Analytical Methodology for Herbicide Orange. Volume II - Special ...

Item I Number 04848 D NotScann8dAuthorFee > D cCorporate AuthorRBDOrt/ArtlGlB Title Analytical Methodology for Herbicide Orange. VolumeII: Determination of Origin of USAF StocksJournal/Book TitleYear1975Month/DayMa vColorDNumber of Images44Dascripton Notes AD-AO 11 598Thursday, February 14, 2002 Page 4848 of 4919

AIVIN L. YOUNG, Major, USAFConsultant, Environmental ScienceonUNCLASSIFIEDfatly-Tied /MUJWojy&r J-WHewJeO.C«7JT-OHCDefense Documentation CenterDefense Logistics AgencyCameron Station • Alexandria, VirginiaUNCLASSIFIEDAEROMEDICAL LIBRARY

A D - A 011 5 y 8ANALYTICAL METHODOLOGY FOR HERBICIDEORANGE. VOLUME II: DETERMINATION OFORIGIN OF USAF STOCKSD. C. Fee, ct alAerospace Research LaboratoriesWright-Patterson Air Force Base, OhioMay 1975DISTRIBUTED BY:National Technical Information ServiceU. S. DEPARTMENT OF COMMERCE

- w f w ' H n i S s s R sADA011598

UnclassifiedSECURITY CLASSIFICATION OF THIS PAGE '*>i*n o«r*REPORT DOCUMENTATION PAGEI REPORT NUMBER J. GOVT ACCESSION NO.RL 75-0110, Vol II4. TITLE (man Submit)Analytical Methodology forHerbicide Orange. Vol.II. Determination of Origin of USAF StocksREAD INSTRUCTIONSBEFOKF. COMPLETING FORM> RECIPIENT'S CATALOG NUMBERSTYPE OF REPORT » PERIOD COVEREDTECHNICAL — FINALDecember 1972 -Dfrnmhpr6- PERFORMING ORG. REPORT NUMBER7. AUTHORS;D. C. Pee, B. H. Hughes, M. L. Taylor, T. 0.Ticrnan (ARL), ind C. K. Hill, Jr. (SRL)9. PERFORMING ORGANIZATION NAME AND ADDRESSARL (AFSC) & Systems Research LaboratoriesChemistry Research Laboratory (LJ)Wright Patterson AFB. Olf 45433 iII.CONTROLLING OFFICE NAME AND ADDRESSARL (LJ)Building 450, Area BWright Patterson AFB, OH 45433MONITORING AGENCY NAME » AODRFSSiil Jill-rent Iran. Cantiotllnl OI/ic«JAir Force Logistics Command (OS)Wright Patterson Air Force Base !Ohio 45433eCONTRACT OR GRANT tJUMBEHf.)F33615-73-C-4099 andin-house10. PROGRAM ELEMENT. PROJECT, TASKAREA « WORK UNIT NUMBERSDOD Element 61102F702306 1412 REPORT DATEMay 197513. KlliuRFfl OF PAGES15 SECURITY CLASS, tel ihlm mporr)Unclassified1S>. DECLASSIFICATION DOWNGRADINGSCHEDULE IS OBSOLETE 'SECURITY CLASSIFICATION OF THIS PAGE ftrhfa Dtlm I

UnclassifiedJtCUHITY CLASSIFICATION OF THIS PAOtfHTian D«l» B

PREFACEThe research and development described in this report were performed inhouseby the Gaseous lonizat r .on and Excitation Processes Group of theChemistry Research Laboratory, Aerospace Research Laboratories (AFSC),Wright Patterson AFB, Ohio.' This work was funded by Air Force LogisticsCommand, Assistant Deputy Chief of Staff/Distribution, Mr. Karl Merrill.Dr. Billy E. Welch, Special Assistant for Environmental Quality, Officeof the Secretary of the Air Force, had overall cognizance for thiseffort which was undertaken to provide analytical chemistry support ofUSAF efforts to dispose of excess herbicide stocks in accordance withEnvironmental Protection Agency guidelines. The in-house work forcewas augmented during these studies via Contract No. F33615-73-C-4099 withSystems Research Laboratories, Inc., Dayton, Ohio 45440. These studieswere performed under Project 7023, Task 702306, Work Unit 70230614,"Advanced Mass Spectrometric Analytical and Diagnostic Techniques forMaterials and Research Applications."The ARL principal investigator ir. these studies was Dr. Thomas 0. Tiernan,ARL (LJ), Wright Patterson AFB, Ohio 45433.

TABLE OF CONTENTSSECTIONIINTRODUCTIONPACE1IIIIIEXPERIMENTALRESULTSREFERENCES3429ill

LIST OF TABLESTABLEPAGEIIIIIIIVVVIVIIVIIIIXIdentification Data on Herbicide-Orange Stocks at Gulfport,Mississippi 5Comparison of Analyses of Duplicate Samples from Same Barrelof Herbicide-Orange (Thompson-Hayward Co., Analysis SequenceControl No. 1) 17Comparison of Analyses of Duplicate Samples from Same Barrelof Herbicide-Orange (Dow Co., Analysis Sequence No. 10) 18Comparison of Analyses of Duplicate Samples from the SameBarrel of Herbicide Orange (Dow Co., Analysis Sequence No. 10)Comparison of Duplicate Samples from the Same Barrel ofHerbicide Orange (Thompson Co., Analysis Sequence No. 5) 20Comparison of Duplicate Analyses of Samples from the SameBarrel of Herbicide Orange (Monsanto Co., Analysis SequenceNo. 4) 21Comparison of Duplicate Samples from the Same Barrel ofHerbicide Orange (Monsanto Co., Analysis Sequence No. 6) 22Summary of Analyses of Herbicide-Orange Stocks from Gulfport,Mississippi 24Characteristic Gas Chromatographic Peaks for Identificationof Herbicide Orange by Transportation Control Uumber 26^9iv

LIST OF ILLUSTRATIONSFIGUREPAGE1 Characteristic Chromatogram of Analysis Sequence Group 8(Hercules Company, TCN 9464 8156 0001); Barrel Numbers 2,7, 11B, and Barrel 99, Which was Mislabeled as Coming fromDiamond Company (TCN FY9461 7165 0001AA) 62 Characteristic Chromatogram of Analysis Sequence Group 14(Hercules Company, TCN 9464 8192 001); Barrel Numbers 17,27, 39, 42, 50, and 59 73 Characteristic Chromatogram of Analysis Sequence Group 18(Diamond Company, TCN FY9461 7165 0001AA) ; Barrel Numbers72 and 110. 84 Characteristic Chromatogram of Analysis Sequence Group 11(Diamond Company, TCN FY9461 8156 001AA) ; Barrel Numbers139, 186, and 217 95 Characteristic Chromatogram of Analysis Sequence Group 1(Thompson Hayward Company, TCN 9463 8155 X032) ; BarrelNumbers 244, 2/'S, 246, 247, 248, and Sample 278 whichwas a DuplicaLd from Barrel 246 106 Characteristic Chromatogram of Analysis Sequence Group 10,Subgroup A (Dow Chemical Company. TCN 9463 8155 X052) ;Barrel Numbers 249, 250, 252, and 233 117 Characteristic Chromatogram of Analysis Sequence Group10, Subgroup B (Dow Chemical Company, TCN 9463 8155 X052) ;Barrel Numbers 251, 254, 255, 256, 257, and 253, andSamples 275 and 276, Which are Duplicate Samples fromBarrels 251 and 256, Respectively 128 Characteristic Chromatogram of Analysis Sequence Group 3(Thompson Company, TCN 9463 7184 X011) ; Barrel Numbers259, 260, and 261 139 Characteristic Chroraatogram of Analysis Sequence Group 5(Thompson Company, TCN 9463 8155 X012) ; Barrel Numbers262, 263, and 264, and Sample 274, Which is a Duplicatefrom Barrel 263 1410 Characteristic Chromatogram of Analysis Sequence Group 4(Monsanto Company, TCN FY9463 7163 X001XX) ; Barrel Numbers265, 266, and 267, and Sample 277, Which is a Duplicatefrom Barrel 266 15

SECTION IINTRODUCTIONCommercial herbicide formulations containing 2,4,5-T (2,4,5-trichlorophenoxyaceticacid) have been used extensively over a period of years forbrush control in the United States, and were applied for defoliation purposesin South Vietnam.^"6 in 1970 it was discovered that some herbicide formulationscontaining 2,4,5-T also contain prohibitive levels (several parts-permillion)of a highly toxic contaminant, TCDD (tetrachlorodibenzo-p-dioxin), 2 " 6TCDD is formed as a by-product in the manufacture o*: 2,4,5-T and is approximatelya million times more toxic than 2,4,5-T. 1 ' 7 TCDD is known to causechloracne and other skin diseases in humans,8-11 endema in new-bornchicks,•'•O>12,13 ancj numerous birth defects in rats, mice, and hamsters. 1^-17In addition, the effects of TCDD may be cumulative.^ By 1970, the hazardsof the TCDD present in 2,4,5-T were well l:nown, and as a result further useof herbicides containing this compound was suspended in South Vietnam. Theuse of 2,4,5-T in the United States was also restricted. The U. S. EnvironmentalProtection Agency placed a total ban on the usa of 2,4,5-T having a"high"dioxin content. The level of TCDD which can be tolerated safely inherbicides is a subject of much controversy, and these limits may be revisedin the near future.The herbicide formulation used in South Vietnam was designated HerbicideOrange and consisted of an approximately 50-50 mixture of the butyl estersof 2,4-D (2,4-dichlorophenoxyacet.ic acid) and 2,4,5-T. When use of thisherbicide in Vietnam was discontinued, large quantities of this material wereon hand,and these remain in the USAF inventory today. Some 2.3 milliongallons of this material are presently stored in 55-gallon drums in twolocations—Gulfport, Mississippi, and Johnston Island in the Pacific Ocean.It is desirable to dispose of this herbicide as soon as practical,by either destroying it or (for those lots containing a "safe" level ofdioxin) using it for brush-killing applications. Either procedure requiresEPA approval or certification, and this, in turn, necessitates data on thechemical couposition and homogeneity of the herbicide on hand.The 15,200 barrels of herbicide presently stored in Gulfport, Miss.,were originally purchased in ten lots from several different manufacturers.Unfortunately, owing to rebarreling and handling of much of the herbicide,some mislabeling has occurred. As a result, extant records may or may notbe useful for assigning a given barrel of Herbicide Orange to one of the tenlots which were originally purchased. It is desirable, therefore, to developa simple and reliable technique for characterizing the Herbicide stocks on alarge-volume basis. The goal of the present work was to determine whether arapid, routine analytical technique such as gas chromatography could beapplied a) to characterize groups within the Herbicide-Orange stocksaccording to manufacturer or manufacturer's production run and b) to demonstratethat such groups are homogeneous, that is, that a given manufacturer'sproduct consistently has the same composition. Achieving these goals wouldgreatly reduce the number of analyses required to characterize the entireinventory since, hopefully, it would reduce a barrel-by-barrel analysisproblem to a gtoup analysis problem.

Reported herein are results of analyses of a limited number of barrelsof Herbicide Orange. The volatile components of the samples of herbicidewere analyzed by temperature-programmed gas chromatography.20 All c'lromatographicpeaks were not resolved. Greater effort could have bp.en made toresolve overlapping peaks through more careful selection of -2 liquid phase,^1porv-injector splitting of the carrier flow and multiple columns in series,22programmed-pressure gas chromatography,^3 trapping ard relnjecting,^ backflushing,25 or complex valving arrangements of multiple columns in series.26-28These techniques, while useful in analyzing mixtures with components of widelydiffering boiling points and physical-chemical properties, increase the timeof analysis or the complexity of the analytical apparatus—both undesirablewhen a barrel-by-barrel determination is being performed. As will be shown,the simple gas-chromatographic analysis performed proved to be quite sufficientto identify homogeneous groups of the Herbicide-Orange stock accordingto manufacturer or manufacturer's production run. The data presented demonstratethe feasibility of identifying Herbicide Orange by its characteristicgas-chromatographic "fingerprint."

SECTION IIEXPERIMENTALSAMPLING PROCEDURESamples of herbicide Orange were collected by personnel from the USAFEnvironmental Health Laboratories, Kelly AFB, Texas, from barrels selected atrandom from groups representative of each of the ten lots purchased. Sampleswere collected in 1- or 2-oz. glass bottles, and an appropriate identificationnumber was etched into each bottle; this number was painted on the correspondingbarrel of herbicide. In order to remove a herbicide specimen froma barrel, a bottle was attached to its own "coat-hanger" plunger, and thesample bottle was plunged about 18 in. into the drum contents and swirled fourto six times. The bottle with attached plunger was allowed to drip the excessherbicide back into the drum. Each bottle was then topped with new aluminumfoil, tightly capped, rinsed by dipping in gasoline, and allowed to dry.Each bottle was rinsed a second time in fresh gasoline before being detachedfrom its plunger, wiped with Kimwipes, and packed for shipment to the AerospaceResearch Laboratories for analysis.INSTRUMENTATIONThe analyses were accomplished with a Varian Model 1440 Gas Chroraatographequipped with a flame ionization detector. The components wereseparated on an 8-ft., l/8-in.-o.d. glass column packed with Gas Chrom Qcoated with 10% DC-200. Following injection of lufcof the sample, the columnwas temperature programmed from 110 to 240°C at a rate of 4°/min. Otheroperating parameters were helium carrier flow, 30 cc/min; injector temperature,275°C; and detector temperature, 275°C. The data were recordedwith a 1-mV strip-chart recorder, and an Autolab System IV computing integratorwas used to measure peak areas.

SECTION IIIRESULTSTable 1 lists the manufacturers of the herbicide lots sampled, the totalnumber of drums of each in stock, the number of samples taken for analysis inthe present study, and the TCDD levels reported earlier by Dow Chemical.Typical chromatograroa for each of these groups of samples are displayed inVigures 1 through 11. Harked differences in the composition of the Herbicide-Orange samples from different lots are immediately apparent. Before thesedifferences are discussed in detail, the overall reproducibility of thesampling and analysis procedures will be discussed.The reproducibility of the herbicide sampling and analysis methods isdemonstrated by a comparison of the results obtained for duplicate samplestaken from the same barrel at different times. Such comparisons are presentedin Tables 11 through VII. In these tables, the area of each peak is normalizedto the total area of all peaks detected for a given sample of herbicide,where the total area is taken to be 100%. The chromatographic peaks areidentified in this analysis by retention time only. The detector responseis assumed to be equal for all components. A thorough examination of TablesII through VII shows that the retention times and peak areas are reproduciblein general to within 4%, with the exception of the data shown in Table II.(The poor peak shapes which are exhibited for this sample in p ig. 5 are probablyresponsible for the lack of reproducibility in the corresponding quantitativedata in Table II.) This reproducibility of duplicate samples to within 4%is characteristic of the precision attainable with gas-chromatographic analysis.These results clearly indicate that a homogeneous sample was obtained from eachbarrel by the sampling procedure which was employed.The results of analyses of all barrels having the same analysis sequencenumber and transportation control number show that peak areas of individualcomponents are reproducible to within 30%, with one exception. (The somewhatlarger uncertainty here in comparing different barrels from the same manufacturermay indicate fluctuations in reaction conditions during a givenproduction run.) The exception is the group of barrels having AnalysisSequence No. 10, where evidence for at least two distinctly different subgroupswere found. Results suggesting two subgroups are shown in Figures 6 and 7. Eachsubgroup showed reproducibility to within 30%. Subgroup A included four of theten barrels sampled. The remaining six barrels sampled belonged to Subgroup B.It may be significant that subgroups were noted only in the analysis sequencegroup composed of the largest number of barrels of herbicide. In all other analysissequence groups (composed of a smaller number of barrels), the analysesshowed similar results (within 30% reproducibility) for all barrels sampled. Thechromatograms of the herbicide samples from all barrels tested in a given groupwere similar to the representative chromatograms which are shown in Flgurt-s 1-11.These results suggest that two or more separate production runs were made in themanufacture of the 6976 barrels of herbicide in Analysis Sequence Group 10, whilethe other analysis sequence groups (containing fewer barrels) were each manufacturedin one production run.**Extensive TCDD analyses presented in Vol. I of this report strongly suggestthe existence of two and probably more subgroups within Dow ASN 10.**The TCDD analyses reported in Vol. I actually indicate that only two of theASN batches are homogeneous. Conclusions above are based on a limited number ofsamples.

TABLE IIDENTIFICATION DATA ON HERBICIDE-ORANGE STOCKS AT CULFPORT, MISSISSIPPIManufacturerHercules Co.Hercules Co.Diamond Co.Diamond Co.Thompson Hayward Co.Dow Chemical Co.Thompson Co.Thompson Co.Monsanto Co.Monsanto Co.TransportationControl No. (TCN)9464 8156 00019464 8192 001FY9461 7165 0001AAFY9461 8156 001AA9463 8155 X0329463 8155 X0529463 7184 X0119463 8155 X012FY9463 7163 X0001XXFY9463 8183 X002XXAnalysisSequenceNo.81418111_103 —546Number ofTCN DrumsSampledTotal Numberof Drumswith Same TCN35006215236034216=154612 d6976468084 C5637 C 2185— -; — 3 -4°TCDD b(nR/kR)

7 Hercules 8uiJU900 1800 2TOOT1ME,S«CFigure 1. Characteristic Chromatogram of Analysis Sequence Group 8 (Hercules Company, TCN 9464 8156 0001);Barrel Numbers 2, 7, 11B, and Barrel 99 which was Mislabeled as Coming from Diamond Company(TCN FY9461 7165 0001AA)

59 Hercutes 14I900 1800 2700TIME, SecFigure 2. Characteristic Chromatogram of Analysis Sequence Group 14 (Hercules Company, TCN 9464 8192 001);Barrel Numbers 17, 27, 39, 42, 50, and 59

09 DIAMOND IIiLJkJJ900TWE.SECFigure 4.Characteristic Chromatogram of Analysis Sequence Group 11 (Diamond Company, TCN FY9A61 8156 001AA);Barrel Numbers 139, 186, and 217

m—is900t1800 2700TME.SecFigure 5. Characteristic Chromatogram of Analysis Sequence Group 1 (Thompson Hayward Company, TCN 9463 8155X032); Barrel Numbers 244, 245, 246, 247, 248, and Sample 278 which was a Dupl-'cate from Barrel246

' 2 * 0 0TME.SECFigure 6.Characteristic Chromatogram of Analysis Sequence Group 10, Subgroup A (Dow Chemical Company,TCN 9463 8155 X052); Barrel Numbers 249, 250, 232, and 253

251 Dow 10s900 1800 2700TIME.SecFigure 7.Characteristic Chromatogram of Analysis Sequence Group 10, Subgroup B (Dow Chemical Company,TCN 9463 8155 X052); Barrel Numbers 251, 254, 255, 256, 257, and 258, and Samples 275 and 276which are Duplicate Samples from Barrels 251 and 256, Respectively

259 THOMPSON 369OOTIME.SECBOOI~'fOOFigure 8.Characteristic Chromatogram of Analysis Sequence Group 3 (Thompson Company, TON 9463 7184 X011);Barrel Numbers 259, 260, and 261

o CL OO900 1800TIME, SecFigure 9.Characteristic Chromatogram of Analysis Sequence Group 5 (Thompson Company, TCN 9463 8155 X012);Barrel Numbers 262, 263, 264, and Sample 274 which is a Duplicate from Barrel 263

BOO27OOTWE.SECFigure 10. Characteristic Chromatogram of Analysis Sequence Group 4 (Monsanto Company, TCN FY9463 7163 X001XX);Barrel Numbers 265, 266, and 267, and Sample 277 which is a Duplicate from Barrel 266

263 MONSANTO 6BOO27QOTOE.SECFigure 11. Characteristic Chromatogram of Analysis Sequence Group 6 (Monsanto Company, TCN FY9463 8183 X002XX);Barrel Numbers 268, 269, 270, 271, 272, and 273, and Sample 279 which is a duplicate from Barrel 270

TABLE IICOMPARISON OF ANALYSES OF DUPLICATE SAMPLES FROM THESAME BARREL OF HERBICIDE ORANGE(THOMPSON-HAYWARD, ANALYSIS SEQUENCE NO. A)Sample I.D. No. 278 Sample I.D. No. 247Retention Time(sec.)Peak Area(rel. %)Retention Time(sec.)Peak Area^re. 1 _%)251131271382514584945245946607828581059139914671535160117381815185818771956206821002112222827310.380.070.050.190.150.180.860.680.050.050.090.171.6034.31.055.701.101.445.290.120.2513.231.30.160.330.100.75261141271382494574935225936587808561056139614641537159817341811185418741951206320982108222427270.390.110.070.230.160.260.880.650.050.050.100.181.6044.90.865.001.001.284.540.110.2410.924.70.130.360.100.7317

TABLE IIICOMPARISON OF ANALYSES OF DUPLICATE SAMPLES FROM THESAME BARREL OF HERBICIDE ORANGE(DOW, ANALYSIS SEQUENCE NO. 10)Sample I.D. No. 251Retention Time(sec.)Peak Area(rel. %)Sample I.D. No. 275Retention Time(sec.)Peak Area(rel. %)260.28270.301260.141280.1425239047675778180888199010541190126513901464161816461668171717591780180318401876197426650.101.240.150.220.090.060.110.091.590.643.0643.20.9644.11.970.080.250.040.110.110.060.070.360.47255393482761818887999106011971272139814701625165416761724178718121884198226770.101.260.150.310.060.110.051.590.582.9943.40.9943.61.990.060.210.090.070.040.360.3318

TABLE IVCOMPARISON OF ANALYSES OF DUPLICATE SAMPLES FROM THESAME BARREL OF HERBICIDE ORANGE(DOW, ANALYSIS SEQUENCE NO. 10)Sample I.D. No. 256Sample I.D. No. 276Retention Time(sec.)Peak Area(rel. %)Retention Time(sec.)Peak Area(rel. %)262543934837648911052120212771403147516311659168117281793181618531889198726800.230.100.33 ,0.120.13 ,0.04 /1.250.422.7045.50.8544.82.190.080.190.100.150.050.120.290.2927258398487768895106612061280140814791635166316851732179618191892199026800.230.100.330.110.130.041.260.472.7845.70.8544.52.190.080.180.100.140.060.290.3919

TABLE VCOMPARISON OF DUPLICATE SAMPLES FROM THESAME BARREL OF HERBICIDE ORANGE(THOMPSON CO., ANALYSIS SEQUENCE NO. 5)Sample I.D. No. 263 Sample I.D. No. 274Retention Time(sec.)Peak Area(rel. %)Retention Time(sec.)Peak Area(rel. %)2742677510315920325428750159462570875610571200121212361264139714641590164926891.60 '0.682.520.990.140.050.070.340.144.270.160.900.210.420.960.140.140.390.5441.00.3638.34.600.382743687610516320825929351060363471776610661209122012451276140714731600165927001.800.622.541.000.140.050.080.360.144.300.160.910.210.420.970.140.170.390.5241.10.3638.24.560.3420

TABLE VICOMPARISON OF DUPLICATE ANALYSES OF SAMPLES FROM THESAME BARREL OF HERBICIDE ORANGE(MONSANTO CO., ANALYSIS SEQUENCE NO. 4)Sample I.D. No. 266 Sample I.D. No. 277Retention Time(sec.)Peak Area(rel. %)Retention Time(sec.)Peak Area(rel. %)264268252491618704•'5110510.701.840.140.411.000.080.050.100.4226437025850162971576310630.701.870.130.400.990.080.050.100.4113981419146115911647169318041861191144.00.440.9141.44.700.160.880.130.18141114321474160416591681170518171873192343.20.450.7141.64.630.050.170.870.130.171975213526840.270.090.541987214826950.260.090.3821

TABLE VIICOMPARISON OF DUPLICATE SAMPLES FROM THESAME BARREL OF HERBICIDE ORANGE(MONSANTO CO., ANALYSIS SEQUENCE NO. 6)Sample I.P.. No. 270Retention Time(sec.)Peak Area(rel. %)Sample I.D. No. 279Retention Time(sec.)Peak Area(rel. %)2642682522854935936187037511052135514651620165317191918213926650.730.880.060.180.04

Quantitative data representing each of the analysis sequence groups aregiven in Table VIII. Identification of each analysis group (or subgroup) canbe made from specific peaks in the chromatograms as shown in Table IX.1) Analysis Sequence Group 8 (Hercules Company, see Figure 1) isuniquely identified by the large peaks at 1773 and 1993 sec. and by the regionbetween 600 and 900 sec. where no peaks are observed.2) Analysis Sequence Group 14 (Hercules Company, see Figure 2) isuniquely identified by the four small peaks at 1773, 1816, 1933, and 1984and by the region between 600 and 900 sec where no peaks are observed.sec.3) Analysis Sequence Group 18 (Diamond Company, see Figure 3) isidentified by the single large peak near the beginning of the analysis (26sec.) and by the six small peaks at 1744, 1773, 1816, 1933, 1984, and 2024sec.4) Analysis Sequence Group 11 (Diamond Company, see Figure 4) has afingerprint identical to that observed for Analysis Sequence Group 18. Theseare the only two groups examined in this study which cannot be distinguishedfrom each other by means of chromatographic patterns.5) Analysis Sequence Group 1 (Thompson Hayward Company, see Figure 5)is uniquely identified by the very large peak at 2070 sec.6) Analysis Sequence Group 10, Subgroup A (Dow Chemical Company, seeFigure 6) is uniquely idnetified by the relatively large peak at 1816 sec.7) Analysis Sequence Group 10, Subgroup B (iDow Chemical Company, seeFigure 7) is uniquely identified by the single large peak early in thechroraatograro (26 sec.), by the large peak at 394 sec., and by the small peakat 1984 sec.8) Analysis Sequence Group 3 (Thompson Company, see Figure 8) isuniquely identified by the four large peaks near the beginning of the analysis,particularly the peaks at 69 and 75 sec., by the peak larger than 4%at 500 sec., by the relatively large peak at 631 sec., and by rhe four smallpeaks at 1744, 1816, 1933, and 1984 sec.9) Analysis Sequence Group 5 (Thompson Company, see Figure 9) isuniquely identified by the four large peaks near the beginning of th=i analysis(69 and 75 sec.),, by the peak larger than 4% at 500 sec., by the relativelylarge peak at 631 sec., and by the absence of the four small peaks at 1744,1816, 1933, and 1984 sec. which are characteristic of the Group 3 chromatogramsnoted above.10) Analysis Sequence Group 4 (Monsanto Company, see Figure 10) isuniquely identified by three peaks at the beginning of the analysis (largepeaks at 26 and 42 sec. and a small peak at 69 sec.), by the absence of peaksat 900 * 50 sec., and by the five small peaks at 1744, 1816, 1875, 1933, and1984 sec.23

TABLE VIIISUMMARY OF ANALYSES OF HERBICIDE-ORANGE STOCKS FROM GULFPORT, MISSISSIPPIRetentionM •(sec.) 1 10A 10B3Analysis Sequence Number 35 4 _ 6 814 181126 0.43 0.36 0.2742 0.366975121 0.15130 0.12208258 0.16 0.11 0.10274291394 0.62413 0.23433460 0.16490 0.11 0.13500 0.93 0.27535 0.66580 0.056001.531.011.870.080.140.100.214.970.221.60 0.71 0.78 0.960.66 1.72 0.94 1.512.39 0.13 0.620.930.080.060.33 0.35 0.19 0.250.13 0.054.17 0.90 1.83 0.420.16 0.080.78 1.002.520.120.16- -0.291 0.550.080.05 0.200.270.150.70 1.370.130.860.130.490.070.240.381.230.11

RetentionTime(sec.6311 10A 10B30.70TABLE VIII (Continued)Analysis Sequence Number 350.8840.086 8 140.1618 116800.050.047130.180.200.050.067587730.110.140.390.380.090.160.22 0.157970.178680.058909090.060.17~-- —— -."_._0.12 0.1110300.16 0.081060115012001.59 1.17 1.420.390.290.960.360.140.410.60 0.58 1.280.78 0.6812602.0 3.060.41138736.9 43.2 43.141.641.944.144.4 41.4 42.446.3 45.814100.214711.02 1.0 0.850.430.370.440.70 0.89 1.60.40 0.3615455.9815971.15 41.8 44.139.540.041.443.5 38.5 42.041.5 42.816612.2 2.24.502.554.703.92 6.0 5.614.1 3.616700.0816940.1417441.95 0.42 0.220.060.240.060.19 0.17

TABLE VIII (Continued)RetentionTime(sec.)1Analysis Sequence Number 310A 10B 3 5 4 6814 18 1117731816187519331984202420702100213021502200223027006.080.2610.724.50.130.270.100.760.23 0.121.57 0.14 0.21 0.660.10 0.06 0.110.53 0.16 0.100.37 0.35 0.41 0.260.230.08 0.120.52 0.39 0.61 0.31 0.47 0.533.330.090.332.220.140.230.370.10 0.25 0.220.10 0.44 0.380.11 0.16 0.150.16 0.35 0.290.11 0.090.46 0.29 0.27See Table I to relate Analysis Sequence Number to TCN. Results listed represent relative peak areasof respective conponents.

TABLE IXCHARACTERISTIC GAS CHROMATOGRAPHIC PEAKS FORIDENTIFICATION OF HERBICIDE ORANGE BY TRANSPORTATION CONTROL NUMBERRetention , , . _ „ . a_.Analysis Sequence NumberTime ' ~(sec.) 8 14 18 11 1 10 10 3 5 4 626+2 0.96+.0.4 0.78±0.1 1.00+0.1 0.86+0.1 0,4310.1 0.36+0.3 0.27+0.1 1.53+0.1 1.60±0.40 0.71+0.2 0.7842+2 1.51+0.2 2.52+0.3 0.36+0.3 1.01±0.2 0.66+0.1 1.72+0.3 0.9469+2 0.12 b 0.13 1.87+0.1 2.39+0.4 0.13 0.0675+2 0.8210.1 0.93+0.2394+5 0.62*'*500±15 0.42+0.1 0.70+0.2 1.37+0.2 1.23±0.1 0.9310.1 0.2710.1 4.97±0.8 4.1710.5 0.9010.1 1.8310.1631+11 0.7010.2 0.88+0.1 0.16890+10 0.12 0.11 0.06909110 0.171744+10 0.19 0.17 1.95+1 0.42+0.2 0.22 0.06 0.24 0.061773120 3.33+0.1 0.10 0.25 0.22 0.23 0.121816+16 0.10 0.10 0.44±0.1 0.3810.1 6.08+1 1.5710.3 0.14 0.31 0.661875+20 0.33 0.26 0.10 0.06 0.111933+20 2.2210.2 0.11 0.16 0.15 0.53 0.16 0.101984+15 0.14 0.16 0.35 0.29 0.37±0.1 0.3510.1 0.41 0.262024+8 0.11 0.09 10.711.42070121 24.5+4.0a See Table I to relate TCN to Analysis Sequence Number. Results listed represent relative peak areas of respectivecomponents.The typical range is ± 202, unless otherwise indicated.

11) Analysis Sequence Group 6 (Monsanto Company, see Figure 11) isuniquely identified by three peaks at the beginning of the analysis (largepeaks at 26 and 42 sec. and a small peak at 69 sec,)., by the absence of peaksat 900 * 50 sec., and by the small peaks at 1744 and 1933 sec.The identification of Herbicide Orange by the characteristic chroir.atogra-nof each analysis sequence group as described above has already proved tobe highly successful. As an example, one barrel of. herbicide used indegradation studies was indicated by extant records to belong to AnalysisSequence Group 18 (Diamond Company). Subsequent fingerprinting of the barrelresidue following these tests clearly established that the herbicide inquestion was from Analysis Sequence Group 8 (Hercules Company). Knowledge ofthe original source of the herbicides is vital if valid conclusions are to bedrawn regarding the effectiveness of degradation techniques, because the compositionof the various lots varies quite markedly. If the decomposition ofspecific herbicide components is being monitored, obviously it is necessaryto know the quantities of these components present in the original herbicidetest sample.IIn summary, the data indicate that among the 15,200 barrels of HerbicideOrange stored at Gulfport, Mississippi, homogeneous groups can be identifiedby using a simple temperature-programmed gas-chromatographic analysis of the'/olatile components of this herbicide. It is thus possible to determine theoriginal manufacturer of any herbicide sample in these stocks by a rapid,simple analysis. This identification does not depend upon knowledge of thechemical identity of any component of the Herbicide Orange. In another, moreextensive report from this laboratory, however, identification of allIndividual components in selected lots of the herbicide stocks has been made byusing combined gas chromatography-mass spectrometry instrumentation.28

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