Document NEQwZgwoyOOGjK9mQzJ2JjmxD

(conoco) Technical Service Report Report No. 2126-79-839-1 To From R.E. Laramy G.tf. Keen Date November 28, 1979 Continental Oil Company Research and Deevvselotoommeant Department Analytical Research Section Ponca City, Oklahoma CONFIDENTIAL ~~ THIS DOCUMENT IS CONFIDE.*TM AND THE PROPERTY OF CONOCO INC Subject The GCMS Analysis of Treatment Influent amnd Effluent Waters from the Lake Charles Vinyl Chloride Plant Object To determine the levels of the organic components in the plant effluent and treatment influent water samples collected In October, 1979. Conclusions 1. The organic components are summarized In Table 1. 2. GC traces and their interpretation are provided for future reference i 3. Headspace and direct injection procedures were used to provide data for ethanol, vinyl chloride, 2-chloroethanol, trichloroacetic acid, and dlchloroacetlc acid. The reported concentrations for these components are approximations. No Internal standards were used. A quantitative, direct injection GC method should be developed if the levels of these components are important. Gary W. Keen Senior Research Scientist jkm Distribution EAS FK AJL CMS vvc 000012814 TSR HO. 2118-79-848-0 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 1001 extraction efficiencies, no losses in the extraction and Kudaraa-Danlsh concentration steps, 1002 purging efficiencies, 1002 trapping efficiencies and equal mass spectrometry response factors. The concentrations of the extractable organics were calculated through the use of a Djn-aathracene Internal standard. The solutions were Injected with a sample site 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 end the intended use of the analytical data obtained do not Justify the cost required to obtain strenuous quantitative results. Experimental Base/neutral and acidic extracts were provided by the Separations Analysis Group. These extracts were analyzed with the Finnigan-4023 GCMS-DS. The 3GM SF2100 glass capillary column was programmed form 60 to 260C at 8/minute. Internal standard# of bromochloromethane, l-chloro-2-bromopropane and 1,4dichlorobutaaa vara added to 5 ml of each sample to be analyzed. The organics were,purged with helium, trapped in a silica gel-Tenax absorber tuba 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 (.22) on Carbopack C proceeded by 2' x 1/4" carboway 1500 (32) on Chromosorb W. The glaas .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 170*C 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 GCKS data: G542A - 551A G554A - 555A VVC 000012815 'JEM-26 6 06 TSR NO. 2126-79-839-1 November 28, 1979 Page 3 TABLE I Summary of Che Organic Components Component Influent to Treatment vinyl chloride ethyl chloride methylene chloride ethanol acetone 1.1-dichloroethane 1.1-dichloroethylene 1.2-dlchloroethylene chloroform 1.2-dlchloroethane carbon tetrachloride trichloroacetic acid trichloroethylene 2-chloroethanol 1.1.2-trlchloroethane tetrachloroethylene dlchloroacetlc acid chlorobenzene toluene 1.1.2.2-tetrachloroethane trichiorobutanes tetrachlorobutanes tetrachlorobutenes pentachlorobutanes pentachlorobutenes hexachlorobutenes dichlorobenzene xylenes bis(chloroethyl) ether 2-chloroethyldlchlorobutyl ether tetrachlorodioxadecanol pentachlorodloxadodecanol 60 ppb 5000-6000 ppb 300-600 ppb * 9000 ppb 0-100 ppb t 200-1700ppb t 10-300ppb t 70-200ppb > 40000 ppb > 200000 ppb + 50-1200ppb * 3000 ppb 60 ppb * 40000 ppb 3000 ppb 10-40 ppb * 70000 ppb 150 ppb 30 ppb 50 ppb 110 ppb 260 nob 400 ppb 100 ppb 10 ppb 40 ppb 40 ppb 30 ppb 400 ppb 28 ppb 15 ppb 9 ppb Effluent 0-10 ppb 20 ppb 10 ppb 10 ppb 8 ppb 12 ppb t The uncertainties In these values were revealed by the headspace and direct injection analyses. The EPA - recommended absorber tubes may be inefficient for 1,1-dichloroethane, dlchloroethylenes and carbon tetrachloride. * These levels were estimated from a direct Injection using no internal standard. I.10J-266U S vvc 00001Z816 TSR NO. 2126-79-839-1 November 28, 1979 Page 4 LCVCP Influent VOA See Figure 1 Sean# 64 85 93 100 120 130 138 150-170 177 246 284 303 477 504 508 564 686 741 782 811 900 Identification ethyl chloride methylene chloride 1,1-dichloroethylene acetone 1a1-dlchloroethane dichloroethylene chloroform 1,2-4ichloroethane carbon tetrachloride 2-chloroethanol branched paraffin 1,1,2-trichloroethane tetrachloroethylene toluene 1,1,2,2-tetrachloroethane chlorobenzene trlchlorobutane tetrachlorobutene xylenes pentachlorobutane dichlorobenzene Concentration 5000 ppb 300 ppb 10 ppb 100 ppb 200 ppb 70 ppb > 40000 ppb > 200000 ppb 50 ppb 300 ppb 60 ppb 3000 ppb 30 ppb 30 ppb 30 ppb 70 ppb 70 ppb 170 ppb 30 ppb 160 ppb 40 ppb Scan # 154 297 LCVCP Effluent 70A See Figure 2 Identification 12-dichloroethane 1*1,2-trlchloroethane Concentration 20 ppb 10 ppb VCM Pump Blank Base Neutrals See Figure 3 Scan# Identification Concentration 92 UO 129 182 257 342 346 549 624 743 1604 4-methyl-4-penten-2-one 4-methyl-3-penten-2-one 4-raethyl-4-hydroxy-2-pentanone tetrachloropropane 3-methyl-2-cyclohexen-l~one trlmethylhexene acetone trimer silastic tubing impurity hexachloropentane diethyl phthalate di(2-ethylhexyl) phthalate 70 ppb 1200 ppb 1200 ppb 70 ppb 20 ppb 20 ppb 20 ppb 150 ppb 10 ppb 40 ppb 13 ppb VVC 000012817 TSR NO. 2126-79-839-1 November 28, 1979 Page 3 VCM Pump Blank Acids See Figure 4 Scan # Identification Concentration 90 4-methyl-4-penten-2-one 30 ppb 107 4-methyl-3-penten-2-one 770 ppb 124 4-methy1-4-hydroxy-2-pentanone 600 ppb 182 tetrachloropropane 30 ppb 257 3-methyl-2-cyclohexen-l-one 30 ppb 343 trimsthyIhexene 20 ppb 744 diethyl pbthalate 11 ppb VCM Effluent Base/Neutrals See Figure 5 Scan # 105 121 180 259 342 390 457 525 559 584 625 685 743 Identification Concentration 4-methy1-3-penten-2-one * 300 ppb 4-methyl-4-hydroxy-2-pentanone tetrachloropropane 3*methy1-2-cyclohexen-l-one * 240 ppb * 30 ppb * 10 ppb trimethylhexane * 20 ppb silastic tubing Impurity silastic tubing Impurity * 60 ppb * 11 ppb 2-chloroethyl dichlorobutyl ether 10 ppb silastic tubing impurity *1700 ppb tetrachlorodloxadecanol 8 ppb hexachloropentane (same as blank) * 10 ppb pentachlorodloxadecanol diethyl phthalate 12 ppb * 9 ppb * These components were observed in the blank. Scan # 105 181 549 VCM Effluent Acids See Figure 6 Identlflcation 4-methyl-3-penten-2-one tetrachloropropane silastic tubing impurity Concentration 120 ppb 11 ppb 90 ppb t.v :.AQ72 VVC 000012818 T3R NO. 2126-79-839-1 November 28, 1979 Pag* 6 TGM Influent to Treatment Base/Neutrals See Figures 7 and 8 Scan # Identification Concentration 97 127 154 181 204 216 241 255 261 273 293 307 323 338 350 364 371 392 419 435 458 476 523 560 585 744 1,1,2-trlchloroethane chlorobenzene 1,1,2,2-tetrachloroethane trlchlorobutene bls(chloroethyl) ether tetrachlorobutane trlchlorobutene tetrachlorobutane tetrachlorobutane tetrachlorobutane tetrachlorobutane tetrachlorobutane tetrachlorobutane tetrachlorobutane tetrachlorobutane tetrachlorobutene tetrachlorobutene allastlc tubing Impurity pentachlorobutene pentachlorobutane silaatic tubing impurity hexachlorobutene 2-chloroethyl dichlorobutyl ether silastic tubing impurity tetrachlorodloxadecanol diethyl phthalate 1200 ppb 40 ppb 50 ppb 20 ppb 400 ppb 30 ppb 90 ppb 24 ppb 200 ppb 11 ppb 100 ppb 24 ppb 60 ppb 300 ppb 10 ppb 16 ppb 20 ppb 120 ppb 8 ppb 100 ppb 15 ppb 37 ppb 28 ppb 1800 ppb 15 ppb 10 ppb Influent to Treatment Acids See Figure 9 Scan # Identification 93 1,1,2-trlchloroethane 183 tetrachloropropane 315 bromocyclohexano1 401 silastic tubing impurity Concentration 11 ppb 12 ppb 12 ppb 50 ppb Influent Direct Injection See Figure 10 Scan # Identification Concentration 26 53 95 171 193 208 293 carbon dioxide >100000 ppb ethyl chloride 300 ppb ethanol 9000 ppb column artifact (caused by water) 12000 ppb chloroform * 30000 ppb 1,2-dlchloroethane 200000 ppb trichloroacetic acid 3000 ppb VVC 000012819 UEY-2660 TSR NO. 2126-79-839-1 November 28, 1979 Page 7 Scan # 327 399 440 Identification 2-chloroethanol 1,1,2-trIchloroethane dichloroacetlc acid Concentration 40000 ppb 3000 ppb 70000 ppb * These concentrations are only eatimatea. The 1,1,2-trichloroethane concentration was assumed to be 3000 ppb as determined by the purgeand-trap analysis. Others were calculated using their response areas relative to Effluent Direct Injection Only carbon dioxide and an artifact peak from the large water slug were observed. Effluent Headspace See Figure 11 This analysis was not designed to replace the classical and more accurate GC headspace analysis, but was run at the time of the other analyses In case the Separation Analysis Group had identification problems In their GC headspace analysis. Scan # Identification Concentration 211 chloroform 224 1,2-dichloroethane 395 syringe Impurity 10 ppb 20 ppb 50 ppb Influent to Treatment Headspace See Figure 12 Scan # Identification Concentration 54 64 107 128 171 195 215 232 262 309 357 413 599 695 vinyl chloride ethyl chloride methylene chloride dichloroethylene 1,1-dlchloroethane dlchloroethylene chloroform 1,2-dlchloroethane carbon tetrachloride trichloroacetic acid trichloroethylene 1,1,2-trichloroethane tetrachloroethylene chlorobenzene 60 ppb 6000 ppb 600 ppb 300 ppb 1700 ppb 200 ppb >40000 ppb >70000 ppb 1200 ppb 10 ppb 60 ppb 3000 ppb 40 ppb 150 ppb In flu e n t V o la tile O rganics (Purge and Trap) VVC 00O1262i MEM-2.540  8 O ro CM CO 21 <c 8CJ CO $ 8 IDI 2aLiUrJ. 1.01-- Figure 'S A fflu e n t V o la t ile Orga /s (Purge and T ra p ) U \ Ul f Q_ltlJ CO Li. L5 CO \ EZ CD <EC`-a<T y *--i t/i Ct i-h M5 V ges,-2660?* O; X o VVC 000012822 s M vvc 000012.823 RIC 10/15/79 10` 02<00 DATA< G557A f t l C A LI5 C1015A #1 SAMPLE* VOt PUMP BLANK CB/fO 10-79 RANGE5 G 1,3500 LABEL' N 0 , 4 .0 QUAN- A 0. 1.0 SCANS 1 M TO 1900 BASE* U 20/ 3 TmH3 .* a< c. c 3 X VVC 000012824 ) )pure Effluent Extract Tlase/Heutrals 'J VVC 0 0 0 0 1 2 8 2 5 CHRO ' OO 'si O E fflu e n t E xtra ct Acids S o^4 8 o I- ro 8 8 -8 o CO 8 s <1 *z i<eS So JO - - fs-^ <ri- i ><r-<_r i-Q^ tonz M- O-l <tuj -5io 5 E03Q <CO J o: u-p ttU-fo oiftUJ - h ^ <r me io <N Z "</'< *8 10 pph Internal standard 32 <r :N . ft ifO ID a ftl . 6) iCVI -CD blar.l* inmirities 0 C-D4 . - IDO * (M v,E,vi-26608D O CL X<_> VVC 000012826 I*4 tf) to ZIU <IZ <cJm*-- Figure 1 In flu e n t E xtra ct 3ase/l!eutr CHPO : VVC 000012827 ucy-2660Sl In flu e n t E x tra c t Base/?J e u tra ls ft vvc 00001Z8Z8 5 L>*WH O 6>f0 IDf'-fJ _ SKVJ .. Q(C O -- inch In flu e n t E xt.a ct Acids CHRQ> ' v^; VVC 000012329 vEV-266083 O o veol o -4 QU3yHi. 4' . U--e034t) C )-266i0.aWSA VVC 000012330 E fflu e n t Headspace In je c tio n  V ri-i: ,;ipure ^ In flu e n t ''eadspace In je c tio n CHRO: MEV-266086 VVC 000012832 iuituji<}io cvruft.i SPECTROSCOPY GROUP Mane<)?, E, -------- Analysis Ho-M^ga. Sample No. S*ie- "'SQ-Tlr^ _____ Notebook No. Spectrum, Film or Plate No. Type of Analysis Requested jg~S^rj^ 4 p<j 33. i m:v- 11 i\\x- ia VC.ITN-^1 vcm-safl a\ "A* < m.K i< < r>. i ri r^, At. M4 v nry n . aa <r. n^s' * O, DnR n,3i Ocl nA Or- ' aa i. ^ fi. 2.1*r>. fM< * e>.03 > 33r\ * ri . i--.:* r\. m * r\. r\ t x, < r>. rj a r>. ptj *<ri. /wa < cj . r> ^ > 3^ < n. oijs ^ r",. 03 C.U nM< <rt>. ra< /\ i ru/ r** --"T" MA l.A O. /3 . r>3 < r^. I Ci ^D.DI G.*<i O. * r>. r. 3 * <**. i C> O1 * n. ID * Cj ,o 1 // 0,^0 *r*. `O.DS *ri,r*g * o. C).^ < pj, W. *rs.C7i? *O.G7S .073 ^ o. oik "Ph <f>. A* <- o. < n. * r>. < n , ^2^ .3 5i < in, 1 crs, / a r>, /i? m <- r^. tc^ Cj - ^L) ~r~l * r\. Sb <* r*, ^r> -c r, r> -=r>. esr. < CN.JSC7 V <o. * r> ,ro$ * c->. rr3^ * n.r^o-=i * < o, r,^)^ * 2k <*% . r*. r* * r>.r*a ^ < d,rs^<> C>. Mr* Ss s ' 77 7" J "3 7 ' C>, ^2_ s J J "7 j,/s > lOOft . in r\. 7 77*7*7 "71"77" rTTTTT >9 // f CifiO - Art ^A A.ol. < *a i 2. < ,01< .0 1 < A .2- Crt.ol < o.e / ft , V <o .6 2<0 -fl / -< rt . 2_ < <T./5 / <o slL 0. a ^ .0 l___ *No line was observed for this element. The < value given is the lowest concentration stand, for this element in our calibration. All < or > values are outside our calibration range, other analytical data are needed contact the Emission Laboratory. Signed JUL. it____ Date )n ng/.'Z.q VVC 000012033 K ELName_______ 4rM ,s*- Sample No. CL*Z. .Ja.xZsfeu L Spectrum, Film or Plate No. ANALYSIS REPORT SPECTROSCOPY GROUP Analysis No. *} $ if Notebook No.____ f?ST Type of Analysis Requested $ fiS_ dASE. .<7 h/f) X2.A Gi-P, <T? Ac Oc2-- ooZ. nr>-> -X^Z'OtZL^ JUO/AC" & 4 ' *No line was observed for this element. The < value given is the lowest concentration st for this element in our calibration. All < or > values are outside our calibration rant other analytical data are needed contact the Emission Laboratory. Signed _ Date ------------- 7 VEV-2660*i: vvc 0000128V*