Document mm7G4dXZKGaVNoOv3KqpvVZNZ

p K f 2.g S' PPB Lev els of 2,3,7,3 Tetrachlorodisenzo-p -d io x in , ET.AL. IN SANTOPHEN7I (P roduction Perio d - May 1979 - S e p t . 1979) \ DATE 5/16/79 5/ /79 5/31/79 6/17/79 5/ /79 6/28/79 7/ /79 V /79 // /79 7/ /79 8/15/79 8/31/79 9/3/79 9/12/79 SAMPLE IDENTIFICATION KL05-90 CMS81J ) KL05-103 (MB754) KL05-109 (MB812) KL06-1W (f!3813 KL06-121 (113753) KLOS-123 (K881D) KL07-129 (MB783) KL07-130 (MB78L0 KL07-13A (MB785) KL07-135 (MB786) KL08-153 (MB817) KL08-159 (MB818) KL09-1S1 (MB789) KL09-153 (I1B790) ppb 2,3,7,8 TCDD, e t .a l . 1 <0,5 2 1 < 0.5 2 < 0.5 <0.5 < 0.5 <0.5 <0.5 1 <0.5 <0.5 Sum ptio n 0 1 . ) Average Lev el <1 ppb 2 . ) 65% Production, ND (<0.5 p p b ) 3 . ) Past 5 months, Ma x . Le v e l of 2 ppb C01 115 Confidential-Subject to r>- Orrlor T. A. Ta u lli Tetrachlorodibenzo- p - dioxih Levels (ppb) in Santophen-1 Production (May 1979-Sept. 1979) Date Sample I d en tific a tio n 9 TCDD I somers 2, 3,7,8 TCDD, ET.AL, 1 ,3 ,6 ,8 TCDD, ET. AL 1,3,7,9 TCDD, ET.AL. Total TCDD'Lev el 5/18/79 5/ /79 5/31/79 KL05-90 013211) ` KL05-103CMB7W) KL05-1Q0( MB812) 5/17/79 ' 6/ /79 6/28/79 7/ /79 7/ m i/ m i/ m KL06-1MCMB813) KL06-121O1B758) KL06-12.3CHBSlif) - KLQ7-129 (M3733) KLO7-J30 ( MB784) 1(17)7-134018785) KL07-135 CMB786) 8/15/79 8/31/79 !<L08-153(MB817) !<LO8-159( MBS IS ) 1.2 <0,5 2.2 1.1 < 0.5 1,7 <0.5 <0.5 <0.5 <0.5 J <0.5 0.8 0.5 <0,5 <0.5 <0.5 <0.5 <0.5 , 2.9 1.2 0.8 1.5 <0,5 <0.5 <0.5 <0,5 0.5 < 0.5 <0.5 . 0,5 * <0.5 <0.5 <0,5 <0.5 ' <0.5 2.0 1.7 <0.5 2,7 1.1 O <0.5 2,2 2.9 1.2 0,8 1.6 <0.5 oCD Lq 13 CV CO "J "COc '= < LCD_ '+"O < SO (i oc 2.8 9/3/79 9/12/79 KL09-16KHB789) KLO9-1631B790) <0.5 <0.5 <0.5 <0.5 <0.5 <0.5 <0.5 .'<0.5 S ummation: [ j AVERAGE (PPB) Range ( p p b ) 2, 1, 1,% ET,.AL, 0.8 <0,5 to 1,3,5 ,8 ET.AL. 0.7 <0,5 to 2,9 1,3,7,9 ET.AL, Total TCDD 0.5 <0,5 to 2,0 1.4 <-7,5 TO 2,9 TcTP/irmnRODIBENZO-P-PIOXIN Levels IPFB; IN SANIUPHbm r u u m n w uwh. JJ/O - nrftiL a.-./ jj Da t e Sa m ple I d e n t if ic a t io n TCDD I somers ______________ ,,2 3 7,8 TCDD, ET.A L. 1,3,6,8 TCDD, 1,3,7,9 TCDD, ET iA L. . ET.A L. To t a l TCDD Le v e l t;o i.5 ;iih ie ct to 8/17/78 ' 8/28/78 9/15/78 9/29/78 10/15/78 11/15/78 iy30/78 12/15/73 12/31/78 KK03-1Q7 (MB794) . KK08-117 (MB795) KKQ9-127 (MB796) KK09-139 (MB797) KK10-151 (MB798) . KK11-16.9. (MB800) KK11-182 (MB801) KK12-191 (HB802) KK12-2Q1 (MB803) 0.5 <0.5 0.5 - <0.5 1.4 <0.5 1 .2 2 .2 2.9 12.0 8.5 ' ' 10.0 . <0.5 ' 30.1 . 11.5 8.3 3.0 0.5 1.7 ' 17.6 <0.5 38.6 1.7 12; 8 9.1 0 .8 7.4 14.2 25.1 10.5 33.6 33.2 24.3 18.6 6.0 10.3 1/ /79 1/30/79 0 / /73 KL01-06 (MB781) KL91-14 (MB804) . KL02-25 (MB653) 2.3 1.1(5 r u n s ) <0.5 7.1 <0.5 0.5 .... .0..5 1.7 2.0 .. 0.5 4.0 9.1 1.5 3/ /79 3/30/79 4/ /79 -4/13/79 4/29/79 KL03-43 (MB698) KL03-67 (MB808) KL04-69 (MB ) KLQ4-74 (MB809) KL04-82 (MB810) <0.5 12.0 - 1 .8 0,5' 2.0 1 1,1(4 r u n s ) <0.5 4.0 2.9 0.5 ' <0.5 SUMMATION: 2,3,7,8 e t .a l . 1,3,6,8 e t .a l . Av e r a g e ( p p b ) R&ur:i: .1 . / n C "ra *f 1 5.7 p _7n i -- <0.5 0.5 <0.5 3,6 : co.5 1,3,7,9 e t .a l . 5,6 1222...800 10.5 0.5 To t a l TCDD 13.2 P x 1 3 e!g Monsanto_ _ _ _ _ _ _ _ ._ _ _ _ _ _ _ _ _ MONSANTO RESEARCH CORPORATION / DAYTON LABORATORY / DAYTON, OHIO 4 5407 ___________ E S C ~ DAYTON_______ (DEPT /SECTION! _______A N A L Y T I C A L TYPE OF R EPO R T REPORT Q Q &oUIo rm CN 0$ Oc> f Dm wM E-* w w o H Q G< n] Eb -04) o he cMn w < '*4 <2: w DDC .. D 3I- <F rm *r REPORT NO.: MDA - 437 XJB/PROJECT NO.: 309.61011 DATE: December 22, 1983 PERIOD COVERED: TITLE: ANALYSIS OF ADIPOSE TISSUE FOR 2,3,7,8-TCDD AUTHORS: F. D. Hileman ABSTRACT: Human adipose tissue samples were analyzed for 2,3,7,8-TCDD concentrations. This-report shows Approved By R. F. Ivory qJ Environmental Sciences Center Service Project Manager Approval Date CONFIDENTIAL SUBJECT TO PROTECTIVE ORDER. COMPANY CONFIDENTIAL TN** etoewmant it tf*a p ro p erty o< M o n aan io R a a a a rc h C o rp o ratio n and tha r*Cf>ont raaponatota tor rt* and d iw o t it c n H c o n t a c t C O N FID E N T IA L IN F O fU A A T IO N w tiic h m u ll not ba rap rodocad. Tvalad 0 im a u th o riia d p araona o f m o I o u u id a U o n u n t t fU a a a rc ti C o ro o ra tx n an d M o n a a n w C o m p any Eight human adipose samples were received for the analysis of 2,3,7,f-tetrachlorodibenzo-p-dioxin (2378-TCDD). The samples were assigned MRC log number 1-83-06-06-02. Each sample was run in triplicate, a sample, a replicate and a low level spike (7 ppt)- This spike level was selected because others have reported finding 1 to 10 ppt of 2378-TCDD in human tissue. Thus a 7 ppt spike could be readily detected in these samples in spite of background levels of 2378-TCDD. In addition, one of the samples was also spiked at a higher level (70 ppt) and a pork fat sample previously found to contain less than 0.7 ppt of 2378-TCDD was included as a blank. The samples were prepared according to the diagram given in Figure 1. The final extracts were analyzed on a Finnigan MAT 212 1/MS system. The gas chromatographic column that was used was a 60 m SP-2330 capillary column. This column was checked daily during this work to ensure that it uniquely resolved 2378-TCDD from the other 21-TCDDs. The mass spectrometer was operated at a resolution of 1000 in the selected ion monitoring mode following two ions characteristic of TCDD (320, 322) and one ion for each of the isotopically labeled TCDDs 37Cli*-2378 TCDD (328) and 13C 12-2378 TCDD (334). Quantitation was achieved by comparing the area of -unlabeled (naturally occurring) TCDD to the 13C i22378-TCDD. The standards used in this work have been cross validated against two separate EPA quality control standards. Qualitative identification was made by requiring the compound in question to coelute with the 13C 1 2-2378-TCDD and to have the correct 320/322 ratio of 0.79 1 0.10- The results of the analyses are given in Table 1. Note that the increase observed for the spikes all agree reasonably well with /he unspiked samples with the exception of sample Number 8. The cause of the problem may be sample inhom'ogeneity but the good precision obtained on the other samples would cast some doubt on this explanation. *# It should be noted that an additional replicate had been analyzed for sample 7. In the initial work this particular sample had the highest level of interferences and this sample was singly carried through the entire workup and analyzed. What is most important is that it was weighed out and worked up by a different individual than the one who did the work up on the rest of the samples. Thus it gives some measure of the operator independence of the method. Mention should also be given to detection limits. The GC/MS system was capable of detecting the equivalent of 0.5 ppt in a 25 gram initial sample. This assumes 100% recovery of the TCDD and no interfering compounds. The absolute recoveries of the 13C i22378-TCDD varied from 35-85% which when combined with any inter ferences would raise the nominal detection limit to approximately 1.0 ppt for these samples. Slightly better detection limits could ^ achieved for the pork fat and the solvent blank due to lower levels of interferenences present. i Analysis of Human Adipose Tissue for the Presence of 2378-TCDD Sample 866-83 2275519-i+ (Rep) (Spike) 881-83 2275519-2 (Rep) (Spike) 890-83 2275519-3 (Rep) (Spike) 928-83 2275519-4 (Rep) (Spike) 959-83 2275519-5 (Rep) (Spike) (Spike) 971-83 2275519-6 (Rep) (Spike) 989-83 2275519-7 (Rep) (Spike) (2nd Rep)* 1009-83 2275519-8 (Rep) (Spike) Pork fat (Rep) (Spike Solvent Blank ppt 2378-TCDD found 1.7 1.9 8.8 4.1 5.1 11.8 3.3 3.1 9.8 4.8 4.8 11.1 5.4 6.2 13.0 67.9 3.5 3.8 10.3 9.2 8.6 14.9 9.5 10.6 9.5 12.6 0.6 1 .0 6.3 0.8 ppt 2378-TCDD added -- 6.8 -- 6.6 -- 6.8 -- 6.6 -- 6.9 ,67 -. 6.8 - , 6.9 -- -- 6.3 -- - 6.7 -- Number to.which samples will be referred. See report for a descript.io 1 of the replicate. Adipose Preparation Spiking ,5-25 grams fat + 13C12TCDD in Acetone Digestion 75mi of 40*KOH + 40mlofEtOH overnight Add 50 ml EtOH + 100ml H ^ Extraction 3 X with 60 mi of Hexane Separate Washes H2S04^ H20 , NaOH Concentrate Column Silica + H2S04 , KOH Hexane Column Alumina - Basic-------- ^ C ^ / H e g n e %50 ch2ci^hexane 'Discard Column Carbopak C HcnfM L-i O ctofttanVCH^Cl^ 75JD-3 CH^CI^ AW OH/B*nn* Discard Toluene Concentrate Dodecane (10^1) + 37Cl4 " TCDD GC / MS Analysis 1 crhpmp for the preparation of adipose