Document ZnYOxQQe2zjee3kaq1ONp99KO

P71--santo r ----- , n ***l a R. F. Ivory - EASC - Dayton Lab - 1250 OAU * 41P *< M I -il S * I TO October 10, 1980 Analysis of Chlorophenols for Dioxin Content MRC Job #320.3010 J. A. Gloeckner Krummrich Plant D. Dahm F. Hilemn T. Maeex RECEIVED MLjvjR :.,.U-i985 HyK Eighty one samples (fifty-five samples, thirteen spikes, seven duplicates, and six method blanks) were analyzed for the presence of chlorinated dibenzo-p-dioxins. The samples wer analyzed on a Hewlett-Packard 5985A GC/MS system using MRC Method #01-GCMS-R2, with the exception that a 1% Dexsil 300 column was used instead of the 3% Dexsil 400.1 An extensive clean up procedure was used to prepare the extracts for GC/MS analysis. Five gram samples of the phenols were dis solved by shaking with 75 ml of 20% KOH for five minutes. Forty ml of petroleum ether were added and shaken with the base for several minutes to extract the dioxins into, the organic layer. The base was then removed, leaving the organic -layer which was subsequently subjected to 20% KOH, concentrated sulfuric-acid and water washes to remove various impurities and matrix components. The organic layer was then dried over sodium sulfate, followed by concentration to about 0.5 ml. This extract was then quantitatively transferred to a mini-chromatographic column packed with 3.0 g of Woelm alumina, and eluted with 2% dichlororaethane in hexane for orthochlorophenoi and 10% dichloromethane in hexane for the para-- chloro and 2 ;4-dichlorophenol. These fractions were discarded. The column was then eluted with 50% dichloromethane in hexane and this fraction collected, concentrated to dryness and submitted for analysis. The results of the analyses are given in Tables 1 through 3. Detection limits achieved are lower than previously attained; in particular for TCDD the detection limit has been reduced by an order of magnitude. Footnotes included with these tables cover the fact -that in certain cases an interference peak was observed which interfered in the analysis of a given dioxin and subsequently raised the lower detection limit. In addition, for those cases where the standard curves were prepared using one isomer of a given chlorodioxin and the unknown was a different isomer (as noted by a different retention time), these samples have been flagged to show that there could be some degree of error in the quantitation. J. A. Fletcher October 10, 1980 Page 2 MRC Method #7 was followed for QA/QC with the exception:that one low spike for the 2,4-dichlorophenol was spilled in processing. If you have any questions contact me at Ext. 417. RFI:dera SUBJECT TO PROTECTIVE ORDER. \. TABLE 1, NANOGRAMS PCDD/GRAM MATERIAL '(ORTHOCHLOROPHENOLS) Sample 8005 Blank 8015 8011 8023 8026 8025 8005 replicate 8001 8001 replicate 8018 8022 8027 Blank 8029 8031 8032 8015 8015 low spike 8015 high spike 8018 8018 low spike 8018 high spike Lower detection limit Mono 6.7 - i" 3.8 -- -- - -- - 34% 21% 56% 23% 2 Di -- - - -- -- - -- - a 99% 84% 88% 1 Tri - - - - - - - -- -- -- - Tetra ... - - -- -- - 66%' ' 72% vv 73% 70% . 1 78% 63% 78% 57% 0.9 a Could not be calculated due to interference at this mass. Penta _ 2.2 - - - - - -- -- -- -- - a 77% a 71% 2 Hexa . - -- - - - - - ** -- - Hepta -_ - - - - - - -- - - 74% 69% 75% - 74% 76% 98% 64% 62% 33 Octa _ 2 -- - - -- - -- - - 2 85% 83% 84% 66% 2 SUBJECT TO PROTECTIVE ORDER TABLE 2. NANOGRAMS PCDD/GRAM MATERIAL (DICHLOROPHENOLS) mi 7003 Sample 7007 7010 7013 Blank 7017 7017 replicate 7022 7023 7024 7025 7027 7029 Blank 7032 7032 replicate. Lower detection limit 7007 7007 low spike 7007 high spike 7023 7023 low spike 7023 high spike Mono 15.6 UT 553 0.9 11.6 :o.9 26% y v 23% 37% 19% 99% 21% 51% T ri . 2 (108a) 112.9/ 4* 6.6 T e tra 2.6* B :n 2. 1* 3.0* 2.5* I" PervteC 13.2* 15* Hexa_V 3.1 2.5** 2.0 2.4a* 3 0.9** 2.7a* 0.9a* 6.8 3 3a * f o S * l.la * 4.4 1.2a* 1.0 4a 45% 31% 59% 56% 1 . 2* 0.t9 58% 43% 114% 89% 90% 48% 3.8 131% 85% 84% 67% MM ir t illi - * * ir 5 2.6 10.6 23 5' 79% 68% 44% 53% 5.7 89% 119% 74% 93% aQuantitation was carried out on an isomer other than that in question. *Interference present which raise the lower detection limit. SUBJECT TO PROTECTIVE ORDER. V s Sample 5002 5006 5011 5011 replicate 5014 5019 Blank 5020 5024 5025 5028 5030 5031 Blank 5035 5037 5040 5040 replicate 5044 5049 5050 5051 5053 5056 5058 5058 replicate 5063 5064 Blank 5065 5068 5070 5072 TABLE 3, NANOGRAMS PCDD/GRAM MATERIAL (PARACHLOROPHENOLS) .Mono Di Tri Tetra Penta Hexa Hepta Octa (continued) / subject to PROTRmi oaoai TABLE 3 (continued) Sample Mono Di Tri Tetra Penta 5014 5014 high spike 5030 5030 low spike 5030 high spike 5056 5056 low spike 5056 high spike 28% 36% 47% _---- - 53% 45% 65% i 71% 66% -- 1* - 42% -- 30% 56% 54% -- 64% 78% _ 59% 51% . 48% 69% 87% 59% 68% Lower detection limit 63 1 0.9 3 ^Interferences were present. ~' Interferences would not allow recovery calculation to be made. Hexa .Hepta Octa 57%. 96% 75% si% _ 48% 71% 61% 40% 74% 56% 44% 52% 59% 92% 57% 3 3 2.5 {