Document 2qEXNNDoBJ0RoGY8g8r2vQmy6

Technical Service Report Report No. 2118--79-848-0 Continental Oil Company Research and Development Department Analytical Research Section Ponca City, Oklahoma To From Date R.E. Laramy G.W. Keen November 8, 1979 CONFIDENTIAL THIS DOCUMENT IS CONFIDENTIAL AND THE PROPERTY OF CONOCO INC. Subject The GCMS Analysis of Treatment Influent and Effluent Water from Aberdeen Ob j ec t To identify and compare the levels of the impurities in the water samples taken before, and after the waste treatment facility. Conclusions 1. The major components are summarized in Table 1. 2. GC traces and their interpretations are provided. 3. Phthalate half-esters disproportionated or thermally decomposed during the analysis to produce phthalic anhydride, alcohols and diesters. 4. All of the impurities were significantly lower in plant effluent than they were in the influent to treatment. Gary W. Keen^ Senior Research Scientist jkm Distribution FAS FK AJL November 8, 1979 Page 2 Discussion The quantitative data in this report have been back-calculated and reported on an original-sample basis. Several assumptions have been made. We have assumed 100% extraction efficiencies, no losses in the extraction and Kuderna-Danish concentration steps, 100% purging efficiencies, 100% trapping efficiencies and equal mass spectrometry response factors. The concentrations of the extractable organics were calculated through the use of a D^g-anthracene internal standard. The solutions were injected with a sample size that would insure the detection of this internal standard and priority pollutants at the 5 ppb level. This obviously leads to extra polation problems when the sample contains contaminants at'the several-thousand ppb level. The reported concentrations, especially the high ones, should be considered order-of-magnitude estimates. Therefore, the quantitative data contained in this report can only be used as a guide to the relative amounts of material in the samples analyzed. The nature of the samples and the Intended use of the analytical data obtained do not justify the cost required to obtain strenuous quantitative results. Experimental These extracts were analyzed with the Finnigan 4023 GCMS-DS. The 30M SP2100 ' glass capillary column was programmed from 60 to 260*C at 8/minute. Internal standards of bromochloromethane, l-chloro-2-bromopropane and 1, 4dichlorobutane were added to 5 ml of each sample to be analyzed. The organics were purged with helium, trapped in a silica gel-Tenax absorber tube at room temperature and driven onto the packed column injector by heating the Tenax tube rapidly to 180C. The GC column was a 6* x 1/4" carbowax 1500 (.2%) on Carbopack C preceeded by 2* x 1/4" carbowax 1500 (3%) on Chromosorb W. The glass column was held below room temperature during the thermal elution of the sample from the Tenax column. It was heated rapidly to 60C, then programmed to 170C at 8/minute. It was held at 170 until the run was finished. Mass spectra were recorded at 1.1 second intervals. References File of GCMS Date: G471A-G479A G485A-G492A SAL 000062033 TSR NO. 2118-79-848-0 November 8, 1979 Page 3 TABLE I Summary of the Major Impurities Influent to Treatment Effluent vinyl chloride 2000 ppb ethylbenzene 70 ppb xylenes 400 ppb 1-hexanol 2200 ppb 2-ethylhexanal 130 ppb a-methylstyrene 300 ppb 2--ethylhexanol * 80000 ppb 1-octanol * 14000 ppb 2--phenyl-2-propanol 80 ppb isodecyl alcohols * 30000 ppb 1-decanol * 10000 ppb tridecane 200 ppb phthalic anhydride * 50000 ppb di(2-ethylhexyl) ether 100 ppb 2-hydroxymethylbenzoic acid lactone 1500 ppb tetradecane 900 ppb hexyl octyl ether 400 ppb BHT 80 ppb n-octyl 2-ethylhexyl ether 30 ppb dioctyl ether 2000 ppb hexyl decyl ether 200 ppb 2-ethylhexyl benzoate 60 ppb 2~ethylhexyl decyl ether 20 ppb octyl decyl ether 2300 ppb didecyl ether 800 ppb phthalate half esters * 85000 ppb dihexyl phthalate 160 ppb n-hexyl n-octyl phthalate 240 ppb isooc'tyl phthalate 160 ppb di(2-ethylhexyl) phthalate * 66000 ppb n-octyl 2-ethylhexyl phthalate 2100 ppb di(n-octyl) phthalate * 28000 ppb di(isodecyl) phthalate * 76000 ppb 2-ethylhexyl n-decyl phthalate 1900 ppb n-octyl n-decyl phthalate * 37000 ppb di(n-decyl) phthalate * 16000 ppb decyl dodecvl phthalate 300 ppb r.rioctyl triraellitaie 300 ppb 2 ppb 6 ppb 45 ppb 5 ppb i 30 ppb 18 ppb 1 ppb 1 ppb 3 ppb 1 ppb 90 ppb 4 ppb t 90 ppb t 4 ppb t 40 ppb + 130 ppb t4. 2 ppb 70 ppb t 20 ppb * These concentrations were 30 high that the quantitative data are suspect. It was necessary to make a 1:90 split injection. t Portions of these components may have resulted from phthalate half ester decomposition and disproportionation during work-up and injection. They had lower concentrations in the base/neutral fraction than in the acid fraction. 00 TSR NO. 2118-79-848-0 November 8, 1979 Page 4 Interpretations of the Attached GC Traces Aberdeen Influent Volatile Organics. See Figure 1 Scan it Identification Concentration 92 vinyl chloride 2000 ppfc 634 ethylbenzene 70 ppb 754 xylene 200 ppb 773 xylene 190 ppb 878 a-methylstyrene 300 ppb 896 2-et.hylhexanol 1&0 ppb Aberdeen Effluent Volatile Organics. See Figure 2 96 vinyl chloride 2 ppb 628 ethylbenzene 6 ppb 748 xylene 23 ppb - 767 xylene 22 ppb 871 a-methylstyrene 5 ppb 892 * 2-ethylhexanol 80 ppb Ponca City water was high in 2-ethylhexanol on the day the glass ware cleaned for this run. This value may be high. The purge and trap blank was high in 2-ethylhexanol. Aberdeen Pump Blank (base/neutral) See Figure 3 Scan it Identification Concentration 108 182 258 343 458 553 625 725 1049 1551 1610 L977 ' 4-methyl-3-penten-2-one tetrachloropropane 3-rae thy1-2-cyclohexene-1-one trimethylhexene silastic tubing impurity silastic tubing impurity hexachloropentane diethyl phthalate dibutyl phthalate dicyclohexyl phthalate di(2-ethlhexyl) phthalate silastic tubing impurity 19 ppb 17 ppb 3 ppb 9 ppb 1 ppb 140 ppb 60 ppb 10 ppb 1 ppb 2 ppb 12 ppb 11 ppb 000062033 SM* November 3, 197 9 Page 3 Aberdeen Pump Blank (acids) See Figure 4 Scan //. Identification Concentration 104 180 257 34.1. 743 1503 1.590 1056 2060 4-methyl-3-penten-2-one tetrachloropropane 3-methyl-2-cyclohexen-l-one trimethylhexene diethyl phthalate di(2-ethylhexyl) adipate dicyclohexyl phthalate di(2-ethylhexyl) phthalate silastic tubing impurity 11 ppb 5 ppb 3 ppb 3 ppb 5 ppb 1 ppb 1 ppb 4 ppb 2 ppb Aberdeen Influent to Treatment (base/neutrals) See Figures 5, 6 and 7 This sample was so loaded with organic materials that it was necessary to make a split (low sensitivity) injection. The following data were from that split injection. The split ratio was about 1:90. Scan # Identification Concentration 135 179 186 208 222 256 289 295 350-450 479 517 525 528 535 554 564 584 591 610 628 650 665 747 771 834 836 859 885 936 1001 1092 I !. 74 1'. i ' 1-hexanol isooctenes 2-ethylhexanal a-methylstyrene isooctanol 2-ethylhexanol 1-octanol 2-phenyl-2-propanol isodecyl alcohols 1-decanol tridecane di(2-ethylhexyl) ether 2-hydroxymethylbenzoic acid lactone 5-, 6- and 7-methyltridecane n-heptylcyclohexane 2-methyltridecane 3-methyltridecane branched C]jj paraffin tetradecane 1-dodecanol n-octylcyclohexane hexyl octyl ether diethyl phthalate octyl 2-ethylhexyl ether dioctyl ether hexyl decyl ether 2-ethylhexyl benzoate octyl isodecyl ether 2-ethylhexyl decyl ether octyl decyl ether decyl isodecyl ether d-tdecvl ether -"-/.v pci.h- ` 1900 ppb 10 ppb 130 ppb 200 ppb 130 ppb 32000 ppb 13000 ppb 80 ppb 16000 ppb 10000 ppb 200 ppb 100 pDb 150 ppb 60 ppb 80 ppb 80 ppb 90 ppb 50 ppb 860 ppb 35 ppb 26 ppb 440 ppb 17 ppb 30 ppb 2000 ppb 200 ppb 60 ppb 20 ppb 240 ppb 2200 ppb 20 ppb POO v >!> . V. 0000&2036 SftV- f-4o-y November 8, 1979 Page 6 1525 1588 1660 1749 1875 1900-2400 2006 2160 2489 2982 3500 hexyl octyl phthalate isooctyl phthalate di(2-ethylhexyl phthalate octyl 2-ethylhexyl phthalate di(n-octyl) phthalate diisodecyl phthalate 2-ethylhexyl decyl phthalate n-octyl n-decyl phthalate di(n-decyl) phthalate decyl dodecyl phthalate trioctyl trimellite 240 ppb 150 ppb * 62000 ppb 2000 ppb * 27000 ppb * 72000 ppb 1800 ppb * 35000 ppb * 15000 ppb 300 ppb 300 ppb overloaded component Aberdeen Influent to Treatment (acids) (split injection) See figures 8, Scan// Identification Concentration 138 256 290 350-450 504 525 833 600-1100 999 1172 1626 1641 1747 1682 2004 2137 2473 2000-2400 1-hexanol 2-eth y lhexano 1 1-octanol isodecyl alcohols phthalic anhydride 2-hydroxymethylbenzoic acid lactone dioctyl ether phthalic anhydride and alcohols (from half ester decomposition octyl decyl ether didecyl ether dihexyl phthalate di(2-ethylhexyl) phthalate n-octyl 2-ethylhexyl phthalate di-(n-octyl) phthalate 2-ethylhexyl n-decyl phthalate n-octyl n-decyl phthalate di(n-decyl) phthalate di(isodecyl) phthalate 300 ppb * 46000 ppb 1200 ppb 14000 ppb * 50000 ppb 1300 ppb 100 ppb * 85000 ppb 110 ppb 30 ppb 160 ppb 4000 ppb 100 ppb 1300 ppb 100 ppb 1800 ppb 500 ppb 3900 ppb Aberdeen effluent (base/neutrals) See Fiugres 11, 12 and 13 Scan // Identification Concentration 257 319 an"1 551 1633 1856 2132 2469 1900-2350 3-methyl-2-cyclohexen-l-one 3,5,5-trimethyl-2-cylohexen-l-one silastic tubing impurity silastic tubing impurity di(2-ethylhexyl) phthalate di(n-octyl) phthalate n-octyl n-Uecyl phthalate di(n-decyl) phthalate di(isodecyl) phthalate 21 ppb 7 ppb 16 ppb 40 ppb 10 ppb 2 ppb 6 ppb 2 ppb 28 ppb Sfrt- 0 OOO^ 2037 Aberdeen Effluent (acids) See Figures 14, 15 and 16 Scan # 252 393 ' 486 551 701 600-1100 834 859 999 1171 1482 1614 1632 1731 1845 1982 2114 2444 1900-2400 Identification 2-ethylhexanol silastic tubing impurity phthalic anhydride silastic tubing impurity pentadecane half ester decomposition products dioctyl ether 2-ethylhexyl benzoate octyl decyl ether didecyl ether di(2-ethylhexyl) adipate hexyl octyl phthalate di(2-ethylhexyl) phthalate n-octyl 2-ethylhexyl phthalate di(n-octyl) phthalate 2-ethylhexyl n-decyl phthalate n-octyl n-decyl phthalate di(n-decyl) pythalate di(isodecyl) phthalate Concentration 34 ppb 45 ppb 18 ppb 16 ppb 2 ppb 90 ppb 1 ppb 1 ppb 3 ppb 1 ppb 3 ppb . 4 ppb 90 ppb 4 ppb 36 ppb 2 ppb 60 ppb 21 ppb~ 100 ppb SAL 000062038 SAL 000062039 `MASS CHROMATOGRAM 09'14^?9 13 44'00 DATA! G472A 4141 C A LI' C914A 41 SAMPLE RANGE' ABERDEEN C 1,150 4 9L8ABINEFLL'UENNT0U, O4A. 0 QUAN' A 0, 1 .0 SCANS t TO 1000 BASE' U 20, 3 MASS CHROMATOGRAM DATA' G474A 4141 09^14/73 1540'0O C A L I' C914A 41 SAMPLE' RANGE' GABERl,Q1E5E0Nd 4 8 EFFLUENT LABEL' N UOO, A4 .0 QUAN' A 0 , 1 0 SCANS 1 TO 1000 BASE' U 20, 3 CD CD <U CM if5 N. O rt f'? f-t* CO ZIUJ IZ 1--i iOl-- CD rt Pump ijia u l; " a s e /iJ e u tr a is SAL 000062041 t * unn B lank A c iis CSS o.O A*' O'oO<Qb TOVtOTi a0 Z3 \n Ci-V* mr j J "s' 1 s ~2J I' u- r2n'-** In flu e n t to treatm ent 3ase/N eutrals _] .. .. ~jCi frDo i--m > -h H* T\2> ?5 C at ft> r ON 1> z. 3> <m0 - c ro V ** 01 w 03 O I02>) o sal 000062043 CD SAL 000062044 In flu e n t to Treatm ent H ase/N eutrals CHRO* 3 SAL 000062045 flu e n t to Treatm ent 3ase/N eutrals om o In flu e n t to T ro a tre a t. A cids In flu e n t to Treatm ent A cids CHRG! J -u/j ~c> 2mI>i CD 3> W m 8 W N g (o0 p <X0 CD H O 04 8 SAL. oooo 620^7 7QM&7Q SAL 000062048 In flu e n t to T re a tp e n t A cids 1400 1600 25=40 29*20 D l500>3500 1600 2000 33*00 36*40 2200 40*20 2400 26O0 44-00 47*40 SCAN TIME SAL 000062049 E fflu e n t R ase/N eutrals CHRO: HtO WO 2I> m2 ZUfi&TQ ro i> 3>v>*-< 3H0 Cl) Z2 \ O r2*- o q mr*x> - n \ -i Cl Vi 0)*mu OZGi 5& m r mm i>r ss rz -i 200 IS 2\ 0I>0I> v>r-i to on v>* --'.JO cD "-n* o*-** 2 - HM I n i-n rr, i--i C 2 rr S3 1 tPt H* '3 ;D O ID r: I--1 rr NJ n P h- cn V *-* o S a c 8 s OJ N N S to o J> 2 to CO -< O 91 2.0^ 00^' sfvV- 00 * -IW Ul W N -I O 8 a. oooo<>2 05 i E fflu e n t "A cids' CHRG 3--)< oj U i'%' *0w 22 O O w mrw SAL 000062052 l SAL 000Q62053 E fflu e n t "A cids" 36*48 45*50 55*00 64*10 TIME