Document jmjw31eDM8Jvj2Lev0vdbXvNp

* I* /r%^ ^ .^dii iS.'HT M O N SA N T O RESEARCH CORPORATION / DAYTON LABO RATO RY / DAYTON, OHIO 4 5 4 0 7 EASC-Davton (DEPT./SECTION) \ Vs ' s* REPORT NO.: MDA-283 a w JOB/PROJECTNO.:, 320.2140 < 2t--:( DATE: February 25 , 1982 ci o PERIOD COVERED: Analvtical TYPE OF REPORT --------- . . . - 7 REPORT -- ---- U TITLE: ANALYSIS OF 2,4-DICHLOROPHENOLS FOR o CHLORINATED DIBENZO-p-DIOXINS cao Vi o ,2 O o B O i"t tH ** G1--( 'ad1-C2KOH -X . CNlo1--I a U. c1 u*; a L> to 1 (--1o U to ro o >- 2 *o a < a u i--< Uh < a ABSTRACT: A sample of 2,4-dichlorophenol from the Krummrich Plant was analyzed at the Dayton Laboratory in the Ultratrace Facility. The samples were analyzed for the presence of chlorinated dibenzo-p-dioxins. Technical Approval : Frederick D. Hileman Senior Research Chemist r o .. X LU '5 H <H tOoO * CN1 I < fr > oltlri oCL. a Approved by: _ Robert F. Ivory Environmental Analytical Sciences Center Service Project Manager Approval date: 2.- J-a'-rf RESTRICTED DISTRIBUTION (see over] COMPANY CONFIDENTIAL This document is the property of Monsanto Research Corporation end the recipient is responsible for its sefekeepng end disposition.' h contains CONFIDENTIAL IN F O R M A T IO N w hich must not be reproduced, revealed to unauthorized persons or s e ^ ^ t^ sjria ^ a o sitfitp pesearch^Cornnretion and Monsanto Com pany I COPY NUMBER 1 E. A. Fay 2 J. D. Wilson 3 R. B. Hudson 4 D. B. Edwards 5 T. A. Taulli 6 R. F. Ivory 7 F. D. Hileman 8 Central Files 9 Tech. Reports 1740 G3WG N3A B2SG NID 1250 1250 1250 R3C ABSTRACT ONLY R. K. Flitcraft-1250 R. M. Scott-1250 NOTE: Distribution of this report is restricted. Requests for additional copies should be made through the principal ' contact at the Monsanto location involved or the Manager, Environmental Analytical Sciences Center, Dayton Laboratory, Dayton, Ohio. i ACKNOWLEDGEMENT Contributions of the following Dayton Laboratory personnel to this project are gratefully acknowledge: Analyses: D. E. Kirk !G O ;M il^ N |V M C :o :i\iF llD l N |i||:l^ l When no longer needed, or upon requ this report to Central Files, Dayton. ( DF.^TTA I SAMPLE PREPARATION AND ANALYSIS One sample of 2,4-dichlorophenol was received for the analysis of chlorinated dibenzo-p-dioxins (CDDS). In addition a sample from a previous analysis, A-102 and 103 was to be reanalyzed. The samples were assigned MRC log number 1-82-02-11-02. The samples were prepared for analysis by dissolving five grams of dichlorophenol in IN KOH. The basic solution was extracted with 40 mL of petroleum ether by shaking the mixture for 15 minutes. The base layer was removed and the petroleum ether was washed with 50 mL of organic free water. This water wash was removed and the petroleum ether was dried over anhydrous sodium sulfate. The petroleum ether was concentrated to 0.5 mL and applied to a chromatography column containing 4 grams of Woelm basic alu mina. Due to some problems in low'er recoveries for the monochloro and octachlorodibenzo-p-dioxin in the previous study the 10% dichloromethane/hexane elution was changed to 2% dichloromethane/hexane. The column was first eluted with 10 mL of this 2% dichloromethane/hexane and this fraction discarded. An additional elution was made with 15 mL of 5'0% dichloromethane/ hexane and 500 uL of dodecane was -added to this eluant as a keeper. The elutant was concentrated to 300 yL and.submitted for GC/MS analysis. The GC/MS analysis was carried out on a Hewlett Packard 5985B GC/MS system. A 50 meter SE-54 capillary column was used for all gas chromatographic separations. The mass spectrometer was used in the selected ion monitoring mode analyzing for ions chracteristic of monochloro through octachlorodibenzo-p-dioxin. The results of the analyses are shown in Table 1. In the case for sample A-102 and 103 the results are given as the -sum total of all isomers of a given degr.ee of chlorination of dibenzo-pdioxin. The spiked samples were readily detected with the exception of the low level monochlorodibenzo-p-dioxin (MCDD) spike. The change in column elution conditions did not improve the recoveries from the last analyses and we are currently trying to resolve this problem. Note that for the low level MCDD spike, the "found" level was below the "Method detection limit". This "found" level reflects the instruments sensitivity while the "Method detection limit" takes into account the poor recovery for the MCDDs.1 1 run ir-- TABLE 1. ANALYSIS OF 2,4-DICHLOROPHENOL FOR CHLORINATED DIBENZO-p-DIOXINS ng CHLORINATED DIBENZO-p-DIOXIN/gm PHENOL (ppb) 0 h-1 00 Sample Cli CI2 Cl 3 Cli Cl 5 Cl6 C I 7 2-7-82 Tank 163 ND* ND ND ND ND ND ND ND 2-7-82 Tank 163 (Rep) ND ND ND ND ND ND ND ND 2-1-82 A-102 and 103 ND ND ND 2.1 4.9 5.4 3.6 5.7 2-2-82 B-101 (Blank) ND ND ND ND ND ND ND ND Method Detection 10 1 1 1 1 1 1 1 Limit N) Spike Level 2-7-82 Tank 163 (found) Recovery % 3.9 1.7 2.0 1.8 3.8 6.4 3.6 7.6 ND 1.0 1.9 1.6 3.6 5.7 3.3 6.1 -- 59 95 89 95 89 92 80 Spike Level 2-7-82 Tank 163 ( found) Recovery % 39 17 20 18 38 64 36 76 .6 14 18 15 34 59 36 55 2 82 90 ' 83 89 92 100 7.2 * ND=none detected at the method detection limit H I Tin j k J H i l W ;'j I N-% .rV ^ ' . " t L * T " \ M O N SA N T O RESEARCH CORPORATION / DAYTO N LABO RATO RY / DAYTON. OHIO 4 5 4 0 7 EASC - Dayton (DEPT./SECTION) Analytical TYPE OF REPORT REPORT Q W E-> < 2 H X O hT X u xoX CO o XX X OX o G co < 2H X 0 H Q1 U X OIj H o J-t CO IS3 0) >*2 TJ 0) U < 2 in < XDCoHoOc -vH.Ju. <P REPORT NO,: JOB/PROJECTNO.: MDA-330 320.2220 DATE: PERIOD COVERED: October 12, 1982 TITLE: ANALYSES OF PARACHLOROPHENOLS FOR CHLORINATED DIBENZO-p-DIOXINS .,, A U T H O R S:^ Sissqjf t.. ABSTRACT: Five samples of parachlorophenol from the Krummrich Plant were analyzed at the Dayton Laboratory in the Ultratrace Facility, The samples were analyzed for the presence of chlorinated dibenzo-p-dioxins. Technical Approval Frederick D. Hileman Senior Research Chemist 1Aa >jC1a . Approved by : A Robert F. Ivory Environmental Analytical Sciences Center Service Project Manager om m I < E 2o Oz I-- Q. LCUC oQo. Approval date: Z Z J /i~ X /- RESTRICTED DISTRIBUTION (see over) COMPANY CONFIDENTIAL Thi* document is the property of Monsanto "Research Corporation end the recpiem a responsible for its M fekee p no end d.sposmon, H contein C ONFIDENTIAL IN FO R M A T IO N w hich must not be reproduced, revealed to unauthorized persons or tent outside M o ns onto Research -CONF!without proper authorust* insantoCompany SAMPLE PREPARATION AND ANALYSIS Five samples of parachlorophenol were received for the analysis of chlorinated dibenzo-p-dioxins (CDD). The samples were assigned MRC log number 1-82-09-14-02. The samples were prepared for analysis by dissolving five grams of the-phenol in IN KOH- The basic solution was extracted with 40 mL of petroleum ether by shaking the mixture for 15 minutes. *The base layer was removed and the petroleum ether was washed with 50 mL of organic free water. This water wash was removed and the petroleum ether was dried over anhydrous.sodium sulfate. The petroleum ether was concentrated to 0.5 mL and applied to a chromatography column .containing 2.5 grams of Woelm basic alumina. .This column was first eluted with 10 mL of 2% dichloromethane/ hexane and this'fraction discarded. An additional elution was made with 15 mL of 50% dichloromethahe/hexane and 300 yL of dodecane was added to this eluant as a keeper. The eluant was concentrated to 300 yL and submitted for GC/MS analysis. The GC/MS analysis was carried out on a Hewlett Packard 5985B GC/MS system. A 30 meter.Se-54 capillary column was used for all gas chromatographic separations. The mass spectrometer was used in the selected ion monitoring mode analyzing for ions characteristic of various CDDs. The results of the analyses are given in Table 1. In all cases the results are given as the sum total of all iosmers of a given degree of chlorination. In the case for the tetrachlorodibenzo-p-dioxins (TCDDs), the 2,3,7,8-TCDD has been listed separately. Thus for KB-5043 there was a total of 2.6 ppb TCDDs, however less than 1 ppb coeluted with the-2,3,7,8-TCDD. In most instances the TCDDs consisted of the 1,3,6,8-TCDD and 1,3,7,9-TCDD. 1 TABLE 1. ANALYSIS OF PARACHLOROPIIENOLS FOR CHLORINATED DIBENZO-p-DIOXINS ng/gm (ppb) Sample ID Cli Cl2 Cl3 Cl ** Cl,,* Cl 5 C1Q CI7 CIq KB-5043 ND ND ND 2.6 ND ND ND ND ND KB-5043 Replicate ND ND ND 2.4 ND ND ND ND ND KB-5044 ` ND ND ND 3.2 ND ND ND ND ND KB-504 5 ND ND ND ND ND ND ND ND , ND KB-504 6 ND ND ND 2.7 ND ,,ND ND ND ND KB-504 7 ND ND ND ND ND 'ND ND ND ND Blank ND ND ND ND ND ND ND ND ND Method Detection Limit 1.0 1.0 1.0 1.0 1.0 1.0 1.0 1.0 1.0 Spike Level 2.5 2.5 2.7 -- KB-5043 2.2 2.5 2.6 -- Recovery % 88 100 96 -- 2.0 2.4 2.3 1.7 1.7 1.9 85 71 83 2.5 2.0 2.4 1.9 96 95 Spike Level KB-5043 25 25 27 -- -- -- 20 24 23 25 20 18 20 22 -- 16 22 21 22 17 Recovery % 72 81 81 .-- 80 92 91 88 85 ,,* r;' ' ~ , '- t . , | ' Vv'. = analysis of .the 2,3,7,8-tefcrachlorodibenzo-prdioxin.; . : r i