Document da5BbqdMJpz0QJw2kYXYGnjxe

(conoco) Technical Service Report Report No. 242-79-350-2 To R. E. Laramy Continental Oil Company Reaaarch and DeveloppmmeennttD1 epartment Analytical R Ponca City, From W. Keen Date April 12, 1979 ' CCn;riOENT/AL AMO '*,PERTY CF CONTINENTAL 0*. Company. Subject THE GCMS ANALYSIS OF WATER SAMPLES FROM THE LAKE CHARLES REFINERY OBJECT: To Identify organic impurities in the effluent water samples CONCLUSIONS: Most of the components were typical of crude oils or heat exchanger fluids. Many aromatic compounds that were below the 10 ppb level were not listed. The following priority pollutants were detected: Component Approximate Concentration diethyl phthalate dibutyl phthalate fluoranthene chrysene dloctyl phthalate benzof1uoranthene 7 ppb 4 ppb 1 ppb 16 ppb 4 ppb 12 ppb 7 fi+A- G. W. Keen Senior Research Scientist Research Group Leader Magnetic Resonance-Mass Spectrometry Group Distribution: FK-EAS-RLH MCD 000002654 TSR No. 242-79-350-2 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 Dio-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. The EPA protocol methods call for reporting "between 10 and 100 ppb" or "greater than 100 ppb" for selected priority pollutants. We have chosen to depart from the EPA protocol-reporting procedure by including all organic materials and by reporting rough quantitative information about these contami nants so that intelligent decisions can be made about ways to clean up the plant effluents. If more accurate determinations are needed, cost and man power estimates can be provided. The Research Triangle Institute and the Gulf South Research Institute have been awarded a $750,000 contract to develop the Master Analytical Scheme (MAS) for the analysis of organics in water. Their procedures are expected to be incor porated into the new EPA protocol. It should be advantageous for us to wait for the MAS, since it is expected to utilize a glass capillary gas chromatography electron impact mass spectrometry data system (GCGCEIMSDS) finish. MCD 000255 TSR No. 242-79-350-2 Page 3 Lake Charles Refinery Blank (Base-Neutral) 3/79 See Figures 1 and 2. Scan # __________ ID 751 791 1036 butyl-cappednonionic isooctanol isodecanol Lake Charles Refinery Blank (Acids) 3/79 See Figure 3. No significant components were observed. Lake Charles Refinery Influent (Base-Neutral) 3/79 See Figure 4. No significant components were observed. Lake Charles Refinery Influent (Acids) 3/79 See Figure 5. Scan # __________ ID 2009 di-2-ethyl hexyl phthalate Concentration 300 ppb 30 ppb 10 ppb Concentration 1 ppb mcd 000002656 TSR No. 242-79-350-2 Page 4 Lake Charles Refinery Effluent (Base Neutral) 3/79 See Figures 6 and 7. Scan # ID 396 527 619 696 ----- 762 824 903 946 1008 1063 1120 1174 1184 1215 1279 1292 1306 1379 1479 1553 1578 1592 1602 1680 1700 1777 1786 1805 1896 1908 2012 2018 2048 2134 2265 2278 2373 possible amino acid butyl-capped nonionic butyl-capped nonionic tridecane butyl-capped nonionic tetradecane branched paraffin pentadecane diethyl phthalate hexadecane branched paraffin heptadecane pristane biphenylcarbaldehyde octadecane branched paraffin dibutyl phthalate nonodecane elcosane fluoranthene heneicosane trimethylphenanthrene trimethylphenanthrene docosane methyl pyrene terphenyl tricosane terphenyl tetracosane chrysene pentacosane dioctyl phthalate methyl benzanthracene hexacosane heptacosane benzopyrene benzofluoranthrene Concentration 25 ppb 80 ppb 26 ppb 10 ppb 1400 ppb 21 ppb 13 ppb 24 ppb 7 ppb 25 ppb 16 ppb 24 ppb 25 ppb 10 ppb 21 ppb 12 ppb 4 ppb 23 ppb 19 ppb 1 ppb 14 ppb 5 ppb 7 ppb 14 ppb 10 ppb 10 ppb 12 ppb 16 ppb 11 ppb 16 ppb 14 ppb 4 ppb 18 ppb 10 ppb 8 ppb 7 ppb 12 ppb MCD OOQoo2657 TSR No. 242-79-305-2 Page 5 Lake Charles Refinery Effluent (Acids) 3/79 See Figure 8 . Scan # ID_________________ 524 butyl-capped nonionic 741 butyl-capped nonionic Concentration 40 ppb 60 ppb Lake Charles Refinery Volatile Organics 3/79 See Figure 9. Scan # ID 79 carbon dioxide 129 internal standard 193 branched C6 olefin 310 hexane 541 internal standard 822 phenol Concentration 200 ppb 20 ppb 10 ppb 210 ppb 20 ppb 10 ppb EXPERIMENTAL: Base neutral and acid extracts were provided by the Separations Analysis Group. The extracted base-neutral and acid concentrates were spiked with deuterated anthracene, which served as an Internal standard. These extracts were analyzed with the Finnigan 4023 GCMS-DS. The 30M SP2100 glass capillary column was programmed from 60 to 260C at 6/minute. Internal standards of bromochloromethane and 1,4-dichlorobutane were added to 5 ml of water, the volatile 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 14" Carbowax (3%) on Chromosorb W followed by 4' Carbowax (.2%) on Carbopack C. The 1/4" thick walled glass column was held below room tempera ture during the thermal elution of the sample from the Tenax column. It was heated rapidly to 60C, held there for .8 minutes, 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 data: G213A-217A, G219A, G241A.B MCD 000002658 CHRO* MCD 000002659 MCD 000002660 Ozawa: IC DATA* G213A #1 S 'lS /TO 9*50*00 CALI* C1214B # t lAMPLE* LC REF BL B'N 3-79 IANGE* G 1,3000 LABEL* N 0, 4 .0 CHJAN* A 25.0-n ?1 0, 1.0 SCANS 130 TO 2100 BASE* U 20, 3 66560.  *4 <M 3 4 O Ch I- fO Q3O 0002662 MCD 000002663 RIC ' DATA* G216A 1 3^16/79 141100 C A L I> C1214B #1 SAMPLE- LC REF INFL ACID 3 -7 9 RANGE: G 1 ,3 0 8 0 LABEL * N 0 , 4 .0 QUAN A 10O.0-1 0 , 1 .0^ SCANS 150 TO 2100 ,, BASE* U 2 0 . 3 20512. FIGURE 6 See Figure 7 8 a in e w (ft 8 (VI (Z<frt u Ul C(<fQct CO g- oozo.3 <tmftUuLHW- r,j \lli - r o O*V-*E<LZU (K&CftCC CJ 8P o*- 88 ro . - ion. '-(VI 8. " <D & "T O H & U> X - in (-ft ro WCD 000002664 ooooo^66 RIC DATA* G217A #1 03'19v?9 8*59*00 CALI* C1214B #1 SAMPLE- LC REF COMP B/N 3 -7 9 RANGE- G 1,3000 LABEL* N 0, 4 .0 QUAN- A 0, 1.0 SCANS 1050 TO 3000 BASE* U 2 0 , 3 <T\ % N O W -* CO CD s 14 f 0*<VC-J(IUJ Q 0\?2 ID hw5i cj O'CHr/O' MOD 000002666 O W 00 (VI N o <r> I- n (St in (VI to z <c o UJ s05 05 <9 <1 Z <E <-ti<nr C> m-o cn cm*3JO =COD3S 'i* <i- <t<r <3 DO Z VDUi (JiOl *<C v_J CHRQ: ZUJ <IE O(S*tV-*Q Git? _G> - 'tf-in "Cvl oo _ CJOJ C%l OOJ .(St Gt CO t<f-9 . C0^- <9 0(9 .<9 V> <-* O OCVI U O^r J_o cvire MCD 000002667