual value is known to be less than value given. L-actual value is known to be greater than value given. U-material was analyzed for but not detected. the number is the minimum quantitation limit. ~-qc indicates that data unusable. compound may or may not be present. resampling and reanalysis is necessary for verification. Page 1 of 1 • • Table I 2,3,7,8-PCDD/PCDF in the Roanoke River White Catfish Samples, Blank Spike, and Blanks RR-RR RR BLANK METHOD SYSTEM SYSTEM METHOD Sample ID 436WCC 436WCCDuo ¾RPD 436WCF SPIKE BLANK BLANK BLANK BLANK Labontory Sample # 39970 39970 39971 39969 39969 39948 Collection Date 6/21/00 6/21/00 6/21/00 I Analysis Date 8/29/00 8n9too 8n9/oo 8/29/00 8/29/00 g/30/00 I 8/31/00 8/17/00 PARAMETER 2,3,7,8-TCDD, ng/kg 4.3 4.7 9 4.5 78 <0.77 <0.7 <0.6 <1.4 1,2,3,7,8-PeCDD, ng/kg 1.2 u 1.4 u nd 6.8 u 210 . 3.1 1.6 2.3 <2.1 1,2,3,4,7,8-HxCDD, ng/kg 1.00 u I.Ou nd 3.3 u 250 5.2 3.0 2.6 <1.5 • 1,2,3,6, 7 ,8-HxCDD, ng/kg 2.3 u 3.0 u nd 8.1 u 210 4.0 3.1 3.3 <1.4 1,2,3,7,8,9-HxCDD, ng/kg 1.4 u 1.5 u nd 6.4 u 210 5.0 2.9 3.5 .. <1.3 1,2,3,4,6,7,8-HpCDD, ng/kg 29 u 30 u nd 24u 210 8.5 5.2 5.6 3.1 OCDD, ng/kg 460 470 2 100 u 450 24 16 17 11 2,3,7,8-TCDF, ng/kg 4.9 5.02 2 27 93 0.78 0.88 0.94 <I. I 1,2,3,7,8-PeCDF, ng/kg <0.54 0.45·u nd 24 220 . 3.4 2.05 2.4 <1.5 2,3,4,7,8-PeCDF, ng/kg 0.93 u 1.0 u nd 20 u 250 3.9 2.8 3.0 <1.6 1,2,3,4,7,8-HxCDF, ng/kg <0.47 <0.44 nd 67 240 4.5 3.0 3.4 2.3 1,2,3,6, 7,8-HxCDF, ng/kg <0.47 <0.44 nd 26 230 4.8 2.8 3.4 2.4 2,3,4,6,7,8-HxCDF, ng/kg <0.59 <0.54 nd 7.9 u 220 6.4 3.8 4.5 <1.7 1,2,3,7,8,9-HxCDF, ng/kg <0.66 <0.61 nd 1.2 u 210 1.5 ; 4.5 4.4 <1.4 1,2,3,4,6,7,8-HpCDF, ng/kg <0.97NDR <0.76 nd 74 280 6.9 4.0 4.8 3.7 1,2,3,4,7,8,9-HpCDF, ng/kg <0.67 <0.6 nd 12 u 230 8.0 4.0 6.4 3.2 OCDF, ng/kg <0.98 <0.98 nd 31 u 300 17 9.4 9.8 6.6 • Total TCDD, ng/kg 4.3 4.7 9 59 78 <0.77 <0.71 <0.65 <1.4 Total PeCDD, ng/kg 1.2 u 1.4 u nd 41 210 3.1 1.64 2.31 <2.1 Total HxCDD, ng/kg 23 25 8 48 680 14 S.99 9.47 <1.4 Total HpCDD, ng/kg 120 110 9 50 220 8.5 6.16 5.60 3.1 Total TCDF, ng/kg 4.9 5.0 2 110 95 3.2 0.88 0.94 <1.1 Total PeCDF, ng/kg 4.8 5.0 4 190 480 7.2 4.84 5.30 <1.5 Total HxCDF, ng/kg <0.54 <0.50 nd 180 920 23 13.72 15.49 5.4 Total HpCDF, ng/kg <1.2 <0.49 nd 97 530 15 7.99 11 7.0 Notes: NOR= analytc not detected due to inco1Tect isotope ration. l:\wpmSn\PJT\00-05112\14\000511214-002.XLS 11129/01 '29AUG_EPA Resolution Check 00/08/29 · 11:13 FUNCTION START END db5_win_perf 00/08/29 11 :15 1 20:00 30:45 solvent 00/08/29 12:06 2 30:45 37:40 cs3_epa_196 00/08/29 12:57 3 37:40 41:30 epa39969_mblank_0813 00/08/29 13:53 4 41:30 44:40 epa39967 _rr_ 436_lbc 00/08/29 14:43 5 44:40 48:10 epa39968_rr_ 436_ran 00/08/29 15:34 I I epa39970_rr_ 436_wcc 00/08/29 16:25 epa39970d_rr_ 436_w~~ 00/08/29 17:15 epa39971_rr~,wcf 7/; 7,{~ N/0/0} 00108/29 18:06 • epa39972_rr_ 440_cor • · 00/08/29 18:56 epa39973_rr_ 440_fir 00/08/29 19:47 epa39974_rr_ 440_1bc 00/08/29 20:38 epa_blkspk_0813 00/08/29 21:28 cs3_epa_197 00/08/29 22:19 solvent 00/08/29 23:10 Resolution Check 00/08/30 7:47 • Page 1 IUXIN:S :SAMt'LI:: ANAL Y:Sl:S EPA -REGION IV SESD, ATHENS, GA Sample 10064 FY 2000 Project: 00-0589 DIOXIN SCAN Facility: Weyerhaeuser Company Program:_ SFE Plymouth, NC ld/Stalion: RR436LBF / Media:OTHER BIOTA D No: 436LB RESULTS 1.6J 1.6J 8.5U 8.5UJ 8.5U 8.5U 8.5U 8.5UJ 8.5U 8.5UJ 17U 3.4U 3.4UJ 8.5U 8.5U 8.5UJ 8.5U 8.5U 8.5U 8.5U 8.SUJ 8.5U 8.5U 8.5UJ 17U 1.6J 0.5 UNITS NG/KG NG/KG NG/KG NG/KG NG/KG NG/KG NG/KG NG/KG NG/KG NG/KG NG/KG NG/KG NG/KG NG/KG NG/KG NG/KG NG/KG NG/KG NG/KG NG/KG NG/KG NG/KG NG/KG NG/KG NG/KG NG/KG % ANALYTE 2,3,7,8-TETRACHLORODIBENZODIOXIN TETRACHLORODIBENZODIOXIN (TOTAL) 1,2,3, 7,8-PENTACHLORODIBENZODIOXIN PENTACHLORODIBENZODIOXIN (TOTAL) 1,2,3,4,7,8-HEXACHLORODIBENZODIOXIN 1,2,3,6, 7 ,8-HEXACHLORODIBENZODIOXIN 1,2,3, 7 ,8,9-HEXACHLORODIBENZODIOXIN HEXACHLORODIBENZODIOXIN (TOTAL) 1,2,3,4,6,7,8-HEPTACHLORODIBENZODIOXIN HEPTACHLORODIBENZODIOXIN (TOTAL) OCTACHLORODIBENZODIOXIN 2,3,7,8-TETRACHLORODIBENZOFURAN TETRACHLORODIBENZOFURAN (TOTAL) 1,2,3, 7,8-PENTACHLORODIBENZOFURAN 2,3,4,7,8-PENTACHLORODIBENZOFURAN PENTACHLORODIBENZOFURAN (TOTAL) 1,2,3,4,7,8-HEXACHLORODIBENZOFURAN 1,2,3,6, 7,8-HEXACHLORODIBENZOFURAN 1,2,3, 7,8,9-HEXACHLORODIBENZOFURAN 2,3,4,6,7,8-HEXACHLORODIBENZOFURAN HEXACHLORODIBENZOFURAN (TOTAL) 1,2,3,4,6, 7 ,8-HEPTACHLORODIBENZOFURAN 1,2,3,4,7,8,9-HEPTACHLORODIBENZOFURAN HEPTACHLORODIBENZOFURAN (TOTAL) OCTACHLORODIBENZOFURAN' TEO (TOXIC EQUIV. VALUE, FROM I-TEF/89) % LIPIDS SAS Number:DIOX Org Contractor: PAS average value. NA-not analyzed. NAl-interferences. J-estimated value. N-presumPtive evidence of presence of material. Production Date: 10/18/2000 12:49 Produced by: Mcconney, John Requestor: Project Leader: BLEWIS · Beginning: 06/21/2000 12:00 Ending: /· I I actual value is known to be less than value given. L-actual value is known to be greater than value given. Li-material was analyzed for but not detected. the number is the minimum quantitation limit. qc indicates that data unusable. compound may or may not be present. resampling and reanalysis is necessary for verification. Page 1 of 1 • f-. 6:'._ T vJJ;f/k,\- File:29AUG _EPA #1-212 Acq:29-AUG-2000 14:43:44 GC El+ Vollage SIR 70S · Sample#S Text:epa39967 _rr _ 436 _ lb\: Exp:DIOXIN _ 1613 373:8208 S:S F:3 SMO(l,3) BSUB(l28,IS,-3.0) PKD(3,2,I,0.10%,6604.0,I0.00%,F,TI 100% / 80 : 60 I ' 40 I 20 j, _ /. _, 0 . \ -:: .. 38:00 A6.44E4 A3.i(E4 375.8178 S:S F:J SMO(l,3) DSUO(l28,IS,-3.0) PKD(J,2,l,0.10%,4396.0,10.00'1',,F,TI IOO 9, 80 i 601 40 . A5.36E4 , 20 ! J-" ·--·· / l -/' ' ''-/'. J ., ·' • 0. -':;~1~··:• .'. /~-~-~ ,. ~ ·. -. -~:i9~i;;_yy_ -··--··•·· ~ I ••••• l. 383.8639 S:5 F:3 SMO(l,3) OSUB(l28,15,-3.0) PKD(3,2,I,0.10%,2648.0,10.00%,F,TI 100 % A9.4.0E7 80 60 40. 20 I I I • I Cl Al.!2E5 I.. A4.07E4 / Al .13E5 Cl .,(_ A5.24E4 A3.~IE4 I I _3.4E4 t . 2.7E4 2.IE4 _3,3E4 .2.5E7 2.0E7 1.5E7 I.OE? 5.0E6 0. -----------------.--------L--'-'=-------------------,----_/:. 38:00 39: 0 40:00 O.0E0 385.86!0 S:5 F:3 SMO(l,3) OSUB(l28,15,-3.0) PKD(3,2,l,0.10%,5620.0,I0.00%,F,n IO0 % Al.78E8 80. 60. 40, 20 I I 41: 0 '· 0. -----------------,--------L._-'-"'---------------------- 40:00 38:00 39: 0 41: 0 Time .-4.7E7 3.7E7 2.8E7 1.9E7 9.4E6 0.0E0 Time • IOXINS SAMPLE ANALYSIS EPA-REGION IV SESD, ATHENS, GA Sample 10065 FY 2000 Project: 00-0589 DIOXIN SCAN Facility: Weyerhaeuser Company Program: •. SFE Plymouth, NC Id/Station: RR436RAN / Media:OTHER BIOTA D No: 436RA RESULTS 2.4U 2.4UJ 5.9U 5.9UJ 5.9U 5.9U 5.9U 5.9UJ 5.9U 6.7UJ 55U 2.4U 3.0UJ 5.9U 5.9U 5.9UJ 5.9U 5.9U 5.9U 5.9U 5.9UJ 5.9U 5.9U 5.9UJ 12U 0.0 0.3 UNITS NG/KG NG/KG NG/KG NG/KG NG/KG NG/KG NG/KG NG/KG NG/KG NG/KG NG/KG NG/KG NG/KG NG/KG NG/KG NG/KG NG/KG NG/KG NGIKG NG/KG NG/KG NG/KG NG/KG NG/KG NG/KG NG/KG % ANALYTE 2,3, 7 ,8-TETRACHLORODIBENZODIOXIN TETRACHLORODIBENZODIOXIN (TOTAL) 1,2,3, 7 ,8-PENTACHLORODIBENZODIOXIN PENTACHLORODIBENZODIOXIN (TOTAL) 1,2,3,4, 7,8-HEXACHLORODIBENZODIOXIN 1,2,3,6, 7,8-HEXACHLORODIBENZODIOXIN 1,2,3, 7 ,8,9-HEXACHLORODIBENZODIOXIN HEXACHLORODIBENZODIOXIN (TOTAL) 1,2,3,4,6, 7 ,8-HEPTACHLORODIBENZODIOXIN HEPTACHLORODIBENZODIOXIN (TOTAL) OCTACHLORODIBENZODIOXIN 2,3, 7 ,8-TETRACHLORODIBENZOFURAN TETRACHLORODIBENZOFURAN (TOTAL) 1,2,3, 7 ,8-PENTACHLORODIBENZOFURAN 2,3,4,7,8-PENTACHLORODIBENZOfURAN PENTACHLORODIBENZOFURAN (TOTAL) 1,2,3,4,7,8-HEXACHLORODIBENZOFURAN 1,2,3,6, 7,8-HEXACHLORODIBENZOFURAN 1,2,3, 7 ,8,9-HEXACHLORODIBENZOFURAN 2,3,4,6, 7 ,8-HEXACHLORODIBENZOFURAN HEXACHLORODIBENZOFURAN (TOTAL) 1,2,3,4,6, 7,8-HEPTACHLORODIBENZOFURAN .1,2,3,4, 7,8,9-HEPTACHLORODIBENZOFURAN HEPTACHLORODIBENZOFURAN (TOTAL) OCTACHLORODIBENZOFURAN TEO (TOXIC. EQUIV. VALUE, FROM I-TEF/89) % LIPIDS SAS Number:DIOX Org Contractor: PAS average value. NA-not analyzed. NAl-interferences. J-estimated value. N-presumptive evidence of presence of material. Production Date: 10/18/2000 12:49 Produced by: McConney, John Requestor: Project Leader: BLEWIS . Beginning: 06/22/2000 07:45 Ending: I I -actual value is known to be less than value given. L-actual value is known to be greater than value given. U-material was analyzed for but not detected. the number is the minimum quantitation limit. -qc indicates that data unusable. compound may or may not be present. resampling and reanalysis is necessary for verification. Page 1 of 1 • • File:29AUG EPk#l-212 Acq:29-AUG-2000 15:34:24 GC El+ Voltage SIR 70S Sample#6 Text:epa39968_rr_ 436_ran · Exp:DIOXIN_l613 373.8208 S:6 F:3 SMO(l,3) BSUB(l28,15,-3.0) PKD(3,2,l,0.10%,6636.0,I0.00%,F,1) 100 \II ' A6.36E4 A6.30E4 ; 80 60 .. A3.6~E4 A2.23E4 < Al.19ES 80 A7.28E4 60 A5.97E4 t\ 40 ( I ' 2 : ~--J,_)~~_Y'~L__:1 './"" ",, 38, o --39Jo ______ ·· -----------·--· 40,00 383.8639 S:6 F:3 SMO(l,3) BSUB(l28,15,-3.0) PKD(3,2,l,0.10%,3708.0,I0.00%,F,1) 100 Al.33E8 80 ,, I' 60 I \ 40 20 I \ 0 38: 0 39: 0 385.8610 S:6 F:3 SMO(l,3) BSUB(l28,15,-3.0) PKD(3,l,l,0.10%,6324.0,I0.00%,F,1) 100 \II . . A2.49E8 80 60 40 20 40:00 I)-. 41:00 41 :00 41:00 2.3E4 . 1.8E4 ;?.'JJli · 1.4E4 ~ [4.SE3 I 0.0E0 3.2E4 1 · __ 2,SE4 l.9FA ' I ! l.3E4 : 6.3E3 ·"! 0.0E0 Time . 3.6E7 ,_ 2.9E7 t I 2.2E7 l.SE7 . 7.3E6. ' r 0.0E0 Time 6.8E7 Ls.4E7 4.1E7 2.7E7 1.4E7 o+----,-----~-~-~-~-~----~-~__,_,,__-=~--,---------~-~-~------38: O 0.0E0. 39: O 40: 0 41: 0 Time • • IXINS SAMPLE ANALYSIS EPA -REGION IV SESD, ATHENS, GA Sample 10066 FY 2000 Project: 00-0589 DIOXIN SCAN Facility: Weyerhaeuser Company Program: SfE Plymouth, NC Id/Station: RR436WCC / Media:OTHER BIOTA D No:436WC RESULTS 4.3 4.3J 8.9U 8.9UJ 8.9U 8.9U 8.9U 23UJ 29U 120J. 460 4.7 4.9J 8.9U 8.9U 8.9UJ 8.9U 8.9U 8.9U 8.9U 8.9UJ 8.9U 8.9U 8.9UJ 18U 5.3 8.7 UNITS NG/KG NG/KG NG/KG NG/KG NG/KG NG/KG NG/KG NG/KG NG/KG NG/KG NG/KG NG/KG NG/KG NG/KG NG/KG NG/KG NG/KG NG/KG NG/KG NG/KG NG/KG NG/KG NG/KG NG/KG NG/KG NG/KG % ANALYTE 2,3, 7,8-TETRACHLORODIBENZODIOXIN TETRACHLORODIBENZODIOXIN (TOTAL) 1,2,3,7,8-PENTACHLORODIBENZODIOXIN PENTACHLORODIBENZODIOXIN (TOTAL) · 1,2,3,4,7.8-HEXACHLORODIBENZODIOXIN 1,2,3,6,7,8-HEXACHLORODIBENZODIOXIN 1,2,3, 7 ,8,9-HEXACHLORODIBENZODIOXIN HEXACHLORODIBENZODIOXIN (TOTAL) 1,2,3,4,6,7,8-HEPTACHLORODIBENZODIOXIN HEPTACHLORODIBENZODIOXIN (TOTAL) OCTACHLORODIBENZODIOXIN 2,3, 7 ,8-TETRACHLORODIBENZOFURAN TETRACHLORODIBENZOFURAN (TOTAL) 1,2,3, 7,8-PENTACHLORODIBENZOFURAN 2,3,4, 7 ,8-PENTACHLORODIBENZOFURAN PENTACHLORODIBENZOFURAN (TOTAL) 1,2,3,4,7,8-HEXACHLORODIBENZOFURAN 1,2,3,6, 7 .8-HEXACHLORODIBENZOFURAN 1,2,3. 7,8,9-HEXACHLORODIBENZOFURAN 2,3,4,6,7,8-HEXACHLORODIBENZOFURAN HEXACHLORODIBENZOFURAN (TOTAL) 1,2,3,4,6, 7 ,8-HEPTACHLORODIBENZOFURAN 1,2,3,4, 7 ,8,9-HEPTACHLORODIBENZOFURAN HEPTACHLORODIBENZOFURAN (TOTAL) OCTACHLORODIBENZOFURAN TEO (TOXIC. EQUIV. VALUE, FROM I-TEF/89) % LIPIDS SAS Number:DIOX Org Contractor: PAS Production Date: 10/18/2000 12:49 Produced by: Mcconney, John Requester: Project Leader: BLEWIS Beginning: 06/21/2000 12:00 Ending: I I erage value. NA-not analyzed. NAl-interlerences. J-estimated value. N-presumplive evidence of presence of material. lual value is knoWn to be less than value given. L-actual value is known to be greater than value given. U-material was analyzed for but not detected. the number is the minimum quantitation limit. indicates that data unusable. compound may or may not be present. resampling and reanalysis is necessary for verification. Page 1 of 1 • • Fllc:~9AUG EPA 11-211Aeq:29-AUG-200016:25:07 GC El+ Voltage SIR 70S Sampicl7 Text:cpa39970 _rr _ 436 _ wee Exp:DIOXIN _ 1613 373.8208 S:7 F:3 SMO(l,3) BSUB(l28,15,-3.0) PKD(3,2,l,0.10%,6956.0,10.00%,F,T) 100 % A4.4~E4 A6.4SE4 80 60 40 20. A2.26E4 i_, 375.8178 S:7 F:3 SMO(l,3) BSUB(J28,15,-3.0) PKD(3,2,l,0.!0%,4048.0,J0.00%,F,T) 100 'lo A8.09E4 80 60 _ 40 A5.87E4 383.8639 S:7 F:3 SMO(l,3) BSUB(l28,15,-3.0) PKD(3,2,l,0.10%,5172.0,10.00%,F,T) 100 % Al.OJ ES A4.S3E4 40,bo 41: 0 · .2.4E4 2.0E4 .l.5E4 9.8E33 't.c£ 4.9E3 0.0E0 Time l.9E4 l.5E4 l.lE4 7.6E3 3.8E3 0.0E0 Time 2.7E7 /·, 80 -I '\ 2.2E7 60 1.6E7 40 I I 1.IE7 20 5.5E6 O+----.-------------,--------LL.,.-"'=-.----,--------~-~--~-~---+-0.0EO Time 40: 0 41: 0 38: 0 39: 0 385.8610 S:7 F:3 SMO(l ,3) BSUB(l 28, 15,-3.0) PKD(3,2, 1,0.10%, 7344.0, 10.00%,F, T) JOO% Al.9~E8 5.2E7 80. 4.2E7 60 3.IE7 40 2.JE7 20 1.0E7 0+----.-------------,--------~'.1,----'-"-.---,-----'a------------~--+O.OEO Time 38: 0 39: O . 40: 0 41: 0 • a 0 c:::, ..t:,. '-.J • Fije:29AUG EPA #1-212 Acq:29-AUG-2000 17:15:41 GC El+ Voltage SIR 70S Sample#8 Text:epa39970d _rr _ 436 _ wee Exp:DIOXIN _ 1613 373.8208 S:8 F:3 SMO(l,3) BSUB(l28,IS,-3.0) PKD(3,2,l,0.10%,4S76'.0¥00%,F,T) 100 % A9.5)E4 p Al.12ES 80 , A9.23E4 -, 60 l?-· :<,Ill 40 A4.JIE4 20 AI.ISE4 ' . · ;'~ , A8.98E3 · ?·4.(E4 A6.04E4 \ A6.25E4 A6.JJE4 \ I I 2.8E4 2.3E4 .. l.7E4 l.lE4 -1:~ 0 _ -./v··· _ 1 _ .'C.✓--' _/..:✓ ..__,-, Jv I I Y" -----/L__L_,---.A./',,, &--- jii;bii .. ·-· ·----,-.. ·--39:bo . .--·~ 4o,bo' ·~---,,-'==c:c~,!__,-:::::: ___ ___:__.:__.1,......h...L):.O.O~~me 375.H I 78 S:8 F:3 SMO(l,3) BSU8(128, 15,•3.0) PKD(3,2, 1,0.10%,2900.0, 10.00%,F,T) 100 'lo A7.0~E4 A4.97E4 Al.l~ES ... r \ AS.24E4 A3.07E4 I '\ I . A2.6~E4 ' A2.3}E4 AJ.93E4 I i 80 I 601 Al.80E4 A3.07E4 40 , AJ.63E4 / ' ' . 20 . . • /. . ,__ L.. Al.20E4 .-,.l : I ,. ' • ✓'· · /' r ~ ,--L' · / '· l _J -, · < ' .... ·'r--v-,,, /. ·· • ... .' '. ·" ,.;', ,.;-, ·. .:_J.""" O ·-•. ...---'-"· ..._,. .. ✓L ,.,,,, ..... J,,...,--l ·1 ____ . -·-'· • -. ~ ""'-..,,--~· _, --~ ··----~ ·c.../, , . -3s,oo .. , ·····--· .. ·······-----39:bo ---·---.-· -4i:bo--···-----··-~o 383.8639 S:8 F:J SMO(l,J) BSUB(l28,1S,-J.0) PKD(3,2,l,0.10%,6880.0,10.00%,F,T) 100 % Al. l~EB 80 ii I I 60. ! \ I I ! i 40 20 l.9E4 J.5E4 l.lE4 7.SE3 3.8E3 0.0E0 Time .2.9E7 2.3E7 l.8E7 J.2E7 S.8E6 0 L.-,--------------,--------A.--1"'=.-----....:.. _______________ _J:.0.0E0 38:00 39: 0 40: 0 41: 0 Time 38S.8610 S:8 F:3 SMO(l ,3) BSUB(l 28, IS,-3.0) PKD(3;2, 1,0. 10%,S440.0, 10.00%,F, T) JOO% A2.JJE8 ·' S.6E7 80 4.5E7 60 3.3E7 40 2.2E7 20 l.1E7 0-+----,------------,--------Ll,.......t""'""_--.--~'-r----.-----~------./:.0.0E0 38: 0 39: 0 41: 0 Time 71,8£1! • • IXINS SAMPLE ANALYSIS EPA -REGION IV SESD,'ATHENS, GA Sample 10067 FY 2000 Project: 00-0589 DIOXIN SCAN F acilily: Weyerhaeuser Company Program:S:~E Plymouth, NC Id/Station: RR436WCF / Media:OTHER BIOTA D No:436WC RESULTS 4.5 59J 8.SU 41UJ 8.SU 8.SU 8.SU 48UJ 24U SOJ 100U 27U 110J 24 20 190J 67 26 8.SU 8.SU 180J 74 12U 97J 31U 26 4.0 UNITS NG/KG NG/KG NG/KG NG/KG NG/KG NG/KG NG/KG NG/KG NG/KG NG/KG NG/KG NG/KG NG/KG NG/KG NG/KG NG/KG NG/KG NG/KG NG/KG NG/KG NG/KG NG/KG NG/KG NG/KG NG/KG NG/KG % ANALYTE 2,3,7,8-TETRACHLORODIBENZODIOXIN TETRACHLORODIBENZODIOXIN {TOTAL} 1,2,3,7,8-PENTACHLOROOIBENZODIOXIN PENTACHLORODIBENZODIOXIN {TOTAL} 1,2,3,4, 7 ,8-HEXACHLORODIBENZODIOXIN 1,2,3,6, 7,8-HEXACHLOROOIBENZODIOXIN 1,2,3, 7 ,8,9-HEXACHLOROOIBENZOOIOXIN HEXACHLORODIBENZODIOXIN {TOTAL} 1,2,3,4,6, 7 ,8-HEPTACHLORODIBENZODIOXIN HEPTACHLORODIBENZODIOXIN {TOTAL) OCTACHLORODIBENZODIOXIN 2,3,7,8-TETRACHLORODIBENZOFURAN TETRACHLOROOIBENZOFURAN {TOTAL} 1,2,3, 7 ,8-PENTACHLORODIBENZOFURAN 2,3,4,7,8-PENTACHLORODIBENZOFURAN PENTACHLORODIBENZOFURAN (TOTAL)· 1,2,3,4,7 ,8-HEXACHLORODIBENZOFURAN 1,2,3,6, 7,8-HEXACHLORODIBENZOFURAN 1,2,3, 7,8,9-HEXACHLORODIBENZOFURAN 2,3,4,6,7,8-HEXACHLORODIBENZOFURAN HEXACHLORODIBENZOFURAN (TOTAL} 1,2,3,4,6,7,8-HEPTACHLORODIBENZOFURAN 1,2,3,4, 7 ,8,9-HEPTACHLORODIBENZOFURAN HEPTACHLORODIBENZOFURAN {TOTAL} OCTACHLORODIBENZOFURAN TEO (TOXIC. EQUIV. VALUE, FROM I-TEF/89) % LIPIDS SAS Number:DIOX Org Contractor: PAS Production Date: 10/18/2000 12:49 Produced by: M~Conney, John Requester: Project Leader: BLEWIS Beginning: 06/21/2000 12:00 Ending: I ' erage value. NA-nol analyzed. NAl-interfetences. J-estimaled value. N-presumptive evidence of presence of malerial. . tual value is known lo be less lhan value given. L-actual value is known to be greater than value given. LI-material was analyzed for but not detected. the number is the minimum quantitation limit. : indicates that data unusable. compound may or may not be present. resampling and reanalysis is necessary for verification. Page 1 of 1 • • . · _ · f//J& l)llj oofc1(01 · · · · Flle,19AUG EPA 11-111Acq:29/A1JG-100018:06:14 GC El+ Voltage SIR 70S Sample#9 Text:epa39971 rr 440/wcr Exp:DIOXIN 1613 373.8208 S:9 F:3 SMO(l)) i\!ltlfi(l28,IS,-3.0) PKD(J,2~1,0.10%,10596.0,10.00%,F~ / 1:: q, _ / Al.07//, 60 / AS.4_7E6 i;:) A,4.0,9E6 I O I/ 1, G) }lo 40 ' I 1·.~.E6 /,~ 20 AI.S2E6 ; \ \) Q Al.75E6 (\'I\(' o +---,--~-~....l,....~J,-.1.....~.....,.c::::::::,,.-...L.~---1.....-.A,.__l--.J:=::=r----4~4~-J::'O:__~~-....--~~~ A5.17E5 41: 0 38: 0 39: 0 375.8178 S:9 F:3 SMO(l,3) BSU8(128,IS,-3:0) PKD(3,2,1,0.IO'To,8788.0,10.00'To,F,1) 100 q, A8,70E6 80 60 40 20 A4.36E6 i I , Al.29E6 A5.82ES 38: 0 39: 0 I 1.40E6 Al.4SE6 ' I / ' /, 383.8639 S:9 F:3 SMO(l,3) BSUB(!28,15,-3.0) PKD(3,2,l,0.I0'To,4276,0,10.00'To,F,1) 100 o/. A9.7?-E7 80 60 40 10 Al.41E6 A4.~7ES o-i------------------~-~-d.,--'-',..,...---,----,----,--'-~-~-~-~-~~-'-~-40: 0 41: 0 38: 39: 0 385.8610 S:9 F:3 SMO(l,3) BSUB(ll8,IS,-3.0) PKD(3,2,l,0.10%,6312.0,!0.00'To,F,1) 100 'To Al.8 E8 80 60 40 20 2.SE6 .2.0E6 · 1.SE6 I.0E6 5.~w o~o Time • 2.0E6 fJ. 7ri f.'/. !.6E6 l.2E6 8.2ES 4.IES C) 0.0EO C) ....... Time N 2.5E7 c.n 2.0E7 !.5E7 !.0E7 • 5.0E6 0.0E0 Time 4.8E7 3.8E7 2.9E7 !.9E7 9.6E6 0.0EO Time 9/22/00 P ASC -Certi'/,:faM b:{!4.nalysis t::.iah.l b ,t 1> :J Page 5 of? • • RR RR RR RR MS/MSD RR Cli,nt ID: 449-LBF 449-LBF 449-LBF 449-LBF RPO 449-WCC lab No.: 039983 00 039983 00 039983 00 039983 00 039984 00 Date Sampled: 00/06/20 00/06/20 00/06/20 00/06/20 00/06/20 Component Units M. Spike MS¾Rec. MS Dup MSD%Rec. % Dilution Factor 1.0 1.0 1.0 Total Tetrachlorodibcnzofurans pg/g 100 100 4.1 Total Pentachlorodibenzofurans 600 560 3.5 Total Hcxachlorodibcnzofurans 1000 1000 6.6 Total Hcptachlorodibcnzofurans 560 560 9.3 Total TetrachlorodibenZO.-·p-dioxins 88 92 2.8 Total Pentachlorodibenzo-p-dioxins 250 240 2.2 Total Hcxachlorodibenzo-p-dioxins 730 740 10 Total HcptachlorodiNft.zo-p-dioxins 250 · 240· · ·•·· .,,, 38 -Internal Recoveries % 2,3, 7,8-T4CDF-l 3CI 2 37 37 81 81 75 74 2,3,7,8-T4CDD-13CI 2 35 35 69 69 ·· 65 62 I ,2,3,7,8-PSCDF-13CI 2· 37 37 81 81 75 80 1,2,3,7,8-PSCDD-13Cl2 44 -14 100 100 78 95 1,2,3,4,7,8-H6CDF-13Cl2 47 47 71 71 41 77 1,2,3,6,7,8-H6CDD-l 3CI 2 55 55 81 81 38 81 1,2,3,4,6,7,8-H7CDF-1 JC! 2 48 48 71 71 39 80 1,2,3,4,6,7,8-H7CDD-l3CI 2 48 48 80 80 50 89 OCDD-l3Cl2 42 42 83 83 66 94 2,3,7,8-Cl4-Dibenzofuran (DBS) pg/g 96 105 97 107 2 4.1 2,3,7,8-Cl4-Dibenzo-p-dioxin 87 ')5 91 101 6 2.8 1,2,3,7,8-CIS-Dibenzofuran 280 122 260 117 4 1.4 2,3 ,4, 7 ,8-CIS-Dibenzofuran 290 129 280 122 6 2.1 1,2;3,7 ,8-CIS-Dibenzo-p-dioxin 250 112 240 104 7 2.2 I ,2,3,4,7,8-Cl6-Dibenzofuran 270 I 18 240 107 10 <1.9 1,2,3 ,6, 7, 8-Cl6-Dibenzofuran 290 128 290 126 2 I. 7 2,3.4,6, 7 ,8-Cl6-Dibenzofuran 280 124 270 I 19 4 2.4 1,2,3,7,8,9-Cl6-Dibenzofuran 140 h3 180 78 21 1.5 1,2.3,4, 7,8-Cl6-Dibenzo-p-dioxin 270 120 290 127 6 2.1 I ,2.3,6,7,8-Cl6-Dibenzo-p-dioxin 260 I 14 230 103 10 3.7 1,2,3, 7 ,8,9-Cl6-Dibenzo-p-dioxin 200 86 220 · 95 10 3.0 1,2,3 ,4,6,7 ,8-Cl7-Dibenzofuran 330 147 310 135 9 <3.7 I ,2,3,4,7,8,9-Cl7-Dibenzofuran 170 76 230 102 29 2.8 1,2,3,4,6, 7,8-Cl7-Dibenzo-p-dioxin 230 100 240 102 2 20 1,2,3,4,6,7,8,9-Cl8-Dibenzofuran 380 so 390 85 6 16 1,2,3,4,6, 7 ,8,9-Cl8-Dibenzo-p-dioxin 460 79 480 95 18 230 2,3,7,8-TCDF (OB225) pg/g 3.5 Internal Recoveries % 2;3 ,7 ,8-TCDF-I 3C 12 69 Client:US EPA Region IV/ESD (ASB) Project:00-0589 I 9/22/00 PASC-CertiftHJPo}Jlnalysis Page 2 of7 • • Method Blank Blank RR RR RR Client ID: Blank Spike Spike 436-WCC 436-WCC 436-WCF lab No.: 039969 00 039969 00 039969 00 039970 00 039970 00 039971 00 Date Sampled: 00/06/21 00/06/21 00/06/21 Component Units % Recovery Duplicate Dilution Factor 1.0 1.0' 1.0 1.0 1.0 Total Tetrachlorodibenzofurans pg/g 3.2 95 4.9 5.0 110 Total Pcntachlorod.ibenzofurans 7.2 --480 4.8 5.0 190 Total Hcxachlorodibenzofurans 23 920 <0.54 <0.50 180 Total Hcptachlorodibcnzofurans 15 530 <1.2 <0.-19 97 Total Tetrachlorodibenzo::p-dioxins <0.77 78 4.3 4.7 59 Total PC:ntachlorodibcnzo-p-dioxins 3.1 210 1.2 1.4 41 Total Hcxachlorodibenzo-p-dioxins 14 680 23 .,25~ 48 · Total HCprachlorodi6crizo-p-dioxins 8.5 220 120 I 10 50 Internal Recoveries % 2,3,7,8-T4CDF -13CI 2 40 31 31 68 74 70 2,3,7,8-T4CDD-l3CI 2 ...... 46 33_ 33 68 70 65 I ,2,3,7,8-P5CDF-l 3CJ 2 40 38 38 70 76 68 1,2,3 ,7 ,8-P5CDD-l3CI 2 47 50 50 84 90 85 1,2,3,4,7,8-H6CDF-13CI 2 49 43 43 73 85 82 I ,2,3,6,7,8-H6CDD-l 3CI 2 53 52 52 74 85 84 1,2,3,4,6,7,8-H7CDF-J 3CI 2 48 48 48 78 90 83 I ,2,3,4,6,7,8-H7CDD-J 3CI 2 56 59 59 81 94 86 OCDD-13Cl2 56 65 65 78 96 82 2,3,7,8-Cl4-Dibenzofuran (DBS) pg/g 0.78 93 93 4_·9 5.0 27 2,3, 7 ,8-Cl4-Dibcnzo-p-diox in <0.77 78 78 4.3 4.7 4.5 1,2,3, 7 ,8-CIS-Dibenzofuran 3.4 220 88 <0.54 0.45 24 2,3,4, 7 ,8-CIS-Dibcnzofuran 3.9 250 IOI 0.93 1.0 20 1,2,3, 7 ,8-CIS-Dibenzo-p-dioxin 3.1 210 84 1.2 1.4 6.8 1,2,3,4, 7 ,8-C16-Dibenzofuran 4.5 240 95 <0.47 <0.44 67 1,2,3,6, 7 ,8-Cl6-Dibenzofuran 4.8 230 93 <0.47 <0.44 26 2,3 ,4,6, 7 ,8-Cl6-Dibenzofuran 6,4 220 90 <0.59 <0,54 7.9 1,2,3,7,8,9-Cl6-Dibcnzofuran 7.5 210 86 <0.66 <0.61 1.2 1,2,3,4,7 ,8-Cl6-Dibcnzo-p-dioxin 5.2 250 102 1.00 1.0 3.3 1,2,3 ,6, 7 ,8-Cl6-Dibenzo-p-diox in 4.0 210 86 2.3 3.0 8,1 1,2,3, 7 ,8,9-Cl6-Dibenzo-p-diox in 5.0 210 84 1.4 1.5 6.4 1,2,3,4,6,7,8-CJ7-Dibenzofuran 6.9 280 II I <0.97 <0.76 74 1,2,3 ,4, 7 ,8,9-CJ7-Dibenzofuran 8.0 230 93 <0.67 <0.60 12 1,2,3,4,6, 7 ,8-Cl7-Dibenzo-p-dioxin 8.5 210 85 29 30 24 1,2,3 ,4,6, 7 ,8,9-Cl8-Dibenzofuran 17 300 60 <0.98 <0.98 31 1,2,3 ,4,6, 7 ,8,9-Cl8-Dibenzo-p-dioxin 24 450 91 460 470 JOO 2,3,7,8-TCDF (DB225) pg/g <0,34 4.7 4.7 <18 Internal Recoveries % 2,3, 7,8-TCDF-l 3C I 2 46 70 71 68 Client:US EPA Region IViESD (ASB) Projecr:00-0589 I . -· • As an option, a rotary evaporator may be used in place of the KD apparatus for the concentration of the rinsate. . 8.3.4.2.4 Transfer the 5 ml concentrate from the KD concentrator tube in 1 ml portions to a 1 ml mini vial, reducing the volume in the minivial-as necessary with a gentle stream of dry nitrogen. 8.3.4.2.5 Rinse the KD concentrator tube with two 0.5 ml portions of hexane and transfer the rinses to the 1 ml minivial. Blow down with dry nitrogen as necessary. 8.3.4.2.6 Just before_ a__n~lysis, add 10. uL recovery standard solution (Table 2) and reduce the volume to its final volume, as necessary (Sec. 7.8.1). No column chromatography is required. · 8.3.4.2.7 Analyze an aliquot following the same procedures used to analyze samples. 8. 3. 4. 2. 8 Report percent recovery of the internal standard and the presence of any PCOO/PCOF compounds in µg/L of rinsate solvent. 8.3.5 Duplicate Analyses 8.3.5.1 In each batch of samples, locate the sample specified for duplicate analysis, and analyze a second 10 g soil or sediment sample portion or 1 L water sample, or an appropriate amount of the type of matrix· under consideration. 8.3.5.1.1 The results of the laboratory duplicates (percent recovery and concentrations of 2,3,7,8-substituted PCOD/PCDF compounds) should agree within 25 percent relative difference (difference expressed as percentage of the mean). Report all results. 8.3.5.1.2 Recommended. actions to help locate problems: 8.3.5.1.2.1 Verify satisfactory instrument performance (Secs. 8.2 and 8.3). 8.3.5.1.2.2 If possible, verify that no error was made while weighing the sample portions. 8.3.5.1.2.3 Review the analytical procedures with the performing laboratory personnel. 8.3.6 Matrix Spike and Matrix Spike Duplicate 8.3.6.1 Locate the sample for the MS and MSD analyses (the sample may be labeled "double volume"). 8290 -42 Revision 0 September 1994 L --./' • • 8.3.6.2 Add an appropriate volume of the matrix spike fortification solution (Sec. 5.10) and of the sample fortification solution (Sec. 5.8), adjusting the fortification level as specified in Table 1 under IS Spiking Levels. 8.3.6.3 Sec. 7. Analyze the MS and MSD samples as described in 8.3.6.4· The results obtained from the MS and MSD samples (cgncentrations of 2,3,7,8-substituted PCDDs/PCDFs) should agree within 20 percent relative difference. 8.4 Percent Recovery of the Internal Standards -For each sample, method blank and ril\"sate, calculate the percent recovery· ·(Sec. 7 .9.2) .-•· -fhe percent recovery should be between 40 percent and 135 percent for a 11 2, 3, 7, 8-subst ituted internal standards. A low or high.percent recovery for a blank does not require discarding the analytical data but it may indicate a potential problem with future analytical data. 8.5 Identification Criteria 8.5.1 If either. one of the identification criteria appearing in Secs. 7.8.4.1.1 through 7.8.4.1.4 is not met for an homologous series, it is reported that the sample does not contain unlabeled 2,3,7,8-substituted PCDD/PCDF isomers for that homologous series at the calculated detection limit (Sec. 7.9.5) 8.5.2 If the first initial identification criteria (Secs. 7.8.4.1.1 through 7.8.4.1.4) are met, but the criteria appearing in Secs. 7.8.4.1.5 and 7.8.4.2.1.are not met, that sample is presumed to contain interfering contaminants. This must be noted.on the analytical report form, and the sample should be rerun or the extract reanalyzed. 8.6 Unused portions of samples and sample extracts should be preserved for six months after sample receipt to allow further analyses. 8.7 Reuse of glassware is to be minimized to avoid the risk of contamination. 9.0 METHOD PERFORMANCE 9.1 Data are currently not available. 10. 0 REFERENCES I. "Control of Interferences in the Analysis of Human Adipose Tissue for 2,3,7,8-Tetrachlorodibenzo-p-dioxin". D. G. Patterson, J.S. Holler, D.F. Grote, L.R. Alexander, C.R. Lapeza, R.C. O'Connor and J.A. Liddle. Environ. Toxicol. Chem. 5, 355-360 (1986). 8290 -43 Revision 0 September 1994 .. UNITED &Es ENVIRONMENTAL PROTECTION .NCY NATIONAL EXPOSURE RESEARCH LABORATORY P.O. BOX 93478 • LAS VEGAS, NV 89193-3478 DEC 2 I 200/ OFFICE QF RESEARCH AND DEVELOPMENT MEMORANDUM SUBJECT: Revised Report "White Fish Dioxin Analysis -Roanoke River Study S. F. Site" FROM: . -/_# KenBrown, Director, TSC /~ Environmental Sciences Divisi~ · TO: Beth Walden, RPM Region IV Beth, the attached report by Dr. Russell Plumb dated December 20, 2001 has an added section titled "Comments on the Weyerhaeuser Data Review (11/13/01 )" please see the last two pages. I hope these added comments and suggestions will be helpful to you. If you have any questions please give me a call at (702) 798-2270. Attachment Recycled/Recyclable • Printed with Vegetable OH Based Inks on 100% Recycled Paper (40% Postconsumer) Ms. Beth Walden Brown Remedial Project Manager US EPA Region JV Atlanta, Georgia- • 20 December 2001 Re: Commen~on Dioxin Analysis of White Catfish Sample from Roanoke Station-436 Dear Beth: You had asked me to reexamine the dioxin data from the White Catfish sample from Station 436. The following comments were developed in response to this request. Number of Congeners Detected Dioxin/furan data were extracted from the draft Remedial Investigation Report for tissue samples that had both carcass and file! analyses. The number of dioxin/furan congeners detected in these samples has been summarized in Table 1. For all of the catfish samples except that collected at Station 436, the number of detected dioxin/furan congeners in the carcass sample is greater than or equal to the number detected in the corresponding filet samples. This trend ( a smaller number of congeners in the file! sample compared to the carcass sample) was also true for the Yellow Catfish and Largemouth Bass samples. The only tissue sample in which more congeners were detected in the filet than carcass was the White Catfish sample from Station 436_. Table 1. Number of Dioxin/Furan Congeners Detected in Fish Tissue Samples. Station Sample Species Carcass 434 White Catfish 435 White Catfish· 436 White Catfish 440 White Catfish 449 White Catfish 440 Yellow Catfish 434 Largemouth Bass 435 Largemouth Bass 436 Largemouth Bass 440 Largemouth Bass 449 Largemouth Bass 736 Largemouth Bass 0 1 2 0 2 1 0 I I 0 2 Fi let 0 0 6 0 0 0 0 0 1 0 0 I • • Concentrations of Detectable Dioxin/Furari Congeners The concentrations of the detected congeners of dioxin and furan were tabulated for each of the samples listed in Table 1. This information is presented in Table 2. For all of the samples except the White Catfish at Station 436, the concentration of detectable dioxin/furan in the carcass was 12 ng/kg, or less and the ratio of file! concentration to carcass concentration was 0.25, or less. However, although the dioxin/furan concentration in the White Catfish carcass was in the range observed for other fish samples, the filet/carcass ratio for the Station 436 samples was almost I 00 times higher-than the other samples due to the high filet concentrations Table 2. Concentration of Dioxin/Furan Congeners Detected in Fish Tissue Samples. Station SampTeSpecies _ Carcass Filet Ratio 434 White Catfish 0 0 435 White Catfish 4.2 0 0 436 White Catfish 9.0 215.5 23.94 440 White Catfish 0 0 449 · White Catfish 6.3 0 0 440 Yellow Catfish 1.4 0 0 434 Largemouth Bass 5.4 0 0 435 Largemouth Bass 0 0 436 Largemouth Bass 6.5 1.6 0.25 440 Largemouth Bass 3.5 0 0 449 Largemouth Bass 0 0 736 Largemouth Bass 12.2 1.3 0.1 I "Total" Concentration ofDioxin/Furan Congeners in Fish Tissue Samples A "total" dioxin/furan concentration was calculated for the fish tissue samples: For the purpose of this calculation, a value equal to one-half the detection limit was used for all results reported as not detected. The result was then tabulated for each of the Roanoke fish tissue samples (Table 3). The calculated"total" concentrations were strongly influenced by the substituted value for non-detectable results because most of the . individual congeners had non-detectable concentrations and the few detectable congeners had relatively low concentrations. As a result, the ratio of the file! "total" to the carcass "total" was close to 1.0 (range of 0.845 to 1.270) for all but two fish samples. One was the Yellow Catfish sample from Station 440 with a ratio of0.52. The low ratio for this sample was not due to any detectable concentrations but to lower detection limits reported for the filet sample. The other sample was the White Catfish sample from Station 436 with a ratio of 3.353. This ratio is due to the elevated furan concentrations in the filet sample. • • Table 3. "Total" Dioxin/Furan Concentrations in Roanoke Fish Tissue Samples. Station Sample Species Carcass Filet Ratio 434 White Catfish 73.5 70.35 0.957 435 White Catfish 71.8 71.75 0.999 436 White Catfish 85.9 288 3.353 440 White Catfish 67.15 85.4 1.270 449 White Catfish 69.7 78.35 1.120 .,· ... 440 Yellow Catfish 115.3 59.9 0.520 434 Largemouth Bass 69.4 67.15 0.968 435 Largemouth Bass 71.55 70.35 0.983 436 Largemouth Bass 73.45 67.05 0.913 440 Largemouth Bass 69.45 63.20 0.910 449 Largemouth Bass 71.1 73.65 1.036 736 Largemouth Bass 72.85 61.55 0.845 Dioxin/Furan Congeners Detected in Roanoke Fish Samples Table 4 lists t_he individual dioxin/furan congeners that were detected in the Roanoke fish samples. In every case, the detected congeners in the carcass samples were 2378-TCDD and/or 2378-TCDF. Also, in every case but one, the detected congeners in the file! samples were limited to the 2378-TCDD congener. The one exception was the White Catfish sample from Station 436 in which 12378-PeCDF, 23478-PeCDF, 123478-HxCDF, 123678-HxCDF, and 1234678-HpCDF were reported .in the filet sample. These congeners were not reported at detectable concentrations in any other fish tissue samples ( carcass or filet). The analytical results for all other Roanoke tissue samples were reviewed for the furans detected in the White Catfish sample from Station 436 (12378-PeCDF, 23478-PeCDF, 123478-HxCDF, 123678-HxCDF, and 1234678-HpCDF). These congeners were not detected in the bioaccumulation study samples, Redear Sunfish samples, Bluegill samples, Corbicula Clam samples, Rangia Clam samples, or whole Largemouth Bass samples. One congener, 123478-HxCDF, was reported in one Bullfrog samples. However, the estimated concentration of 0.1 ng/kg, was more than 20 times lower than the detection limit reported for the other samples and more than 200 times lower than the concentrations· reported in the White Catfish filet sample. Discussion The review identified several issues that cast doubt on the validity of the White Catfish filet sample result from Station 436. These issues exist at several levels: the individual White Catfish sample (Station 436), the species level (White Catfish in the Roanoke River), and the system level ( other tissue samples from the lower Roanoke River system). • • Table 4. Dioxin/Furan congeners reported in Roanoke Fish Tissue Samples. Station Sample Species Carcass Sample Filet Sample 434 White Catfish none none 435 White Catfish 2378-TCDD none 436 White Catfish 2378-TCDD 2378-TCDD 2378-TCDF 12378-PeCDF 23478-PeCDF. 123478-HxCDF · 123678-HxCDF 1234678-HpCDF 440 White Catfish none none 449 White Catfish 2378-TCDD none White Catfish 2378-TCDF 440 Yellow Catfish 2378-TCDD none 434 Largemouth Bass 2378-TCDD none 435 Largemouth Bass none none 436 Largemouth Bass 2378-TCDD 2378-TCDD 440 Largemouth Bass 2378-TCDD none 449 Largemouth Bass none none 736 Largemouth Bass 2378-TCDD 2378-TCDD 2378-TCDF One of the hazards associated with chlorinated hydrocarbons such as dioxins and furans is their ability to bioconcentrate in organisms. Since these contaminants are hydrophobic, they tend to accumulate in the fats and lipids associated with tissue. One problem this raises with the Station 436 White Catfish file! sample is that the concentration of detected dioxin and furan congeners in the filet are higher than in the carcass even though the lipid content of the carcass is more than twice that of the filet (8.7 percent vs 4 percent)(Table 2). A consideration of the differential lipid content would suggest that more dioxin and furans should be present in the carcass. A second problem is that more individual dioxin and furan congeners were detected in the filet than in the carcass (6 vs 2)(Table I). Its not conceivable that a hydrophobic contaminant would be taken in by the fish (either by ingestion or through the gills) and pass directly to the muscle (filet) without • • some residue in other tissues. Degradation doesn't seem plausible since the congeners detected in the filet but not the carcass have higher levels-of chlorination (i.e., the filet congeners have 5, 6, and 7 substituted chlorine atoms per molecule but the carcass only has 4 substituted chlorine atoms per molecule). The relative abundance and congener distribution in the White Catfish sample from Station 436 is not what would be expected based on the chemistry of dioxins and furans and the lipid distribution of the sample. A comparison ofthe White Catfish sample results from Station 436 with other Roanoke Catfish samples also suggests that the Station 436 sample result is suspect. The other Catfish samples had between !rand 2 detected dioxin or furan congeners andihe Station 436 catc·ass sample had 2 detected dioxin and furan congeners (Table I). Thus, the Station 436 carcass sample is consistent with other Roanoke Catfish samples. However, there were no detected dioxin or furan congeners in any other White Catfish file! sample except that at Station 436 that had 6. The . calculated sum of the dioxin and furan congener concentrations for White Catfish carcass samples in the Roanoke were in the range of 0 to 6.3 ng/kg. The calculated sum for the Station 436 carcass sample was slightly higher at 9 ng/kg. However, the filet/carcass ratio for all other catfish samples was 0 but the ratio for the Station 436 sample was 23.94. If the White Catfish had some capacity to selectively transfer and store dioxin/furan contamination in the filet, one would expect to see some level of contamination in the other catfish samples. However, without this, the ratio for Sample 436 appears to be anomalously high due to the reported filet results. A filet/carcass ratio was also calculated for the 16 dioxin/furan congeners used in the fingerprinting process (a value of one-half the reported detection limit was substituted for non°detectable results for this calculation). The results of this exercise (Table 3) indicate that the Roanoke 'White Catfish ratio was in the range of 0.957 to 1.270. By comparison, the calculated ratio for the Station 436 sample was 3.353. Again, the results for the Station 436 White Catfish sample are outside the range for other Roanoke samples and appear to be anomalously high. [ A check of the high volume water sampling results indicates that the concentration for the congeners reported in the Station 436 filet sample, 12378-PeCDF, 23478-PeCDF, 123478-HxCDF, 123678-HxCDF, and 1234678-HpCDF, were reporte~ as non-detectable across the project area. Thus, the Sample 436 concentration can not be shown to be attributable to a concentration increase in that area.]. The Station 436 White Catfish carcass sample is within the range defined· by other Roanoke White Catfish samples. However, the Station 436 White Catfish filet sample has a greater number of dioxin/furan congeners, at higher concentrations, and at distinctly elevated concentration ratios than all other catfish samples from the lower Roanoke Basin. The Station 436 White Catfish results were compared to all other tissue analyses results in the study. All other carcass results had between 0 and 2 dete_ctable dioxin/furan congeners (Table 1), the detected congeners were 2378-TCDD and/or 2378-TCDF (Table 4), and the sum of the detectable concentrations were in the range of 0 to 12.2 ng/kg (Table 2). The White Catfish carcass sample results from Station 436 were consistent with all these values (2 detected congeners, 2378-TCDD and 2378-TCDF, total detectable concentration of 9 ng/kg). All other filet samples had between 0 and 1 detectable congener, the only detected congener was 2378-TCDD, and the concentrations were in the range of 0 to 1.6 ng/kg. Also, Station 436 sediments were used in the bioaccumulation studies. The only congener detected in the test species following exposure was 2378-TCDD (i.e., the 5 furan congeners reported in the Station • • 436 White Catfish filet sample were not detected in the organisms used in the bioaccumulation study). As discussed above, the Station 436 White Catfish file! had 6 detectable congeners (including 5 not detected in any other tissue sample) at a concentration that was two orders of magnitude higher than was seen in any other tissue sample. The type and level of dioxin/furan contamination reported for the Station 436 White Catfish carcass is consistent with all other Roanoke tissue analyses. However, the type and level of dioxin/furan contamination reported for the Station 436 ~ite Catfish filet sample appears to be anomalously high. Comments on the Weyerhaeuser Data Review (11/13/01) The data review performed by RMT identified several potential quality c"iih(!-ol problems associated with the sample set that included the White Catfish samples from Station 436. These included analysis of the tissue samples immediately following a spiked blank analysis, apparent contamination of the blank samples, poor recovery of labeled standards, and a poor precision on the MS/MSD samples. While these comments could not be independently verified with the information provided, these factors could cause or contribute to the anomalous results reported for the White Catfish filet sample frorri Station 436. Carryover during sample analysis is a possibility as pointed out in the RMT review. However, there are some inconsistencies. First, if the samples were analyzed sequentially according to Laboratory Sample ID, the White Catfish carcass samples _would have been analyzed after the spiked blank (sample ID 39970 vs Sample ID 39969). This sample does not show indication of furan contamination but the White Catfish filet sample (ID 39971) does. Second, the dioxin congeners that _are present in the blank spike sample at the same concentrations as the furan congeners do not show up in any of the catfish samples. There is no explanation as to why some ofthe analytes in the spiked sample would have carried over but not others. The results in the Draft RI and the RMT data review were compared and some differences were noted. First, the RMT review listed generally lower detection limits. Second, there were some differences in the listed values (Draft RI listed 2378 TCDF as 27 u in 436WCF and RMT had 27 i_n the same sample; Draft RI listed 23478-PeCDF as 20 in 436WCF and RMT had 20 u in the same sample; Draft RI listed 2378-TCDF as 4.7 in 436WCC and RMT had 4.9 in the same sample). Third, the RMT review listed values as"u" or"<" (i.e, they did not consistently use the same convention for flagging data). Summary This review indicates that the validity of the sample results for the White Catfish filet sample from Station 436 is highly questionable. The contaminants reported in the filet were not even detected in the carcass sample from the same location even though the carcass had a higher lipid content. The carcass sample results from Station 436 were consistent with other White Catfish carcass samples collected throughout the Roanoke basin. The contaminants detected in the White Catfish filet sample from Station 436 were not detected. in any other tissue sample (White Catfish, Yellow Catfish, Largemouth Bass, bioaccumulation study) in the study area. The RMT data review identified several lapses in quality assurance that could have contributed to the anomalous results reported for the White Catfish filet sample from Station 436 and there was no discussion of whether any type of corrective action was taken. Sample cross-contamination is a • • possibility considering the relatively high congener concentrations in the spiked blank sample compared to the concentrations reported in the questionable file! sample. Other factors that could have contributed to transcription errors are the missing chromatograms and the sample log-in inconsistencies pointed out in the RMT review. A consideration of the properties of the dioxin/furan congeners and their reported distribution in the lower Roan~e Basin suggests that the results for the White Catfish file! sample from Station - 436 are atypical. The data quality review performed by RMT identified several factors that could have compromised the integrity of the sample after collection and/or during analysis. While some of the i'ttl!ntified issues may be minor, there are too ·many issues that indic.aied the Station 436 "filet results are non-representative. At best, the results for this sample ( 436WCF) should be considered an outlier and at worst the results shoulc!_1irobably be considered erroneous. Should you have any questions on this review, please fee free to contact me as your schedule permits. Very Truly Yours, Russell H. Plumb Jr. UNITED stTES ENVIRONMENTAL PROTECTION .. NCY NATIONAL EXPOSURE RESEARCH LABORATORY P.O. BOX 93478 • LAS VEGAS, NV 89193-3478 DEC 20 2001 MEMORANDUM OFFICE OF RESEARCH AND DEVELOPMENT ...... SUBJECT: White Fish Dioxin Analysis -Roanoke River Study S. F. Site FROM: TO: Ken Brown, Director, TSC Environmental Sciences Divis· Beth Walden, RPM Region IV Beth, please find attached an assessment of the white catfish sample dioxin data provided by Dr. Russell Plumb dated December 19, 2001. As you will-note, Russell completed a number of data calculations and comparisons with other fish samples. I hope the attached will be helpful to you and your co-workers at the subject Superfund site. If you rieed additional assistance please give me a call at (702) 798-2270. I di_d receive your e-mail pertaining to Nardina's request for Wayne Sovocool to examine the analytical data for sample D05FH-8B70, Case 28218. I talked to Wayne yesterday and he will begin to examine the data. Attachment Recycled/Recyclable• Printed with Vegetable Oil Based Inks on 100% Recycled Paper (40% Pos1consumer) • Ms. Beth Walden Brown Remedial Project Manager US EPA Region IV Atlanta, Georgia::. • 19 December 2001 Re: Comments on Dioxin Analysis of White Catfish Sample from Roanoke Stati9n 436 -· . . ---•·-· .. Dear Beth: You had asked me to reexamine the dioxin data from the White Catfish sample from Station 436. The following comments were developed in response to this request. Number of Congeners Detected Dioxin/furan data were extracted from the draft Remedial Investigation Report for tissue samples that had both carcass and filet analyses. The number of dioxin/furan congeners detected in these samples has been summarized in Table I. For all of the catfish samples except that collected at Station 436, the number of detected dioxin/furan congeners in the carcass sample is greater than or equal to the number detected in the corresponding file! samples. This trend (a smalier number of congeners in the filet sample compared to the carcass sample) was also true for the Yellow Catfish and Largemouth Bass samples. The only tissue sample in which more congeners were detected in the filet than carcass was the White Catfish sample from Station 436. Table 1. Number ofDioxin/Furan Congeners Detected in Fish Tissue Samples. Station Sample Species Carcass Fi let 434 White Catfish 0 0 435 White Catfish I 0 436 White Catfish 2 6 440 White Catfish 0 0 449 · White Catfish 2 0 440 Yellow Catfish I 0 434 Largemouth Bass I 0 435 Largemouth Bass 0 0 436 Largemouth Bass 1 1 440 Largemouth Bass I 0 449 Largemouth Bass 0 0 736 Largemouth Bass 2 I • • Concentrations of Detectable Dioxin/Fu ran Congeners The concentrations of the detected congeners of dioxin and furan were tabulated for each of the samples listed in Table I. This information is presented in Table 2. For all of the samples except the White Catfish at Station 436, the concentration of detectable dioxin/furan in the carcass was 12 ng/kg, or less and the ratio of file! concentration to carcass concentration was O .25, or less. However, although the dioxin/furan concentration in the White Catfish carcass was in the range observed for other fish samples, the filet/carcass ratio for the Station 436 samples was almost 100 _times higher than the other samples due to the high file! concentrations Table 2. Concentration ofDioxin/Furan Congeners Detected in Fish Tiss!.!~ SamJlles. - Station Sample Species Carcass Fi let Ratio 434 White Catfish 0 0 435 White Catfish 4.2 0 0 436 White Catfish 9.0 215.5 23.94 440 White Catfish 0 0 449 White Catfish 6.3 0 0 440 Yellow Catfish 1.4 0 0 434 Largemouth Bass 5.4 0 0 435 Largemouth Bass 0 0 436 Largemouth Bass 6.5 1.6 0.25 440 Largemouth Bass 3.5 0 0 449 Largemouth Bass 0 0 736 Largemouth Bass 12.2 1.3 0.11 "Total" Concentration of Dioxin/Furan Congeners in Fish Tissue Samples A "total" dioxin/furan concentration was calculated for the fish tissue samples. For.the purpose of this calculation, a value equal to one-half the detection limit was used for all results reported as not detected. The result was then tabulated for each of the Roanoke fish tissue samples (Table 3). The calculated "total" concentrations were strongly influenced by the substituted value for non-detectable results because most of the individual congeners had non-detectable concentrations and the few detectable congeners had relatively low concentrations. As a result, the ratio of the filet "total" to the carcass "total" was close to 1.0 (range of0.845 to 1.270) for all but two fish samples. One was the Yellow Catfish sample from Station 440 with a ratio of0.52. The low ratio for this sample was . not due to any detectable concentrations but to lower detection limits reported for the filet sample. The other sample was the White Catfish sample from Station 436 with a ratio of3.353. This ratio is due to the elevated furan concentrations in the file! sample. ' -• • Table 3. "Total" Dioxin/Furan Concentrations in Roanoke Fish Tissue Samples. Station Sample Species Carcass File! Ratio 434 White Catfish 73.5 70.35 0.957 435 White Catfish 71.8 71.75 0.999 436 White Catfish 85.9 288 3.353 4.40 White Catfish 67.15 85.4 1.270 4219 White Cat.fish 69.7 78.35 1.120 -440 Yellow Catfish 115.3 59.9 -·0.520 434 Largemouth Bass 69.4 · 67.15 0.968 435 Largemouth Bass 71.55 70.35 0.983 436 Largemouth Bass 73.45 67.05 0.913 440 Largemouth Bass 69.45 63.20 0.910 449 Largemouth Bass 71.1 73.65 1.036 736 Largemouth Bass 72.85 61.55 0.845 Dioxin/Furan Congeners Detected in Roanoke Fish Samples Table 4 lists the individual dioxin/furan congeners that were detected in the Roanoke fish samples. In every case, the detected congeners in the carcass samples were 23 78-TCDD and/or 2378-TCDF. Also, in every case but one, the detected congeners in the file! samples were limited to the 2378-TCDD congener. The one exception was the. White Catfish sample from Station 436 in which 12378-PeCDF, 23478-PeCDF, 123478-HxCDF, 123678-HxCDF, and 1234678-HpCDF were reported in the file! sample. These congeners were not reported at detectable concentrations in any other fish tissue samples ( carcass or file!). The analytical results for all other Roanoke tissue samples were reviewed for the furans detected in the White Catfish sample from Station 436 (12378-PeCDF, 23478-PeCDF, 123478-HxCDF, 123678-HxCDF, and 1234678-HpCDF). These congeners·were not detected in the bioaccumulation study samples, Redear Sunfish samples, Bluegill samples, Corbicula Clam samples, Rangia Clam · samples, or whole Largemouth Bass samples. One congener, 123478-HxCDF;was reported in one Bullfrog sample .. However, the estimated concentration of0. l ng/kg, was more than 20 times lower than the detection limit reported for the other samples and more than 200 times lower than the concentrations reported in the White Catfish file! sample. Discussion The review ic\entified several issues that cast doubt on the validity of the White Catfish filet sample result from Station 436. These issues exist at several levels: the individual White Catfish sample (Station 436), the species level (White Catfish in the Roanoke River), and the system level ( other ' tissue samples from the lower Roanoke River system). • • Table 4. Dioxin/Furan congeners reported in Roanoke Fish Tissue Samples. Station Sam11le S11ecies Carcass Sample File! Sam11le 434 White Catfish none none 435 White Catfish 2378-TCDD none 436 White Catfish 2378-TCDD 2378-TCDD 2378-TCDF 12378-PeCDF 23478-PeCDF -· 123478-HxCDF. 123678-HxCDF 1234678-HpCDF 440 White Catfish none none 449 White Catfish 2378-TCDD none White Catfish 2378-TCDF 440 Yellow Catfish 2378-TCDD none 434 Largemouth Bass 2378-TCDD none ' 435 Largemouth Bass none none 436 Largemouth Bass 2378-TCDD 2378-TCDD 440 Largemouth Bass 2378-TCDD none 449 Largemouth Bass none none 736 Largemouth Bass 2378-TCDD 2378-TCDD 2378-TCDF One of the hazards associated with chlorinated hydrocarbons such as dioxins and furans is their ability to bioconcentrate in organisms. Since these contaminants are hydrophobic, they tend to accumulate in the fats and lipids associated with tissue. One problem this raises with the Station 436 White Catfish file! sample is that the concentration of detected dioxin.and furan congeners in the filet are higher than in the carcass even though the lipid content of the carcass is more than twice that of the file! (8.7 percent.vs 4 percent){Table 2). A consideration of the differential lipid content would suggest that more dioxin and furans should be present in the carcass. A second problem is that more individual dioxin and furan congeners were detected in the filet _than in the carcass (6 vs 2)(Table I). Its not conceivable that a hydrophobic contaminant would be taken in by the fish ( either by ingestion or through the gills) and pass directly to the muscle (file!) without some residue in other • • tissues. Degradation doesn't seem plausible since the congeners detected in the file! but not the carcass have higher levels of chlorination (i.e., the file! congeners have 5, 6, and 7 substituted chlorine atoms per molecule but the carcass only has 4 substituted chlorine atoms per molecule). The relative abundance and congener distribution in the White Catfish sample from Station 436 is not ' what would be expected based on the chemistry of dioxins and furans ad the lipid distribution of the sample. A comparison of_the White Catfish sample results from Station 436 with other Roanoke Catfish samples also suggests that the Station 436 sample result is suspect. The other Catfish samples had between O and 2 detected dioxin or furan congeners and the Station 436 carcass sample had 2 detected dioxiR.and furan congeners (Table 1 ). Thus, the Station 436 carcass sampl~ is consistent with other Roanoke Catfish samples. However, there were no detected dioxin or furan congeners in any other White Catfish file! sample except that atStation 436 that had 6. The calculated sum dfthe dioxin and·furan congener concentrations for White Catfish carcass samples in the Roanoke were in the range of O to 6.3 ng/kg. The calculated sum for the Station 436 carcass sample was slightly higher at 9 ng/kg. However, the filet/carcass ratio for all other catfish samples was O but the ratio for the Station 436 sample was 23.94. If the White Catfish had some capacity to selectively transfer and store dioxin/furan contamination in the filet, one would expect to see some level of contamination in the other catfish samples. However, without this, the ratio for Sample 436 appears to be anomalously high due to the reported file! results. A filet/carcass ratio was also calculated for the 16 dioxin/furan congeners used in the fingerprinting process (a value of one-half the reported detection limit was substituted for non-detectable results for this calculation). The results of this exercise (Table 3) indicate that the Roanoke White Catfish ratio was in the range of0.957 to 1.270. By comparison, the calculated ratio for the Station 436 sample was 3.353. Again, the results for the Station 436 White Catfish sample are outside the range for other Roanoke samples and appear to be anomalously high. A check of the high volume water sampling· results indicates that the concentration for the congeners reported in the Station 436 file! sample, 12378-PeCDF, 23478- PeCDF, 123478-HxCDF, 123678-HxCDF, and 1234678-HpCDF, were reported as non-detectable across the project area. Thus, the Sample 436 concentration can not be shown to be attributable to a concentration increase in that area. The Station 436 White Catfish carcass sample is within the range defined by other Roanoke White Catfish samples. However, the Station 436 White Catfish filet sample has a greater number of dioxin/furan congeners, at higher concentrations, and at distinctly elevated concentration ratios than all other catfish samples from· the lower Roanoke Basin. The Station 436 White Catfish results were compared to all other tissue analyses results in the study. All other carcass results had between O and 2 detectable dioxin/furan congeners (Table 1 ), the detected congeners were 2378-TCDD and/or 2378-TCDF (Table 4), and the sum of the detectable concentrations were in the range of Oto 12.2 ng/kg (Table 2). The White Catfish carcass sample results from Station 436 were consistent with all these values (two detected congeners, 23 78-TCDD and 2378-TCDF, total detectable concentration of 9 ng/kg). All other file! samples had between 0 and I detectable congener, the only detected congener was 23 78-TCDD, and the concentrations were in the range ofO to 1.6 ng/kg. Also, Station 436 sediments were used in the bioaccumulation studies. The only congener detected in the test species following exposure was 2378-TCDD (ie, the 5 furan congeners reported in the Station 436 White Catfish file! sample were not detected in the organisms used in the bioaccumulation study). As discussed above, the Station 436 White Catfish filet had 6 • detectable congeners (including 5 not detected in any other tissue sample) at a concentration that was two orders of magnitude higher than was seen in any other tissue sample. The type and level of dioxin/furan contamination reported for the Station 436 White Catfish carcass is consistent with all other Roanoke tissue analyses. However, the type and level of dioxin/furan contamination reported for the Station 436 White Catfish filet sample appears to be anomalously high.