Document O3Ewy7YLjKqRp44VwgKkv0ZKw

3.1 SITE SELECTION The three study akeals selected by EPA were; Calvert City, Kentucky: Location of the B.F. Goodrich facility Lake Charles, Louisiana: PPG facilities Location of the Conoco and New Orleans, Louisiana: Location of the Shell Oil and Union Carbide facilities. PEDCo, with the assistance of an EPA meteorologist, selected 1 meteorological and 12 sampling sites at each study area. Each site is described below in detail. 3.1.1 Location of Calvert City, Kentucky, EDC Study Sites A map of the study area is presented in Figure 3-1. The location of the maid e thylene dichloride emission source is 373'5"N., 8819136"W. at an elevation of 150.88 meters (at stack exit). Stack height is 45.72 meters. The study area is located in the lands bn both sides of the Tennessee River near Calvert City, Kentucky. B.F. Goodrich's chemical plant is lo cated on the flat land south of the river. Sites 1 through 4 were placed near the plant; site 5 was located on the river east of the plant; and sitds 6 through 12 were located in low, parti ally wooded hills north of the river. Site 1 Location Warren petroleum Co. Calvert City Terminal Calvert City, Kentucky This site was located within the fenced area of the Warren Petroleum Co., Calvert Ci ty terminal, 800 meters and 130 south east of the B.F. Goodrich plant. Propane gas (only) is stored at oooo* 23*>3 N* *0 rr <\t O o o o o > > this site. Elevation was 105 meters. A meteorological system and an EDC sampler we re at this location. Exposure was excel- lent. Site 2 Location Residence of Roy Springer Highway 282 Calvert Ci|ty, Kentucky This site was located in the front yard of the Springer residence, 1280 meters and 217 southwest of the B.F. Goodrich plant. Elevation was 107 meters. The area between the B.F. Goodrich plant and the site was open, with scattered trees. There was a small woods to the south of the site. Site 3 Location Residen ce of Carl Deekes Highway 28 2 Calvert Ci ty, Kentucky This site was located atop a small building next to the Deekes residence, 1260 meters and 197 south-southwest of the B.F. Goodrich plant. Elevation was 107 meters, with the roof 3 meters above the grou nd. Exposure was excellent. The area between the site and the plant was open, with scattered trees. Site 4 Location Residen ce of James Stowe Routes 282 and 1523 Calvert Ci ty, Kentucky This site was located in the front yard of the Stowe resi dence, 1960 meters and 153 south-southeast of the B.F. Goodrich plant. Elevation was 107 meters. The area between the site and the plant had scattere d woods. Exposure was good Site 5 Location Guinn F isl Camp Gilbert svi lie, Kentucky This site was loc^at^d on the floating boat dock at the Guinn Fish Camp, 3440 meters and 120 east-southeast of the B.F. Good rich plant. Elevation was 91 meters. The dock was floating in the Tennessee River, 10 meters from the shoreline. Exposure to emissions channeled up the river valley was excellent. 8 WC 0000X2365 Site 6 Location Farm ofl Gerald Devine Granh Rivers, Kentucky This site was located behind a tool shed on the Devine pig farm, 3200 meters ^ndi 89 east of the B.F. Goodrich plant. The sampler was set on a small grassy knoll, with excellent exposure in all directions. Elevation was 119 meters. Site 7 Location Farm of Willard Jones Grand River, Kentucky This site was .oc ated on the Jones pig farm, 2860 meters and 70 east-northeastJ of the B.F. Goodrich plant. The farm was situated on the side of a small valley running down to the Ten nessee River. The sampler was placed atop a small wellhouse. Ground elevation at this site was 122 meters, with the wellhouse roof being 2 meters ab Dve the ground. Site 8 Location Resi&enhe of Charles Johnson Grand River, Kentucky This site was located in the backyard of the Johnson residence, 3700 meters and 44 northeast of the B.F. Goodrich plant, Open pasture land liy in the area between this site and the banks of the Tennessee Rive r. Exposure was excellent. Elevation at this site was 128 miteirs Site 9 Location Residence of Ed Gillum Grani River, Kentucky This site was located in the front yard of the Gillum resi dence, 2680 meters and 35 northeast of the B.F. Goodrich plant. Elevation was 113 metiers. The area between this site and the B.F. Goodrich plant was open farmland. Site 10 Location Pinks Bkrbegue Smitlkland, Kentucky This site was located in an open area behind the Pinks Barbeque Stand, 3000 meters and 8 north of the B.F. Goodrich 9 oooot Z366 ^>/C plant. Elevation was 11 0 meters. Because it was in a heavily wooded valley, this d id not appear to be a very good site, but local residents stated that smells from the plants located across the Tennessee River alWa^s seemed worse in this valley. Site 11 Location Farm of Ralph Bloodworth Smithland, Kentucky This site was lo<t ated in a large open area near the barn on the Bloodworth farm. Distance from the B.F. Goodrich plant was 2540 meters and 355 north. Elevation was 119 meters. The area between the site and the plant was open farmland. Site 12 Location Residen ce of Preston Bloodworth Smithla nd, Kentucky This site was located in the large backyard of the Blood worth residence, 2750 meters and 329 north-northwest of the B.F. Goodrich plant. Elevation was 107 meters. The area between this site and the plant was open farmland. Exposure was excellent. 3.1.2 Location of Lake Charles, Louisiana, EDC Study Sites A map of this study area is presented in Figure 3-2. The location of the principal ethylene dichloride emission source is 3015 * 9"N., 9317'5"W. , at an elevation of 49.68 meters (at stack exit). Stack height is 45.11 meters. The study area is in the flat coastal plains o f southern Louisiana, west of the junction of the Calcasieu river with Lake St. Charles. The town of West- lake, in which the Conoco plant is located, consists of residen tial and industrial areas. All samplers, except as indicated in individual site descript ions, were located on the ground at an elevation of 5 to 10 meters above sea level. 10 vvc 000012367 Site 1 Location* Residence of John C. Dyson Rt, 2, Box 1145 Westlak^, Louisiana This site was llodated in the front yard of the Dyson resi dence, about 1200 meters and 178 south of the main vent stack of the Conoco plant. Trousdale Road, a tree-lined, north-south road in front of the Dyson residence, terminated at the plant property line just south of tlhe'main vent stack. When winds were from the north, this road channeled emissions from the plant to site 1. The sampler was lpcated in a large (30 x 30 meters) section of the front yard that was open to Trousdale Road. The area to the northeast and south was scattered with trees, the area to the west was heavily wbodJed. An EDC plant operated by Pittsburgh Plate Glass (PPG) i^s located approximately 1800 meters south of the point. ii Site 2 JJ Location Resi<^ende of Irene Gray Rt. 2,, Ejox 735 Westljak^, Louisiana This site was llodated in the front yard of the Gray resi dence, 590 meters a|ndl2280 southwest of the main vent stack of the Conoco plant. |Thp area consisted of tall trees with very little undergrowth. , Streets ran north-south and east-west. The neighborhood was an old subdivision with many vacant lots that had become overgrowd. * The eastern side of the area bordered the Conoco property. Dhriikg periods of little or no wind, emissions from the plant drifted (into the area. The sampler wa^f located in an area of the front yard that had no trees within 10 Imeters. Site 3 Location Residence of Paul Victoria Rt. 2', Box 794 M westlkkej, Louisiana This site was |lopated in the front yard of the Victoria residence, 940 meters and 275 west of the main vent stack of the Conoco plant. Located at the fringe of the residential area described in site 2,1 tdis location was well exposed, with only a few small trees. Thd skmpler was located so as to have excellent exposure in all direptibns. 12 oooo^fea VVC 0 0 0 0 1 2 3 6 9 F ig u re 3 -2 . Map o f Lake C h a rle s , L o u is ia n a , s tu d y -a re a . Site 4 Location Residence of Oriese Thomas Rt. 2, Box 748 Westlake, Louisiana This site was ocated in the front yard of the Thomas resi- dence, 570 meters td 242 southwest of the main vent stack of the Conoco plant, id in the same residential area as described for site 2. The ampler was located near the corner of two streets and had goo exposure, even though the area was wooded. Vehicle traffic in t: ie neighborhood was very light. Site 5 Location Thomas Body Shop Midhiban Avenue and Old Spanish Trail Westlake, Louisiana This site wa s ].ocated on the roof of the Thomas Body Shop, 870 meters and 219 southwest of the main vent stack of the Conoco plant. Tlje Jroof area, being 7 meters above the ground, had good exposure in all directions. Work activities at the body shop were confined to a few hours in the evening. No painting, degreasing, or gasoline services were done on site. Site 6 Location Mossville Elementary School Old Spanish Trail Weitl.ike, Louisiana This site was located at the Mossville Elementary School, 1140 meters and 244 southwest of the main vent stack of the Conoco plant. The dchool was in a large open area between West- lake and the village of Mossville. The sampler was placed on the roof of one of t^ie auxiliary buildings, and was 4 meters above the ground. Site 7 Location Residence of Jerry Harding Everg::een Drive Westlake, Louisiana This site wa s located in the backyard of the Harding residence, 2770 meter s and 297 northwest of the main vent stack of the Conoco plant, The area between the plant and this site was open, with very fdw trees. 13 VVC 000012370 Site e Location Resi derice of Shirley Bunch Ever green Drive West Laide, Louisiana This site was lobated in the front yard of the Bunch residence, 2570 meters and 313 northwest of the main vent stack of the Conoco plant, The area between the plant and this site was open, with very few tr ees. Site 9 Location Residence of Gerald Bult Powell Lane Westllake, Louisiana This site was located 1800 meters and 323 northwest of the main vent stack of tlfe Conoco plant. An EDC sampler and meteorological tower wire located in a large open field behind the Bult residence. Nb large obstructions were present within 200 meters. The area between the plant and the site was open with the exception of a fevj trees. Site 10 Location Residence of John Hyde Rt. 2, Box 1586 Westtarie, Louisiana This site was loc ated in the backyard of the Hyde residence, 1190 meters and 343 o north of the main vent stack of the Conoco plant. The area ne ar the sampler was open, with the exception of a few scattered pin s trees. Site 11 Location Residence of Herman Dyson 2215 Margaret street Westlarie, Louisiana This site was located in the backyard of the Dyson residence, 880 meters anh 70 east of the main vent stack of the Conoco plant. There were a few trees in the vicinity of the sampler, but the aiea between this site and the Conoco plant was open. 14 vvc 0000 12371 Site 12 Location Residence of Harold Daily 913 Carroll Street Westlake, Louisiana This site was located in the backyard of the Daily residence, 202 0 meter s And 117 southeast of the main vent stack of the Conoco plant, afhis was a residential area, and the site had a large open yard c ontaining only a few small trees. Exposure was good in all d^re^tions. 3.1.3 Location of New Orleans, Louisiana, EDC Study Sites A map of the New Orleans, Louisiana, study area is presented in Figure 3-3. The principal EDC emission sources are: Shell C hemical Plant, Norco, Louisiana, at 30o0'15MN., 9025'3 )"W., and an elevation of 36.5 meters (at stack exit). Th'2 stack height is 33.53 meters. Union Carbide, Hahnville, Louisiana, at 2959'061' 9026T15n W., and an elevation of 18.29 meters stack exit). The stack height is 15.24 meters. stack is eijuipped with an incinerator. N. , (at The The study arlea is in the flat delta lands on both sides of the Mississippi Ri^er north of New Orleans, Louisiana. All samplers, except as indicated in individual site descriptions, were located on the ground at an elevation of 3 to 6 meters above sea level. A lofmeter-high levee runs along both sides of the Mississippi River aind along the Bonnet Carre floodway, which connects the Mississippi River with Lake Pontchartrain. The study area is residential, intermingled with chemical plants and oil refineries. A large swamp area is located south of the Union Carbide plant. 15 000012372 VVC. Site 1 Location Hodkihs Fruit Stand Highway 61 and Prescott Road Laplace, Louisiana This site was located 4000 meters and 343 north-northwest of the Shell plart; and 6000 meters and 5 north of the Union Carbide plant. Adja sent to the site was the Bonnet Carre floodway, a flat woodfed area 2000 meters wide running between the Mississippi River and Lake Pontchartrain. Route 61, a four-lane highway with moderate traffic, passed within 30 meters of the site. The sampler was located on top of a small cooler next to the fruit stand. The sampler inlet was 3 meters above the ground. Site 2 Location Res id^nce of Neil Madere 195 Evangeline Road Lap lade, Louisiana This site wai located 4050 meters and 295 northwest of the Shell plant; and 42bo meters and 310 northwest of the Union Carbide plant. Located in an area of new homes with large open yards, this site had good exposure in all directions. Site 3 Location Res idcsnce of Joseph Calcayvno Rt. 1, Box 731 Lap lade, Louisiana This site was located in the front yard of the Calcayvno residence, 3025 metei's and 275 west of the Shell plant; and 2675 meters and 331 northwest of the Union Carbide plant. The area around the Calcayvno residence was open for 200 meters in all directions, giving excellent exposure. The 10-meter-high Bonnet Carre floodway levee was 250 meters to the east. The Mississippi River levee of the same height was 500 meters to the south. Site 4 Location U.d. /irmy Corps of Engineers Bonnet Carre Maintenance Area Noxtco, Louisiana This site wafe 1 ocated inside the fenced area of the Bonnet Carre maintenance fci cilities, U.S. Army Corps of Engineers. A meteorological sydterk and an EDC sampler were located here. The 17 yt3 ov* ^>|C ooo 7 site was 400 meters and 299 southwest of the Shell plant; and 2700 meters and 37 nor[theast of the Union Carbide plant. The Bonnet Carre floodway levee was 50 meters to the west; and the Mississippi River levee was 300 meters to the south. Under calm wind conditions, emissions from the Shell plant could be held in the pocket formed by ijlie | junction of the two levees. Site 5 Location Residence of R.V. Jacob 524 Alleman Street Norco, Louisiana This site was located in the backyard of the Jacob resi dence, 825 meters and 32 northeast of the Shell plant; and 3500 meters and 37 northeast of the Union Carbide plant. Located in a residential area df the west part of Norco, this site had excellent exposure to Ithe Shell plant. Site 6 Location Residence of Corrine Woods Post Offic e Box 454 KiIlona, ouisiana This site was located in the front yard of the Woods resi dence, 6050 meters akd 266 west of the Shell plant; and 4600 meters and 289 northwestl of the Union Carbide plant. Located at the eastern edge of Killona, the site had excellent exposure to the north, east, and south. Site 7 Location Marie * s Cafe Rt. 18 Hahnvil le. Louisiana The sampler at this site was located on the roof of Marie's Cafe, at a height of ,5 meters above the ground. The site was 2850 meters and 24 sojithbest of the Shell plant; and 1000 meters and 314 northwest of the] Union Carbide plant. The 10-meter-high Mississippi River levee was 40 meters north of the site. Expo sure in all directions was good. Site 8 Location Residence of Leona Triche Rt. 1, Box 10 Hahnville, Louisiana 18 vvc 000012375 This site was I located in the backyard of the Triche resi dence, 1850 meters andi212 southwest of the Shell plant; and 850 meters and 60 norttkea4t of the Union Carbide plant. Exposure in all directions was |excellent. The Mississippi River levee was 100 meters north of this site. Site 10 Location Residence of Adolph Lorio Rt. 1L Rost Office Box 95 Hahn^ilie, Louisiana This site was located in the front yard of the Lorio resi dence, 2075 meters land 155 southeast of the Shell plant; and 2575 meters and 85 east of the Union Carbide plant. There were no trees in the aria if the sampler. Exposure was good in all directions. this site. The Mississippi River levee was 110 meters north of Site 11 Location Resid enc e of Sam Alleman Box 3 33 Hahnv ill e, Louisiana This site was loc ated in the backyard of the Alleman residence, 2950 meters and 168 southeast of the Shell plant; and 2450 meters and 109* ekst of the Union Carbide plant. The area of the yard was open wi th excellent exposure. Site 12 Location Residencle of Ray Doucet Post Office Box 3455 Paradis, Louisiana This site was located in the backyard of the Doucet resi dence, 14,450 meters and 189 south of the Shell plant; and 12,200 meters and 181 south of the Union carbide plant. The area between this site and the Union Carbide plant was heavily forested swampland. | Residents of the house stated that they could often smell the chemical plant when the wind was from the north. 3.2 FIELD SAMPLING After the sites we|re selected, PEDCo contacted the property owners and made arrangements for placement of the sampling equip ment. These arrangements were documented in an Agreement to Use 19 \0QX Property form (Figure 344). This document defined PEDCo*s level of liability and removed liability from EPA. The following equipment was used in the studies: Twelve EPA samplers modified by PEDCo so that duplicate samples coujLd [be taken at fia flow rate of 65 cc/min for 24 hours (see Figure 3-5). One Bendix Ker ovane Model 141/120 wind speed/direction system with a 10-meter tower. One Weather Measure Corporation Model H-311 hygrothermograph to measure temperature and relative humidity. The 12 sampling sites were selected for their position on the perimeter of the study area, as close as possible to the places where EPA meteorologists had predicted maximum impact. The wind system and h^grothermograph were located at the sampling site most representative of meteorological conditions in the study area. 3.2.1 Routine Sampling Activities The following slj:ep--by-step procedure was followed by the PEDCo field technician at each sampling site. Inspect the sampling site and equipment for possible vandalism or anything unusual. Record findings in the study log bo ok. Record the adsorption tube number, site location, and sampler location on the sample data form (Figure 3-6). Record the vacuum reading, which must be in excess of 375 mm. If vacuum is less than 375 mm, check sampler for leaks or r.eplace sampler with the spare supplied. i Connect two tubes in tandem, as shown in Figure 3-7. Break the adsorption tube ends and connect the tube to the sampler. 20 VVC 000012377 lAGREEMENT TO USE PROPERTY (PRINT) the Undersigned, for dollars, receipt of whiclji is, hereby acknowledged, and other good and valuable consideration hereby agrees to the following; 1. PEDCo Environmental, Inc., (PEDCo) as an agent of the U.S. Environmental Protection Agency (EPA) may set up and opqrat^ an air monitoring station at for the pe riod of to 2. PEDCo shall bd permitted vehicular access to said station as required for its installation, maintenance, and removal 3. The undersigned shall supply and pay for all electrical energy req|Jired to operate the air quality monitors located at the station. PEDCo agrees to .he following: 1. At the termination of this agreement the air monitoring station and all equipment related thereto will be re moved and the property restored to its original condi tion at no expanse to the Undersigned. Undersigned PEDCo Environmental, Znc. Figure 34-4 Property use agreement document. 21 VVC 000012378 *,/T%RAIN SHIELD I roUR SAMPtt TUBES HIGH DENSITT POLYPROPYLENE TUBING 5 ft hour inte^rnf-.od sampler for EDC monitorinr \0 0 0 0 SAMPLE DATA FORM Site Number: Site Location: Operator: Start Date End Date Time Time Tube Numbers Front Back Running Time Mete r Final ___ Start ___ Sample Time Flow Rate Start Mid Final Average Vacuum in. Ug Start ______ Mid ______ min. Final ______ cc/ir.in. cc/min. ce/min. cc/min. Average Flew Rate X Total Sample Time Sample Volume cc. Remarks: Weather Conditions Fig ure 3-6. Sample data form* 239 000x 23 ^>4C FRONT TUBE BACK TUBE !*---------------- 7 cm--------- 7 cm -------------------- GLASS TUBE FIBERGLASS URETHANE FOAM GLASS TUBE FIBERGLASS URETHANE FOAM 7~ ^ tun i ro (Id) i TO VACUUM SOURCE 20-40 MESH ACTIVATED COCONUT CHARCOAL TEFLON TUBING AUG SIZE *3 BROKEN END OF TUBE 20-40 MESH ACTIVATED rnrnwiiT rujornii VVC 0 0 0 0 1 2 3 8 1 Figure 3 7- Diagram of tandem charcoal tubes for EDC sampling showing broken ends* Connect tie jrotameter to the other end of the adsorption tube anld record the initial flow derived from the rotameter calibration curve; record on the sample data form and in ithe operator's log. The flow rate should be 65 + 5 c4/min. Take remedial action if the rate is not withiri this range. Remove th4 rotameter from the adsorption tube. 10. 11. 12. Record the dtarting date and time on the sample data form and in the operator's log. Return to thd sampling site midway through the sampling period; measure and record the flow rate and vacuum. Return to thje sampling site after 24 hours and record the date, time, and final vacuum reading. Connect the rotameter; measure and record the final flow as in Step 5. Disconnect the adsorption tube and place plastic caps on each end- Place the i adsorption tube and the record sheet in the refrigerated Isample custody case. 13. Store the , samples in complete darkness at 0C during transfer tip tlhe laboratory and until they are analyzed. 3.2.2 Meteorological Measurements The meteorological station was installed at the sampling site where the mo^t jrepresentative meteorological conditions prevailed. A Bendix pjlodel 120 sensor/transmitter was used in conjunction with a Bendix Model 141 recorder to measure wind speed and direction. he sensor/transmitter was located at the top of a 10-meter to\j?er|. Before and after the 10-day operation period, the system was checked for proper orientation and bearing wear as described in the manufacturer's manual. The recorder was also calibrated at 25 0ooov^aZ the same intervals, by pitting into the unit known voltage levels representing the response from the transmitters. Wind speed and direction were recorded on dual chart paper, with wind speed tracing the top portion of the chart and wind direction the lower portion. The chart paper was premarked to show hourly increments. Recorder charts were marked each day with the correct time and date. At the end of each 10-day study, the chart was removed ant wind data reduced. Wind speed was nlea^ured in miles per hour. The data were reduced to find an avfera ge for a specific hour by visually drawing a line (based on judgment) through the middle of the wind speed trace, and recording that figure on a meteorological data record sheet. Wind direction was measured in degrees. A template was placed proportionately between two hourly indicators stamped on the chart, and the prevailing direction was recorded on the data sheet. A wind rose for e ach 24-hour sampling period was then con structed from the redu ned data. A Model H-311 hygrothermograph was used to measure tempera ture and relative humidity. This model uses a bimetallic strip for measuring temperature and a human hair bundle for measuring relative humidity. Temperature and relative humidity were re corded simultaneously on !a 18-cm chart mounted on a clock-driven drum. Temperature was; recorded on the upper half of the chart, and relative humidity on the lower half. 26 VVC 000012383 The hygrothermograph was housed in a louvered shelter mounti ed at the 2-meter l^vep. of the meteorological tower. The correct time and date were majrked on the recorder charts each day. At the end of a 10-day study the chart was removed, and the temper ature and relative humidity data were reduced and recorded on the meteorological data 1 form. 3.3 LABORATORY ANAIJjYS t S 3.3.1 Sample Handling All samples collected in the field were stored in the dark at 0C within a small refrigerator. Under these conditions, they were hand-carried to he PEDCo laboratory. At the laboratory, they were logged ik the sample receipt record and assigned a laboratory sample code. Samples were selected for analyses after referring to information about the prevailing meteorological i; conditions for each,24fhour sampling period. Samples from sites downwind of the emi ssi on source and from background sites were selected for analysi s. Each day, 50 to 70 percent of the exposed tubes were selected for, analysis. In addition to the analyses of duplicate field samples, about 10 percent of the desorbed samples were selected for teplicate analysis. Internal standard solu tions and check samples were also analyzed. 3.3.2 Sample Analyses The samples wetfe desorbed in carbon disulfide and analyzed by gas chromatographic separation and mass spectrographic de tection. An internal Standard was added to the carbon disulfide 27 OOOOU^ vvc desorbing solution to provide a specific ion abundance, which was used to monitor the perational characteristics of the mass spectrometer during Analyses. This internal standard, in con junction with a seri es of external standards of EDC in carbon disulfide, was used to identify and measure the amounts of EDC present in the field samples. One analytical run consisted of a series of three standards, followed by ten samples and four to five quality assurance Samples. This analytical scheme was then repeated. Details of the method used to analyze EDC in samples from charcoal adsorption tubes are presented in Appendix A. 28 VVC 000012385 SECTION 4 iDATA PRESENTATION Ambient levels df &DC and meteorological data for the three study areas are presjentpd in tabular and graphic form for each 24-hour sampling peribdJ iI ii The precision of| th analytical method, based on statistical analysis (relative standard deviation) of replicate standard solutions, was determined to be 3 percent. The precision of both the analytical and spmpjLing methods, based on statistical anal ysis (relative standard deviation) of replicate samples, was determined to be 6 p^rc^nt. Standard check samples prepared by EPA and by PEDCo wejtre .used to determine the accuracy of the analytical method. Thel EPA check samples yielded an average recovery of 72 percept ;j and the PEDCo samples, an average re covery of 97 percent. I id an attempt to find the reason for this discrepancy, a statispic41 evaluation was made of the possibility of EDC decay on the Jtutje between the times of preparation and analysis; but no biases I were observed. Because the reason for the discrepancy couldj n^t be ascertained, the accuracy of the analytical method canl odly be estimated as between 72 and 97 percent. i! 29 WC 000012386 4.1 CALVERT CITY , KENTUCKY, STUDY AREA A preliminary 3-^ay field study was conducted to evaluate the sampling and analytical approach. This study demonstrated that the sampling approach and the analytical methodology were capable of meeting th^ objectives of the study. The EDC levels found during the studp' in Calvert City, Ky.# are summarized in Table 4-1; refer to mbsection 3.1.1 for site locations. The EDC levels and prevailing meteorological conditions for each day of the study have been plotted on maps of the study area, and these are presented in Figutes 4-1 through 4-13. The reduced meteor ological data collected during the study period are presented in Appendix B. 4.2 LAKE CHARLES, LOUISIANA, STUDY AREA The EDC levels found during the Lake Charles, La., study are summarized in Tablfe 4-2; refer to subsection 3.1.2 for site locations. The EDO levels and prevailing meteorological conditions for each day if this study have been plotted on maps of the study area, and are presented in Figures 4-14 through 4-25. The reduced meteorological data collected during the study period are presented in Appendix C. 4.3 NEW ORLEANS, LOUISIANA, STUDY AREA The EDC levels determined during the New Orleans study are summarized in Table 4-3; refer to subsection 3.1.3 for site loca tions. The EDC levels and prevailing meteorological conditions 30 ooool for each day during I the study have been plotted on maps of the study area, and are presented in Figures 4-26 through 4-35. The reduced meteorological data collected during this study period are presented in Appe ndix D. 31 VVC 000012368 TABLE 4-1. DATA SUMMARY OF EDC LEVELS (ug/m3)a IN CALVERT CITY, KY., STUDY AREA Date sampled 8-26-78 k 8-27-78 ^ 8-28-78 b q_ Q--7 R 9-10-78 9-11-78 9-12-78 9-13-78 9-14-78 9-15-78 9-16-78 9-17-78 9-18-78 Site location 1 2 3 4 5 6 7 8 9 10 25.5 4.1 1.4 10.6 <0.5 18.0 54.0 12.2 <0.5 n no 7 16 8 7 ? 14.4 41.3_____4.8 rf> -- ----1--7 37.7 37.8 18.0 12.1 15.7 3.5 <0.5 <0.5 <0.5 1.7 6.1 24.7 10.8 <0.5 0.6 6.9 0.7 30.2 <0. 5 <0.5 2.5 35.8 59.9 3.3 <0.5 <0.5 <0.5 36.3 15.2 21.4 <0.5 <0.5 <0.5 <0.5 <0.5 9.0 <0.5 <0.5 <0.5 8.2 <0.5 0.7 <0.5 <0.5 <0.5 <0.5 <0. 5 <0.5 <0.5 67.8 12.0 <0.5 <0.5 <0.5 <0.5 24.5 30.0 11 12 28.7 m* 4.7 10.7 <0.5 55.0 <0.5 <0.5 <0.5 <0.5 46.4 <0.5 For conversion, lyg/m3 is equivalent to 0.247 ppb. Preliminary study, with sampling conducted from 8 a.m. All other study periods were midnight to midnight. > CD VVC 00001 VVC 0 0 0 0 1 2 3 9 0 VVC 0 0 0 0 1 2 3 9 2 Figure 4-3. Results of preliminary ethylene dichloride study Calvert City, Ky., for 8-28-78 (8 a.m.) to 8-29-78 (8 a.m.). EDO concentration given in jig/m^. 00001239 YVC 0000X2394 F ig u re 4 -5 . R e su lts o f e th yle n e d ic h lo rid e s tu d y , C a lv e rt C ity , K y., 9-10-78. EDC c o n c e n tr a tio n g iv e n in u g /m 3 . tO O O VVC 0 0 0 0 1 2 3 9 6 Figure 4-7. Results of ethylene dichloride study, Calvert City, Ky., 9-12-78. EDC concentration given in pg/m^. 40 VVC 000012397 F ig u re 4 -8 . R e s u lts o f e th y le n e d ic h lo rid e s tu d y , EDC C a lv e rt C ity , c o n c e n tra tio n K g y iv .f e n 9 i-n1 3 -7 8 pg/ m ^ . vvc 000012390 F ig u re 4 -9 . R e s u lts o f e th y le n e d ic h lo rid e s tu d y , C a lv e rt C ity , K y ., 9-14-78. EDC c o n c e n tr a tio n g iv e n in u g /m ^ . 000 OO^ZIOOOO Figure 4-11. Results of ethylene dichloride study, Calvert City, Ky., 9-16-78. EDC concentration given in ug/m^. F ig u re 4 -1 2 . R e s u lts o f e th y le n e d ic h lo rid e s tu d y , C a lv e rt C ity , K y ., 9-17-78. EDC c o n c e n tr a tio n g iv e n in u g /m ^ . VVC 0 0 0 0 1 2 4 0 2 TABLE 4-2. DATA SUMMARY OF EDC LEVELS (jjg/mV IN LAKE CHARLES, LA. , STUDY AREA 7* Site locat: Lon - Date sampled 1 2 34 5. 6 7 8 9 10 11 V 9-24-78 43.8 107.0 1.8 <0.5 <0.5 9-25-78 112.4 167.0 64.9 114.8 <0.5 <0.5 9-26-78 32.1 227.7 0.7 61.6 172.5 8.6 1.6 <0.5 9-27-78 103.2 152.9 <0.5 7.6 120.1 3.9 <0.5 0.8 9-28-78 39.5 267.4 <0.5 18.2 88.7 3.2 <0.5 <0.5 0.5 9-29-78 1.4 651.7 40.0 7 44.8 383.3 171.6 <0.5 0.9 <0.5 9-30-78 77.0 193.7 230.7 120.8 89.7 0.9 10-1-78 227.6 199.9 20.5 87.8 122'. 0 42.0 1.9 0.6 5.7 51.0 10-2-78 76.7 6.0 5.1 5.8 10.7 7.1 324.3 10-3-78 225.2 147.3 52.3 41.0 295.5 33.6 27.3 32.8 30.2 36.2 581.6 10-4-78 47.6 472.5 60.3 274.8 280.1 96.2 21.6 14.9 14.9 3.1 10-5-78 269.5 387.4 67.2 182.2 248.4 96.4 28.5 19.9 15.0 12 <0. 5 <0.5 <0.5 2.2 3.2 0.8 0; 9 9.7 19. 2 497.8 39.6 24.2 For conversion, 1 pg/m3 is equivalent to 0.247 ppb. vvc 000012403 VVC 0 0 0 0 1 2 ^ 0 4 9-25-78. in o 9-27-78. VVC 0 0 0 0 1 2 M I8 9-29-78. VVC 0 0 0 0 1 2 4 0 9 VVC 0 0 0 0 1 2 4 1 0 VVC 0 0 0 0 1 2 4 1 1 VVC 0 0 0 0 1 2 4 1 2 Figure 4-22 Results of ethylene dichloride study. Lake Charles, La., 10-2-78 EDC concentration given in yg/m^. Cl^ZTOOQO OAA VVC 0 0 0 0 1 2 4 -1 4 0) u 3 CT> H Em OOOOl^^15 58 vvc -2 5 . R e s u lts of e th y EDC lceonne c edni ct rha ltoi or ni d e g i st ve u n d iyn. Lake C h a rle s , yg/m ^. L a ., 1 0 -5 -7 8 . TABLE 4-3 DATA SUMMARY OF EDC LEVELS (yg/m3)a IN NEW ORLEANS, LA., STUDY AREA \ Site location Date sampled 1 2 3 4 5 6 7 8 9 10 10-10-78 10-11-78 <0.5 <0.5 0.7 5.8 43.2 &t. d 0.9 <0.5 1 6 ft 6.8 12.8 5.5 8.7 0.5 10-12-78 2.9 2.5 7.4 <0.5 20.7 24.3 1.8 1.5 10-13-78 0.6 2.7 5.2 23.7 <0.5 0.8 6.5 6.7 10-14-78 <0.5 <0.5 0.6 <0.5 0.6 1.1 17.6 0.7 10-15-78 1.2 0.8 37.8 3.1 2.0 14.0 0.7 13.1 10-16-78 3.7 9.4 3.6 3.9 8.6 10.0 3.0 10-17-78 6.2 117.4 <0.5 <0.5 5.3 10.8 6.2 3.6 10-18-78 <0.5 1. 1 2.4 169.0 9.1 <0.5 29.1 6.2 6.0 10-19-78 <0.5 31.2 <0.5 9.7 3 For conversion, 1 yg/m is equivalent to 0.247 ppb. <0.5 7.1 3.8 11 8.7 <0.5 4.4 3.2 1.1 <0.5 <0.5 12 6.4 5--6---------0.7 1.2 2.6 2.0 6.2 VVC 0 0 0 0 1 2 4 1 6 VVC 0 0 0 0 1 2 4 1 7 VVC 0 0 0 0 1 2 4 1 8 w e 0000X2419 vvc 000012420 ZZ*7ZT0 0 0 0 t zrftoooo ^Z to o o o VVC 0 0 0 0 1 2 4 2 5 vvc 000012426 SECTION 5 QUALITY ASSURANCE PROGRAM Because of the importance of the data being collected, adherence to strict quhlity control procedures was needed in sample collection, hahdling, and analysis. 5.1 SAMPLE COLLECTION Duplicate samples ( consisting of two sets of tandem charcoal adsorption tubes) were collected at each site, and a rotameter was used to take flow m easurements. Readings were taken at the beginning, at midpoint, and at the end of the 24-hour sampling period. The rotametelr vr as calibrated with an NBS traceable soap bubble meter at the bejj inning and end of each 10-day sampling period. The length of tlhe sampling period was measured by a time meter attached to each sampler. All meters were checked for proper operation before sampling commenced, and they were found to be within 0.1 pe::ce at. The actual start and stop times each day were controlled by a 24-hour timer that started and ended each sampling period at midnight. 70 VVC 000012*27 5.2 SAMPLE HANDLING Each tube wa numbered with the date and site location, Tube seals were btokten on the site. During sample collection, the charcoal tubes were protected from light and rain by a metal shield. After be: ng removed from the sampler, the tubes were capped and refrige raied at 0C until brought to the laboratory for analysis. 5.3 SAMPLE ANALYSES The GC/MS ir strument was calibrated with three external standard solutions be fore sample analysis. An internal standard was also incorporated to monitor the response of the mass spec- trometer. None of th sse standards could deviate by more than 5 percent from the average. A standard was analyzed after each 10 samples analyzed, and was required to meet the same criterion of 5 percent. If a standard response was beyond this limit, immediate correctirve action was taken before continuing sample analysis; but no corrections were made to previous analyses. One out of every 10 samples analyzed was an EDC quality control check sample, were analyzed bliijid. These samples were prepared by the EPA and Twenty percent of all duplicate samples collected from eac i 4tudy area were analyzed, and extracts of 10 percent of all t tie samples analyzed were reanalyzed. PEDCo generated its own se ts of internal quality control samples, and analyzed them with e ich batch of samples from the field. These data were used to measure the internal accuracy of the analytical 71 VVC 0000124-28 method. The specific q uality control data are presented in the following sections. 5.4 QUALITY CONTROL DATA PRESENTATION 5.4.1 Quality Control heck of Solvents, Charcoal Tubes, and Standard Refer enc e Materials Solvents-- The solvent used fo r the desorption of EDC from the charcoal tubes was Fisher Rea<ent Quality carbon disulfide. Lot No. C184 was used for the an alysi es in this study. The solvent was analyzed by GC/MS more i;ha:i 30 times (several analyses were made on each bottle opened), and no EDC was detected. Charcoal Tubes-- More than thirty 150-mg charcoal tubes (see Figure 5.1) of Lot No. 107, manufact tured by the SKC Corporation, Pittsburgh, Pennsylvania, were a ijialyzed by GC/MS during the analyses of the field samples, and no EDC was detected. Analyses of Field-Exp^>sed Charcoal Tubes-- During the three field studies, about 60 charcoal tubes were exposed with one end open to the ambient air for a period of 24 hours. This test was conducted to find out if EDC would migrate into a tube before or affter dynamic sampling was initiated. Over 20 tubes were select ed at random from those used in the three study areas, and an 4ly4is for EDC was performed. No EDC was detected by the GC/MS an alysis of these tubes. 72 000012429 vvc E! ~ (: 3 -- i E <_> U CD X h- '' CO CO < _] o <1) s 4-> I--I rd 0 _l u < O o cr JrCd, o < Cn x uo in h- d o *U u0 o u g cud O' <d H Q I in 0u) D O' *H n oooov^30 73 ^MC Purity Check of EDC Standard-- Ethylene dichloride supplied by Chem Services, West Chester, Pennsylvania (Lot No, 0-642), with a purity quoted by the manu facturer at 99+ percent, was used for the preparation of EDC external standard solutions. A GC/MS analysis of this material, using the same conditions as for the analysis of field samples, did not show the presence of contamination from other compounds. The manufacturer's assay of 99+ percent was, therefore, assumed to be accurate; and no corrections were made with respect to the purity of this reagent when it was used for the preparation of external standard solutions. 5.4.2 Evaluation of EDC Breakthrough While Sampling High Levels of EDC The preliminary te sts of the methodology did not include breakthrough tests at extremely high EDC levels. During the study at Lake Charles, Louisiana, high levels were encountered. To detect breakthrough, TEDCo analyzed the second 150-mg charcoal tube in the series for the presence of EDC. Several tubes were selected for analysis, and EDC was detected in the backup tubes of two. Breakthrough was experienced only at the EDC range of 200 to 600 [jg/m^ (60-18(1 ppb), and amounted to about 1 percent. The breakthrough could result from nonhomogeneous charcoal pack ing within some of the tubes, because it was not detected in all samples in that range. Table 5-1 summarizes these tests. 74 vvc ooooiz^31 TABLE 5 -1. ANALYSIS OF BACKUP TUBES FROM HIGH LEVEL EDC SAMPLING Date samp! .ed 9-25-78 9-26-78 9-29-78 10-1-78 10-3-78 10-3-78 10-4-78 Site No. 1 1 2 1 2 11 2 EDC yg/m^ Front Back 114.7 <0.5 35.9 <0.5 651.7 <0.5 216.5 1.5 141.0 581.6 <0.5 6.2 457.4 <0.5 75 OOO oi* ^C. 5-4.3 Analysis of Collocated Samples All of the sampling was performed in duplicate. About 10 percent of the collocated samples were selected for further statistical analysis, to establish the total sampling and ana lytical error. Tables 5-2 through 5-4 present the results of these analyses for the three study areas, together with the arithmetic means and Standard deviation of the results from the collocated samples. These data show [thalt the standard deviation of EDC concen trations, as determined by collocated sampling, increases as the EDC concentration increases. The relationship between the stan dard deviation and the mean EDC concentration is most clear in the data from Lake Charles, La. (Table 5-3). A graphic presen tation of this relationship for all the collocated samples is given in Figure 5-2. Because of the apparent relationship between the standard deviation and the mean, the variability between concentrations (based on the collocated sampling) is expressed in terms of the relative standard devd.atjon [i.e., s/x (100)]. Regression anal ysis showed the relative standard deviation for these data to be approximately 6 perceht. This variability is a measure of the precision of both th^ Sampling and the analytical procedures. 5.4.4 Duplicate Analysis of Desorbed Field Samples The relative standard deviation of 6 percent is an estimate of the combined precisiorl of sampling and analysis. To derive an 76 00GiZV33 TABLE 5-2. ANALYSIS OF COLLOCATED SAMPLES FROM CALVERT City, KENTUCKY, STUDY AREA Date sampled 8-26-7 B 8-27-78 8-27-78 9-9-78 9-9-78 9-9-78 9-10-78 9-12-78 9-12-78 9-14-78 9-14-78 9-14-78 9-15-78 9-16-78 9-17-78 Site NO 12 9 8 2 1 10 10 10 9 9 7 1 7 7 10 x: Mean s: Standard deviation EDC concentration, uq/m^ | Sample A Sample B X 27.7 29.7 28.70 55.2 52.7 53.95 16.6 17.3 17.95 74.3 70.0 72.15 26.6 25.4 26.0 1.1 1.2 1.15 3.0 3.9 3.45 29.2 31.1 29.65 0.8 0.5 6.50 19.9 22.9 21.40 38.0 34.5 36.25 3.6 3.0 3.30 9.0 8.9 8.95 0.9 0.5 0.7 13.3 10.7 12.0 s 1.41 1.77 0.92 3.04 0.85 0.07 0.64 1.34 0.21 2.12 2.47 0.42 0.07 0.28 1.84 77 OOOOl^* ---------Pi -- <Z f TABLE 5-3. A LAKE CH YSIS OF COLLOCATED SAMPLES FROM ES, LOUISIANA, STUDY AREA Date sampled 9-24-78 9-25-78 9-25-78 9-26-78 9-27-78 9-28-78 9-29-78 9-30-78 10-1-78 10-1-78 10-2-78 10-2-78 10-3-78 10-4-78 10-5-78 Site No 1 1 2 1 1 L L L L 2 1) 1* ! : 5 EDC concentration, yg/m^ Sample A Sample B 43.6 44.0 X 43.8 s 0.28 114.7 110. 1 112.4 3.25 159.9 178.1 169.0 12.87 28.3 35.9 32.1 5.37 124.7 135.6 13*.15 7.71 37.9 41.0 39.45 2.19 1.3 1.5 1.4 0.14 71.2 82.9 77.05 8.27 238.7 216.5 227.6 15.7 188.0 207.7 197.85 13.9 6.3 7.9 7.1 1.13 18.2 20.2 19.2 1.41 141.0 153.5 147.25 8 . B4 457.4 487.6 472.5 21.35 236.3 260.4 248.35 17.0 x: Mean s: Standard devi itic n 78 1Z43* 0000 TABLE 5-4 AllALYSIS OF COLLOCATED SAMPLES FROM NEW 0 RLEANS, LOUISIANA, STUDY AREA Date sampled Site No. 10-10-78 10-11-76 10-11-78 10-12-7B i l 10-12-78 7 10-12-78 9 10-13-78 10-14-78 10-14-78 10-14-78 ') , ci i; 10-15-76 4 10-15-7B t 10-16-76 4 10-16-7B 8 10-16-78 1] 10-17-76 4 10-18-78 10-19-78 E 4' 10-19-7B 10-19-78 i x- : Mean i a; Standard deviation EDC concentration (uq/m3) Sample A Sample B 11-1 0.6 8.9 3.2 25.8 1.2 7.4 0.6 17.9 1.2 37.6 14.2 8.5 9.1 3.2 146.9 28.9 32.2 9. B 6.7 14.5 0.8 8.4 2.6 22.8 1.8 6.0 0.7 17.4 1.1 38.0 13.8 10.3 8.1 3.2 195. B 29.3 30.1 9.6 7.5 *s 12.8 0.7 2.4 0.14 8.65 0.35 2.9 0.42 24.3 2.12 1.5 0.21 6.7 0.99 0.65 0.22 17.65 0.35 1.15 0.07 37.B 0.26 14.0 9.4 0.28 1.27 8.6 0.71 3.2 0 171.35 34.56 29.1 0.28 30.65 1.48 9.7 7.1 0.14 0.57 79 v^`* 000 il < n< o o o o M f\J UJ -4 STANDARD D E V IA T IO N , ug/nv ARITHMETIC MEAN EDC CONCENTRATION, pg/m3 Figure 5-2. Standard deviation and arithmetic mean concentration of EDC for collocated samples. estimate of the pr^ciLion of the analytical method alone, dupli cate EDC analyses j^f Idesorbed samples were run on 10 percent of all the samples ^na]|yzed. Table 5-5 through 5-7 present the results of the du^li^ate analysis, together with the mean and standard deviationsj fcjr each set of duplicates. The relationship between the mean pnd|the standard deviation is presented graph ically in Figure 5|-3 .| As with the analysis of collocated sam ples, the standard|deviation of the duplicate samples is propor tional to the avprape concentration. The relative standard deviation (i.e., p>rie|ecc|ision) of the analytical method is approxi mately 3 percent. 5.4.5 Precision o Ambiient EDC Measurements The precision1 (^.e., relative standard deviation) of an individual EDC measurement is approximately 6 percent. This estimate, which is based on the analysis of ambient EDC measure ments in the threel study areas, includes the precision of both the sampling techniquL and the analytical method. Precision of the analytical metJiod^ alone, as derived from duplicate analyses of desorbed samples!, iL approximately 3 percent. 5.4.6 Analysis of kxtJernal Quality Control Unknown Solutions The GC/MS analysis of samples from the field studies were conducted by several Ichemists over a period of 2 months. Each chemist was scheduled |a work period in which to prepare standards from a master stocjk jsolution and analyze a batch of 30 to 40 samples. Another cjhenjiist, independent of the one performing the 81 ooooiz^8 vvc TABLE 5-5. D UPL ICATE ANALYSIS OF DESORBED SAMPLES FROM CA LVE RT CITY, KENTUCKY, STUDY AREA Date sampled 9-9-78 9-10-78 9-12-78 9-13-78 9-14-78 9-15-78 9-16-78 9-16-78 9-17-78 S ite No. 10 1 10 11 7 7 9 2 10 EDC, yq/m^ Run 1 Run 2 ND 38.4 37.0 28.3 30.2 55.8 54.3 39.0 9.0 37.1 8.6 ND 8.2 ND 8.2 13.0 13.6 Xs 37.7 0.99 29.3 1.34 55.1 1.06 38.05 1.34 8.8 0.28 8.2 0 13.3 0.42 x: Mean s: Standard deviation ND: Not detected 82 000012439 VVC rCO- i CN 1 o> VVC 0 0 0 0 1 2 ** TABLE 5-6. DUPLICATE ANALYSIS OF DESORBED SAMPLES FROM LAKE CHARLES, LOUISIANA, STUDY AREA Date sampled 9-25-78 9-27-78 9-28-78 9-29-78 10-3-78 10-5-78 10-5-78 10-4-78 Site No. 1 4 5 1 6 12 4 10 2 EDC, yg/m^ Run 1 Run 2 43.6 45.4 66.4 121.6 63.1 119.3 37.0 38.8 164.8 178.4 503.3 185.2 493.4 179.5 19.7 19.9 504.2 471.9 X 44.5 64.8 120.5 37.9 171.6 498.4 182.4 19.8 488.1 s 1.3 2.33 1.62 1.3 9.6 7.0 4.0 0.14 22.9 x: Mean s: Standard deviation TABLE 5-7. DUPLICATE ANALYSIS OF DESORBED SAMPLES FROM NEW ORLEANS, LOUISIANA, STUDY AREA EDO f yg Date sampled Site No. Run 1 Run 2 X s 10-10-78 10-10-78 10-12-78 10-12-78 10-13-78 10-14-78 10-15-78 10-16-78 10-17-78 10-17-78 10-18-78 10-19-78 4 ND ND ]2 6.5 6.1 6.3 0.28 4 7.6 7.2 7.4 0.28 9 1.5 2.2 1.85 0.49 9 6.0 6.1 6.05 0.07 I2 1.1 0.7 0.9 0.28 11 4.0 4.7 4.35 0.49 8 8.1 8.0 8.05 0.07 6 ND ND 7 5.8 4.9 5.35 0.63 8 29.2 28.6 28.9 0.42 30 4.2 3.5 2.85 0.49 x: s: ND: Mean Standard deviatic n Not detected 84 s/vc 000 OlZ^1 0 50 100 150 200 250 ARITHMETIC MEAN - DUPLICATE ANALYSES , yg(m3) Figure 5-3. Standard deviation and mean concentration of EDC for duplicate analyses of selected samples. analyses, would prepare an external check standard from an inde pendent stock solution EDC, and submit it to the analyst. The data from this quality control check on the working standard solutions are presented :.n Table 5-8. To develop a relationship between the amount of EDC in the standard solution and that found by the PEDCo analyst, PEDCo analyzed these results by regression analysis. The assumption was made that the precision of the amount of EDC added was sub stantially better than the precision of the amount determined by the GC/MS analysis. The relationship between the quantity of EDC determined by the GC/MS analysis and that in the prepared standard solution can be expressed as y = 0.\2 -f 0.97x where y = ng/|jl EDC determined by the GC/MS x = ng/pl EDC in the standard solution Based upon this relationship, the recovery of EDC in the standard solution by the GC/MS procedure varies from 109 percent at 1 ng/pl to 98 percent at l ng/pl. 5.5 EVALUATION OF QUALITY CONTROL CHECK SAMPLES Two sets of quaj.itf control check samples, with known lev els, were prepared b^ the EPA Environmental Monitoring and Sup port Laboratory (EMSI^ ) and by the PEDCo Laboratory. These sampies were analyzed a long with the routine analysis of samples collected in the field. 86 VVC 000012443 TABLE 5-8. ANALYSES OF UNKNOWN EXTERNAL STANDARD SOLUTIONS OF EDC Date anal} zee 1 EDC concentration, ncr/u Added Found 10-19-7E 1.25 1.50 10-20-7E 10-20-78 10-20-78 1. 43 5.04 3.67 1.44 5.03 4.40 10-23-78 6.25 5.71 10-23-78 10-24-78 6.25 1.58 5.83 1.69 10-24-78 1.58 1.68 10-24-78 6.25 6.22 10-26-78 3.13 3.26 10-31-78 11-10-78 2.60 0.78 2.64 0.89 11-13-78 0.65 0.50 11-13-78 12.43 12.33 11-14-78 11-15-78 6.28 3.26 6.78 3.21 11-16-78 4.96 4.67 11-17-78 2.71 2.67 11-28-78 6.94 6.65 11-29-78 3.49 3.53 11-30-78 3.14 Average 10 L 3 + a 9.6 3.10 87 VVC 000012444 5.5.1 Check Samples Pre pared bv EPA The EPA provide d 48 samples ranging from 1.18 to 8.26 pg. These samples were prepared by using an EDC permeatj-io^ tube, which was gravimetrically cali- brated, and a dilution system. Each charcoal tube was charged with EDC by sampling !at a known flow rate of about 65 cc/min from the dilution system. By varying the sampling time for each tube produced, the analyst w as able to calculate the content of EDC adsorbed on the tube. Table 5-9 presents the results of the PEDCo analysis (by GC/MS) of the 48 EPA check samples. The quantity of EDC found by PEDCo was significantly less than that reported by EPA. In nine EPA samples reported to contain 1.18 |jg EDC, for example, PEDCo found an average of 0.81 pg, for a recovery rate of only 69 percent. In 17 samples reported to contain 5.90 pg EDC, PEDCo found an average of ^.64 pg, for a recovery rate of 79 percent. Table 5-9 also shows the standard deviation for the repli cate analysis for each of the levels of EDC added by EPA to its check samples. It is Apparent that the standard deviation in creases as the level of EDC is increased. Over the range of EDC levels added by EPA, thi relative standard deviation varies from 20 to 25 percent. 5.5.2 Check Samples Prebared by PEDCo PEDCo prepared a ket of 16 quality assurance samples, 8 having an EDC level of 4.51 pg, and 8 at a level of 9.02 pg. The samples were prepared by using a standard gas mixture of EDC 88 vvc 000012445 9 00 10 < -c o o o o TABLE 5-9. QUANTITY OF EDC FOUND IN EPA QUALITY ASSURANCE SAMPLES (EDC in yg) 1. 18 Sample NO. EDC found ---------C G J 22 25 26 27 31 33 0.53 0.66 0.89 0.89 0.64 1.05 0.95 0.99 0.65 Mean 0.81 Std.dev. 0.19 Recov- ery, * 69.00 Relative std. dev., 1 23.00 Amount of EDC added by EPA 2. 36 3.5 4 5. 90 Sample-- _____EDC--------- ----- Sample------ ------ EDC-------- sample No. found No. found No. EDC found D 1.37 H 1.27 I 1.50 N 1.13 R 2.07 T 1.31 X 1.68 10 0.94 13 1.76 14 1.11 15 2.14 17 1.95 20 1.64 A 2.62 E 5.45 L 4.67 M 4.84 P 3.56 V 7.47 W 3.89 11 4.14 12 2.72 16 l.27a 18 6.83 19 4.90 21 2.56 23 4.86 24 4.85 28 4.13 29 4.70 30 4.51 32 4.79 1.54 0.39 2.62 0 4.64 1.22 65.00 74.00 79.00 8. 26 Sample No. EDC found B 4.47 F 6.75 K 6.07 O 7.49,, Q 0.45 U 6.64 Y 4.81 6.04 1,18 73.00 25.00 0 26.00 20.00 a Deleted -- gross error. (contained under pressure in a cylinder), and a dilution system. Figure 5-4 is a diagram of this system, with which the two series of check samples weire prepared simultaneously. Critical flow orifices were selected to provide a sampling rate of 65 1 cc/min. An excess flow of the EDC gas mixture was established through the eight-port glass sampling manifold. Eight tubes were connected to the critical flow orifices. Sampling was conducted for 15.0 minutes to produce the low-level check samples, and 30.0 minutes to produce the high-level ones. The amount of EDC adsorbed on each tube w is then calculated from the concentration of EDC, as assayed by the ^ supplier, and derived from the sampling rate and time period. Table 5-10 presents the results of PEDCoT s analysis (by GC/MS) of these quality assurance samples. For the eight samples prepared at the level of 4.51 pg, the average amount of EDC found was 4.45, or a recovery rate of 99 percent. For the eight sampies prepared at the level of 9.02 pg, the average amount of EDC found was 8.61 pg, o^ a recovery rate of 95 percent. The standard deviations were 0.30 pg and 0.27 pg for the 4.51 and the 9.02 pg EDC levels, respectively. There is no significant change in the standard deviatioh for the two levels of EDC considered in this analysis. 5.5.3 Comparison of Analyses of EPA and PEDCo Check Samples The results from he analyses of the two sets of quality assurance samples di ::fei: considerably. The EDC recovery rates VVC 000012447 90 VACUUM VVC 0 0 0 0 1 2 4 4 0 Figure 5-4 Apparatus for generator and sampl ing gas mixtures of EDO on charcoal tubes. TABLE 5-10. QUANTITY OF EDC FOUND ASSURANCE SAMPLES (EDC in yg) IN PEDCO QUALITY Mean Std. dev. Recovery, % Relative std dev % Amount of EDC added by PEDCo 4.51 9.02 EDC found EDC found 4.67 4.27 4.12 4.63 4.86 4.71 4.31 4.05 8.29 8.83 8.31 8.72 8.88 8.65 8.28 8.91 4.45 0.30 99.00 6.7 8.61 0.27 95.00 3. 1 WC 000012A49 92 for the samples pr^pa^red by EPA were between 65 and 79 percent; but the rates for jthej samples prepared by PEDCo were 95 and 99 percent. Further, | tbfe standard deviation for the EPA samples increased as the Eljc jl.evel increased: from 0.19 pg at the 1.18 pg level, to 1.18 ^g &t the 8.26 pg level. Because the analytiii cal methods were ^dei^tical for both sets of samples, the dif ference in the resiiltk cannot be explained without further in vestigation. |I 93 -- 0000 VVC REFERENCES 1. PEDCo Environmental, Inc. Monitoring System for the Col lection and Analyses of Ambient Levels of Ethylene Dichlo ride in Urban [Atmosphere. U.S. Environmental Protection Agency Contract No 68-02-2722, Task No. 7 and 12. nati, February 1 9791. Cincin- 2 . NIOSH Method S 122 for the Determination of Ethylene Di chloride. NIOSH Manual of Analytical Methods, Part II. 2nd edition. DHEW Publication No. 77-157-B, April 1977. 3 . American Petrole um Institute, by Gulf Science and Technology Company. Method for the Determination of Benzene in Ambient Air (Integrated Sampling). Pittsburgh, July 1977. 4. PEDCo Environmental, Inc. Monitoring System for the Col lection and Analyses of Ambient Levels of Benzene in Urban Atmosphere. Coijtr^ct No. 68-02-2722, Task No. 7. January 1979. 5 . Yasuda, S.K., ar.d E.D. Lounghron. Air Sampling Methods for Tetrachloroethane and Other Related Chlorinated Hydrocarbons. Journal of C hromatography, 137:2, pp. 283-292. 1977. 6. Lodge, J.P., et al The Use of Hypodermic Needles as Crit- ical Orifice in A ir Sampling. J. Air Pollution Control Association, 16:4, pp. 197-200. 1966. 94 0000 APPENDIX A TENTATIVE METHOD FOR THE DETERMINATION OF ETHYLENE DICHLORIDE IN THE ATMOSPHERE BY 24-H OUR INTEGRATED SAMPLING A-1 yyC 000012^52 APPENDIX A TENTATIVE METHO D FOR THE DETERMINATION OF ETHYLENE DICHL 3RIDE IN THE ATMOSPHERE BY 24- HOUR INTEGRATED SAMPLING This method has l)>een drafted from available information, as presented in the bibl iography, and from laboratory and limited field evaluation. It is still under investigation and is subject to revision. 1. Principles of the Method (a) A known volume of air is drawn through a charcoal tube for a period of 24 h^urs to trap the ethylene dichloride (EDO vapors present. (b) The charcoal in the tube is transferred to a small, stoppered sample container, where it is desorbed with a solvent mixture of carbon disulfide and an internal standard compound (1-bromohexane).* (c) An aliquot lof the desorbed sample is injected into a gas chromatograph that, uses a mass spectrometer as the detector. (d) The ratio of the peak area for EDC to the peak area for 1-bromohexane is determined and compared with the ratio of peak Warning: Because EDC is a suspected carcinogen, care must be taken to protect operators from breathing fumes. Carbon disul fide is toxic, and its vapors form explosive mixtures with air; therefore, this material should be handled in a well-ventilated room with a fume hood, VVC 0000!*^ areas obtained from 4 standard, to ascertain the amount of EDC present in the sampleJ 2* Range and Sensitivity. The limit of detection is approxi mately 1 pg/nr (0.3 ppb). The maximum of the range is approxi mately 500 pg/m3 (125 ppb); it may be increased by diluting the sample after extraction. This method was evaluated over an EDC range of 2 to 320 3 pg/m (0.6 to 95 ppb), cit temperatures of 25 and 30C and rel ative humidities of 44 and 99+ percent, respectively. The sam pling rate was 65 cc/ritin at 760 mm Hg for 24 hours. The charcoal adsorption tube (Figure A-l), which consists of two sections of activated charcoal separated by a section of urethane foam, contained 150 mg charcoal.; and each tube was backed with a second tube to determine breakthrough. The evaluations yielded an average total method ^ff:.ciency (i.e., adsorption and desorption) 3 m excess of 90 percent for EDC levels of 3 to 30 pg/m (10 to 100 ppb). 3 At concentrations of 30 pg/m (100-ppb), 10 percent of the EDC was found on ti}e second (backup) charcoal tube. At an EDC concentration of lapproximately 15 pg/m (0.5 ppb), the overall method efficiency w^s 80 percent. The backup tube was anal- yzed, but the amount of EDC it contained could not be measured because of the detection limit of the GC/MS system. A small peak was observed, however , indicating the presence of breakthrough. Although no effect from humidity was observed at the 65 cc/min sampling rate, water condensing within the charcoal tube A-3 VVC 000012454 > 4 mm I (id) FRONT TUBE 7 cm BACK TUBE TO VACUUM SOURCE ^ z to o o o n Figure A-l. Diagram of tandem charcoal tubes for EDC sampling during sampling will affect the adsorption efficiency. Sampling for 24 hours at rates collection efficiency. in excess of 65 cc/min will affect the 3 At an EDC concentration of 10 yg/m (30 ppb), tests conducted at a flow rate of 500 cc/min and a relative humidity of 99 percent Resulted in an overall method efficiency of less than 20 percent. If a particular atmosphere is suspected of containing a high ievel of EDC, a shorter sampling time should be used. 3. Interferences. It is extremely unlikely that any common pollutants now in the aijibient atmosphere have sufficient concen trations to interfere with the measurement of EDC. Several criteria must be met f02' identification and quantification. The retention time, and the specific mass ions of 49, 62, 98, and 100, are monitored simultaneously. All four of these ions should be presented by a p^ak of the same retention time as EDC to obtain positive EDC i quantification. The data system of the spectrometer will use! the response of mass ion 62 for quantifi cation. 4. Precision and Accuracy. Replicate GC/MS analyses of stan dard liquid mixtures and sample aliquots must not deviate by more than 5 percent. No information is presently available on accur acy for the total methocj. The precision of the analytical meth od, based on statistica| analysis (relative standard deviation) of replicate standard solutions, was determined to be 3 percent. A-5 VVC 000012456 The precision of bbth the analytical and sampling methods, based on statistical analysis (relative standard deviation) of repli- cate samples, was determined to be 6 percent. Standard check samples prepared by EPA and by PEDCo were used to determine the accuracy of the analytical method. The EPA check samples yielded an average recovery of 72 percent; and the PEDCo samples, an average recovery ojf 9^ percent. In an attempt to find the reason for this discrepancy, a statistical evaluation was made of the possibility of EDC decay on the tube between the times of prep aration and analysis; but no biases were observed. Because the reason for the discrepancy could not be ascertained, the accuracy of the analytical jnet^iod can only be estimated as between 72 and 97 percent. 5. Advantages anc. Disadvantages of the Method. The sampling device is small an|l portable, and it uses no liquids. Interfer ences are minimal, anmost can be eliminated by altering chroma tographic conditions. The amount of sample that can be taken, however, is limited by the sampling rate and by the capacity of the tube. When the sample value obtained for the backup tube exceeds 10 percent of that found on the f^.rst tube, the possibility of sample loss exists. Although a GC/MS system for separation and detection is more expensive than an :?id detection system, it is the only one readily available that has the required sensitivity and provides the A-6 vvc 00001Z*57 maximum number of conditions that must be met before a chromato graphic peak is integrated. Other detection systems (FID, elec trolytic conductivity, and electron capture) were attempted, but they presented problems that could not be circumvented. 6. Apparatus and Materials (a) Sample collection materials-- Pump: Capable of maintaining an air pressure differ sntial greater than 0.5 atmospheres at the desire flow rate. Critical orifice: needle to control cc/min 30-gauge, 1/2-in. hypodermic flow rate at approximately 65 Filter cartridge: Disposable 47 mm diameter, 0.45 Mm filter porosity. (Millipore Filter Corp., Bedford, Massachusetts). Charcoal adsorption tubes: 150-mg, standard NIOSH type, connected in tandem as shown in Figure A-l. Vacuum gauge: 0 to 760 mm Hg. Airflow meter: Rotameter type 0 to 120 cc/min, calibrated against an NBS traceable bubble meter. (b) Sample recovery materials-- Muffle furnace: For operation at 250C. Syringe: 0 to 1 ml, gastight, with Teflon plung er. Vials (sample): 2-ml capacity. Caps: vials. Screw type, with septum hole for 2-ml Serum cap liners: Teflon-coated sealing vials and caps. rubber, for Ultrasonic cleaner: 1/2- to 1-gal capacity. (Bronson Cleaning Equipment, Sheldon, Connecticut) A-7 VVC 000012458 (c) Analytical Equipment-- Gas chromatograph with mass spectrometer: Hew lett-Packard 5992-A or equivalent, with glass jet separator and data system. Chromatographic column: Nickel, I .D. containing Supe lcoport. 10 percent SP 6.1 m x 2 mm 1000 on 80/100 Micr o syringes: 0 to 10, 0 to 100, and 0 to 500 micr oliter range. Vial sere (sample): caps and 5-ml and 50-ml capacity, with Teflon-lined serum cap liners. Pipettes: Volumetric Class A, 50-ml, 5-ml, and 1-ml. (d) Reagents used- Chromatographic quality carbon disulfide, , -1 2 dichloroethane, reagent grade, 1-br omohexane, reagent grade, Puri fied helium. 7. Procedure (a) Cleaning o^ Equipment: All glassware used for the laboratory analysii s hould be washed with detergent, thoroughly rinsed with tapwat^r and distilled water, dried, and placed in a muffle furnace at 350C for 30 minutes to remove traces of or ganic compounds. (b) Collection of Samples: Duplicate tandem tubes, con sisting of two 150-mg charcoal tubes, are used for sampling; each is identified as being either the front tube or the backup tube. A 30-gauge, 1/2-in. hypodermic needle is installed for critical A-8 VVC 000012459 orifice flow control The ends from each tube are removed by breaking the glass bdad off with pliers or a small wirecutter. The two tubes are conn scted with Teflon tubing (5-mm I.D.) so that the large (100-mg) section of charcoal will be exposed to the sampled air when 'zhe tubes are connected to the sampler. The tubes are then conneote i to the sampler, and the pump is acti- vated. Figure A-2 shows a diagram of the sampler, A record is kept c f the initial vacuum starting time, the adsorption tube numbe::, and the site location. The sampling rate is measured by connecting a rotameter (which has been calibrated with an NBS traceabl^ tjubble meter) to the inlet of the tandem charcoal sampling tube; the initial flow is then recorded. The shield to protect frc m ^ight and rain is placed over the adsorp- tion tubes, and samplin g is continued for 24 0.25 hours. At the end of the sampling period, the time, final vacuum, and flow rate are read and reoor led as before. Samples are then removed from the sampler, plas tic caps are placed on the adsorption tubes, the tubes ark vrapped in aluminum foil, and they are stored in a freezer 4*- '*c or less until laboratory analyses can be performed. One of ev^ry 20 tubes used for field monitoring is retained and returned to the laboratory as a blank. (c) Sample Recovery: The contents of the 150-mg charcoal tube are transferred into a clean, 2-ml vial, and a Teflon serum cap liner is placed on tie vial and secured with a screw cap. By use of a 1-ml, gastight syringe, 0.750 ml of a cold (0C) mixture A-9 VVC 000012460 <. c Figure A-2 Sketch of 24-hour integrated sampler for EDC monitoring. O t^ z io o o o of carbon disulfide and 1-bromohexane is injected through the septum into the vial containing the charcoal. See Section 8(a) for the preparation of this desorption reagent. The vial is placed in an ultrasohic cleaner, which contains ice and water, for 30 minutes. sample, containing the charcoal in contact The with the carbon disulfidp, is then stored at 0C or less until GC separation and analyses are performed. (d) Analyses: Column preconditioning--Before its initial use. the chromatographic column is treated with heat to remove impurities. To do this, a flow of 20 to 30 ml/min of pure helium is established through the column, knd the temperature of the column is raised^ from ambient by 2C/min to 200C. This temperature is maintained for 40 hours. GC/MS bonciitions--The typical operating conditions for the analyses of EDC when specific ion monitor ing is done on a Hewlett-Packard 5992-A analyzer are as follows: Helium - vacuum gauge reads 0.45 atmosphere. Injector temperature - 170C. Oven temperature - 120C isothermal Solvenj: elution time - 5.3 min. Run time H 12.5 min. Electron multiplier voltage - as indicated from the au :otune. Ion masses for EDC - 62, 49, 98, 100, and 102 amu. Ion ma^set for 1-bromohexane - 57, 85. Dwell times - 750.0 ms for ions 62, 49, 57, 85; and 500-0 ms for 98, 100, 102. A-11 VVC 000012462 Select:.ve ion monitoring window sizes 0.10 amu. Amount of CS2 injected - 4 pi. Rete ntion time of EDC - 6.4 min. Ret: ntion time of 1-bromohexane - 9.0 min Sample injection--The first step in the analysis is the injection of the sample into the gas chro matograph. To eliminate difficulties arising from blovbaek or distillation within the syringe nee dle, the solvent flush injection technique should be used. A 10-pl syringe is flushed with solvent several times to wet the barrel and plunger, then 1 pi cf pure CS2 is drawn into the syringe. The needle is removed from the solvent, and the plung er is pulled back about 0.5 pi to separate the solvent flush from the sample; a pocket of air is used ais a marker. The needle is then immersed in the sample, and a 4-pl aliquot is withdrawn. The volume of the needle must be carefully selected, because the sample contained in it will be com pletely injected. After the needle is removed from the sample and before it is injected into the gas chromatograph, the plunger is pulled back 1 pi to minimize evaporation of the sample from the tip of zhe needle. Observe that the sample occupies 3.9 to 4.0 pi in the barrel of the syringe. When duplicate injections of a solution are made, no more; than a 3 percent difference in area can be expected when using the same syringe. Measurement of area--The areas of the EDC and 1-bromohexane peaks are determined by an elec tronic integration system that is capable of determining the area of all ions that are monitor:d at the same retention time. A printout of the area, expressed in integration units, is obtained. The most predominant ion or base peak in zhe mass spectrum of EDC, m/e 62, is selected for quantitation of the EDC. For 1-bromohexane, m/e 85 is selected for quantitation; this ion is not the base peak, but it is less subject to interference from other compounds than the base peak. A-12 vvc 000012463 8. Standards, Calibj -at: Lon, and Analyses (a) Preparation of Desorbing Solution and Standards: 0 Prepare iti< on of desorbina solution (prepared --Jweekly ^dd 5.0 [i 1 of 1-bromohexane into a 250-ml volumel:ri<z flask containing 240 ml CS2 and bring to vol ume with carbon disulfide. Thez concentra tion 0 f t te 1-bromohexane solution is 23.5 ng/pl. 0 Prepare iti<on of stock standard solution (prepared weekly) ^dd 5.0 pi of pure EDC to a 10-ml volu- metric fl ask containing 9.8 ml of the desorbing solution and bring to volume with the desorbing solution. This gives an EDC concentration of 0.628 &9/1 j1. 0 Preparati<on of workinq standard procedure (pre- pared <iai Ly)--Take 20 pi of the stock standard soluti< >n, put it in a 5.0-ml volumetric flask con- rtainin< 4 ,8 ml of the desorbing solution and bring to vo! um* s with the CS2-n-bromohexane desorbing soluti< >n. This gives an EDC concentration of 2.512 i ig/ 11. (b) Calibration 0: the GC/MS system: The GC/MS system is set up according to the conditions described above in 7(d). Before being used, the instrument is autotuned in the manner described in the manufacturer1 s operations manual. Four micro- liters of the working sitandard are injected onto the GC column and analyzed. A resp ons;e ratio, based on the area obtained from the EDC peak (ion 62) and divided by the area obtained from the 1-bromohexane peak (ion 85), is calculated and used to find the concentration of EDC in real samples. The following equation indicates how the res^on^e ratio is obtained: A. Response ratio = =R where = area of the EDC ion in integration units. A2 = area cf the 1-bromohexane ion in integration units. A-13 VVC 000012464 Since R is a ratio instead of an absolute area, variations among injections in the .mount of sample or the detector response will not affect its value. The average response ratio is determined; and any single res ?or se ratio must not deviate from the average by more than 5 :per cent. If a response ratio is beyond this limit, an error has occurred in the injection of the sample or in the preparation of th 2 working standard or there is a problem in the instrument that must be corrected. (c) Analyses of Samples: Four microliters are withdrawn from the desorbed s ample, containing the contents of the charcoal tube and the 750 Ml of CS^-l-bromohexane used as the eluting reagent. The areas of the mass 62 ions from EDC and mass 85 ions from 1-bromohexane a:re recorded. An injection of 4 pi of a standard, which is m the range of the samples being analyzed, is made into every tenth sample. The response ratio is calculated and compared with ^he original calibration, as in 8(b). A blank tube, prepared as described in 7(b), is analyzed in the same manner. Any area Resulting from the specific ion of mass 62 is recorded. 9. Calculations (a) uncorrected Sample Volume: The volume of air sample is not corrected to Stlan4&rd Temperature and Pressure because of the uncertainty associate: d with 24-hour average temperature and atmospheric pressure changes during sampling. The air sample volume taken for arialj sis is determined as follows: A-14 VVC 000012^65 Fi + F: Vm = x T x 10 -6 where: Vm = the volume of as sampled (uncorrected), rtf F^ = the measured fl ow rate before sampling, ml/min = the measured flow rate after sampling, ml/min T = the sampling time, min (b) Ethylene Di^hl^ride Concentration: Calculation of the EDC collected on the adsorption tube. From th e integrated areas for ion masses 62 and 85, as discuss ed in 8(c), the EDC content collected on the charcoal tube and corrected for the blank is cal- culated as fol Lows : W EDC (R spL Rblk> R xCxV :3td where: WEDC = Welght ED 2 1 n nanograms R spl R blk R std area SDC area 1-brbmohexane from samPle area ED area 1-br omo hexane from blank area ED C area 1-br omo hexane from standard C = concentra tio n of standard in ng/pl V = volume o f C2S2 and 1-bromohexane mixture used to aesorb the charcoal is 750 pi undler normal conditions). desorbing solution tube (this volume A-15 vvc 000012*66 Calculation of Epc concentration.* The concentration of EDC as p g/m in the sampled ambient air is cal- culated as fdllows: c =^ x 10 -3 EDC vm where: Cpnr is the colice :itration of EDC in the ambient air sampled, EDC in pg/m3 WEDC is the weight of EDC, corrected for the blank, in ng Vm is the voium 2 of air sampled under sampling conditions. in m3 If desired, the concentration of EDC may be calculated as parts per billion EDC; ppb = pg/m3 x 0.247 10. Effects of Storac e. Few data are available on the storage of charcoal tubes cont aining adsorbed EDC; however, some evidence indicates that compou nds with similar chemical characteristics are adversely affected by strong sunlight and heat. Tubes should be stored in a d^rk place and at a low temperature. Carbon disulfide-l-bromohekan e solutions of EDC in the pg/m3 range are stable for at least one month if they are refrigerated in a sealed serum bottle w ith minimum head space. No information is available on the sto rage of samples containing other active substances commonly: fc und in ambient air. The overall method fficiency has been determined to be 90 + 10 percent A correct! on factor of 1.1 can be used if desired, CEDC multiplied py 1.1 to obtain the concentration corrected for method efficileni y. For levels in excess of 10 pg/m^, the backup adsorptiop ti(ibe can be analyzed and the concentration added to the result^ from the first adsorption tube. In this case, no correction factor is recommended. A-16 ooooiz^61 VC BIELIOGRAPHY FOR APPENDIX A American Petroleum l| istitute, by Gulf Science and Technology Company. Method for | .he Determination of Benzene in Ambient Air (Integrated Sampling)J Pittsburgh, July 1977. Levadie, B., and S. Taken on Charcoal. Analytical Chemistry, MaJcAskill. Analysis of Organic Solvents Tube Samples by a Simplified Technique. 48Jl, p. 76. January 1976. Lodge, J.P., et al Th Orifice in Air Sampling 16:4, pp. 197-200. 1966 Use of Hypodermic Needles as Critical J. Air Pollution Control Association, NIOSH Method S 122 for the Determination of Ethylene Dichloride, NIOSH Manual of Analy^ ical Methods, Part II. 2nd edition. DHEW Publication No. 77-15 -B, April 1977. PEDCo Environmental, ilnc . Monitoring System for the Collection and Analyses of Ambient Levels of Benzene in Urban Atmosphere. Contract No. 68-02-2722, Task No. 7. January 1979. PEDCo Environmental, Inc. Dichloride in Ambient Aib. 8. December 1978. Sampling and Analyses for Ethylene EPA Contract No. 68-02-2722, Task No. Vinyl Chloride Monitor ing Near the B.F. Goodrich Chemical Company in Louisville, Kentuc Icy.I Region IV, U.S. Environmental Protection Agency, Surveille nci and Analysis Division, Athens, Georgia. EPA Contract No. 68-02 -1^75, Task No. 20. June 24, 1974. Yasuda, S.K., and ElD. Lounghron. Air Sampling Methods for Tetrachloroethane and Other Related Chlorinated Hydrocarbons. Journal of Chromatogr4phy, 137:2, pp. 283-292. 1977. A-17 VVC 000012468 APPENDIX B NE ti: OROLOGICAL DATA FROM CAL VEILT CITY, KENTUCKY, STUDY B-l VVC 000012469 HOUR 00 01 02 03 04 05 06 07 08 09 10 11 12 13 14 15 16 17 18 19 20 21 22 23 METEOROLOGICAL DATA WIND Speed, n ph Direction, Temp., F Rel. Hum., % 2 120 72 90 2 150 76 88 2 150 76 83 1 - 80 76 2 360 83 67 2 360 85 62 2 120 85 63 2 140 86 60 2 140 87 55 1 - 86 56 0 - 85 64 0 - 81 78 0 - 77 91 0 - 75 94 0 - 74 95 0 - 73 95 LOCATION: Calvert Cit y, Ky. DATE 8/26/78 B-2 VV,C 000012^ me: TEOROLOGICAL DATA HOUR 00 01 02 03 04 05 06 07 08 09 10 11 12 13 14 15 16 17 18 19 20 21 22 23 Speed, mph 0 0 0 0 0 0 0 0 2 2 2 3 3 4 6 5 6 5 3 2 1 1 2 2 D Direction, 180 200 220 210 210 240 220 220 220 220 230 250 190 180 * Recorder malfunction LOCATION: Calvert Ci 1;Y' Temp., F 73 73 72 72 72 72 72 73 76 80 84 87 88 90 90 90 90 89 87 83 81 79 78 76 DATE > Rel. Hum., % 95 93 94 93 94 94 94 91 85 76 65 61 57 54 52 51 52 * * * * * 8/27/78 vvc 000012471 B-3 METEOROLOGICAL DATA HOUR 00 01 02 03 04 05 06 07 08 09 10 11 12 13 14 15 16 17 18 19 20 21 22 23 W IND Speed, mi h Direction, 2 180 0002 190 4 210 4 210 4 220 6 220 6 240 6 230 7 220 7 220 6 230 10 290 11_ 2 230 6 280 8 290 1 1_ 2 250 2 260 * Recorder malfunction LOCATION: Calvert City, Ky, Temp., F 76 73 72 71 72 73 72 74 76 79 82 84 85 87 84 79 83 84 82 77 74 73 72 71 Re1. Hum., % i*e * * * * * * * * 76 71 67 63 60 59 76 82 72 66 71 80 87 91 95 DATE 8/28/78 B-4 00001247Z HOUR 00 01 02 03 04 05 06 07 08 09 10 11 12 13 14 15 16 17 18 19 20 21 22 23 METEOROLOGICAL DATA WII4D Speed, mph Direction, 2 270 110012 210 2 210 2 210 Temp., F 70 70 70 70 70 70 70 70 70 Rel. Hum., % 95 96 97 97 97 97 97 96 96 LOCATION: Calvert Cj-ty ' Ky- DATE fl/?q/7R B-5 vvc 000012473 HOUR 00 01 02 03 04 05 06 07 08 09 10 11 12 13 14 15 16 17 18 19 20 21 22 23 METEOROLOGICAL DATA W IND Speed, mt h Direction, 0-- 00000000002 110 2 120 2 130 2 130 1116 080 3 080 0-- 000- Temp., F 69 69 68 67 66 66 66 66 67 68 69 69 69 70 74 75 78 79 80 78 74 72 71 69 Rel. Hum., % 93 90 90 90 93 95 95 95 94 93 93 92 88 86 84 82 81 78 74 75 76 75 79 84 LOCATION: Calvert cit^ KY- DATE 9/9/78 B-6 VVC 000012474 HOUR 00 01 02 03 04 05 06 07 08 09 10 11 12 13 14 15 16 17 18 19 20 21 22 23 ETEOROLOGICAL DATA I WIND Speed, mpH Direction, 0_ 0 0 0 0 0_ 0 0_ 0 0 0 1 2 120 3 no 1 1_ 1_ 0 0 0 0 0 0 0_ Temp., F 69 68 67 67 66 65 65 66 68 72 78 80 83 84 85 85 85 84 82 79 73 72 69 69 Rel. Hum., % 87 88 91 91 91 90 88 86 80 76 73 70 63 61 59 56 51 52 59 67 84 90 94 95 LOCATION: Calvert City, DATE 9/10/78 B-7 VVC 000012475 HOUR 00 01 02 03 04 05 06 07 08 09 10 11 12 13 14 15 16 17 18 19 20 21 22 23 METEOROLOGICAL DATA W IND Speed, m^: h Direction, 0-- 000000-- 1-- 2 210 1 200 2 170 3 160 3 160 5 150 4 200 7 230 7 230 7 230 6 240 4 240 3 260 1 200 3 200 1 190 Temp., F 67 67 66 65 65 65 64 64 67 70 75 78 80 80 82 83 82 79 74 69 69 69 68 67 Rel. Hum., % 95 95 95 95 95 95 95 95 94 89 83 76 67 60 59 56 51 56 67 83 95 94 94 94 LOCATION: Calvert Cit -y, Ky. DATE 9/11/78 B-8 VVC ooooiz^76 HOUR 00 01 02 03 04 05 06 07 08 09 10 11 12 13 14 15 16 17 18 19 20 21 22 23 METEOROLOGICAL DATA 1 Speed, mph 0 1 1 1 0 0 0 0 0 0 0 4 4 5 5 5 3 1 0 1 2 2 1 0 D Direction, - 220 210 210 220 220 210 190 190 - Temp., F 66 66 66 66 67 67 67 67 68 68 69 70 71 73 77 79 80 80 78 77 75 75 73 72 Rel. Hum., % 95 95 94 94 94 93 94 95 94 93 91 93 87 88 78 71 70 69 73 80 87 89 88 92 LOCATION: Calvert Ci ty f Ky. PATE 9/12/78 B-9 VVC 000012477 METEOROLOGICAL DATA HOUR 00 01 02 03 04 05 06 07 08 09 10 11 12 13 14 15 16 17 18 19 20 21 22 23 W IND Speed, mpii Direction, 9 200 7 200 7 200 4 200 6 220 7 230 6 230 7 230 3 200 4 210 5 210 5 250 4 230 4 230 5 240 6 220 3 200 3 180 1- 4 180 4 180 5 190 8 200 10 180 Temp., F 70 70 69 69 68 67 67 68 70 73 76 78 79 76 77 79 78 77 77 75 74 73 72 72 Rel. Hum., % 95 95 94 94 96 96 96 96 94 91 85 78 73 71 82 80 73 73 75 76 80 77 79 85 NOTE: 0.75" rain fr<bm 2000 to 2400 hours. LOCATION: Calvert C itV , Ky. PATE-...... 9/13/78 B--10 vvc 0000l2^78 METEOROLOGICAL DATA HOUR 00 01 02 03 04 05 06 07 08 09 10 11 12 13 14 15 16 17 18 19 20 21 22 23 Wit'ID Speed, mph Direction, 0 9 200 7 200 7 210 4 210 7 220 8 230 7 230 7 230 6 240 8 250 9 250 6 250 4 220 7 240 6 270 5 260 6 270 5 280 2 280 00000- Temp., F 71 71 70 69 69 69 70 70 71 72 74 75 77 77 78 78 79 81 81 80 76 73 70 68 NOTE: 2.3" rain, from 0000 to 0300 hours. LOCATION: Calvert Ci Ky. DATE Re1. Hum., % 88 89 91 92 91 91 91 91 91 90 87 84 80 79 78 77 77 72 67 64 74 85 94 96 9/14/78 B-ll VVC 000012479 HOUR 00 01 02 03 04 05 06 07 08 09 10 11 12 13 14 15 16 17 18 19 20 21 22 23 METEOROLOGICAL DATA Speed, rci] 0 0 0 0 0 2 0 0 0 1 2 2 2 2 1 2 3 0 0 0 0 0 0 1 tfIND Direction, - 190 - 180 180 200 210 - 290 280 - Temp., F 67 67 67 66 65 64 64 64 65 66 70 71 76 78 79 80 81 82 81 76 70 69 67 66 Rel. Hum., % 96 96 96 96 96 96 96 96 96 96 94 91 84 76 74 74 71 63 63 64 85 93 95 95 LOCATION: Calvert Cit|y> Ky- DATE 9/15/78 B-12 o0ooi^a0 N/'Jt METEOROLOGICAL DATA HOUR 00 01 02 03 04 05 06 07 08 09 10 11 12 13 14 15 16 17 18 19 20 21 22 23 W IN 0 Speed, mph Direction, 2 230 2 230 3 220 10111110002 240 3 270 5 270 5 250 6 260 2 240 0002 190 2 210 NOTE: 0.01" rain. LOCATIC)N: Calvert Cit Ll. Ky. Temp., F DATE Rel. Hum., % 9/16/78 B-13 0000lz^81 XMt HOUR 00 01 02 03 04 05 06 07 08 09 10 11 12 13 14 15 16 17 18 19 20 21 22 23 METEOROLOGICAL DATA WIND Speed, m ph Direction, 3 220 3 210 3 210 2 190 1000- 3 230 5 230 4 230 5 240 5 240 5 240 6 230 5 230 5 210 4 200 3 200 11-- 13 200 3 210 Temp. , F 69 68 67 67 66 65 65 65 68 72 76 81 83 84 85 86 86 85 83 81 77 75 75 75 Rel. Hum., % 94 95 95 95 95 95 95 95 95 91 82 73 65 56 49 47 47 53 59 63 69 74 82 82 LOCATION: Calvert City, Ky. DATE 9/17/78 Wc 000012482 HOUR 00 01 02 03 04 05 06 07 08 09 10 11 12 13 14 15 16 17 18 19 20 21 22 23 m: :TEOROLOGICAL DATA WlfcD Speed, mph| Direction, 10 180 10 190 7 180 5 71 180 170 8 170 10 l 180 13 1 200 10 200 13 |, 200 9 | 210 12 210 10 210 10 210 10 i 230 12 1 220 81 4 220 200 5 180 5 170 4 160 4 160 01 5 170 Temp., F 75 75 75 74 73 72 71 71 74 76 80 81 84 85 86 87 87 87 85 82 78 74 73 72 Rel. Hum., % 84 86 88 89 89 91 94 94 93 90 83 78 69 64 67 63 58 57 55 58 65 77 89 88 LOCATION: Calvert City, Ky. B-15 DATE 9/18/78 0O0012*83 MVC APPENDIX C METE OROLOGICAL DATA FROM LAKE CH &RLES, LOUISIANA, STUDY C-l HOUR 00 01 02 03 04 05 06 07 08 09 10 11 12 13 14 15 16 17 18 19 20 21 22 23 METEOROLOGICAL DATA W IND Speed, mph Direction, 4 010 3 020 4 020 5 020 6 020 5 020 7 020 7 020 4 020 7 020 7 020 7 030 4 030 5 030 5 030 7 030 6 020 3 030 3 030 3 010 5 330 5 340 4 010 6 020 Temp., F 73 72 71 69 69 68 67 67 72 76 80 82 83 82 82 83 83 81 77 74 70 71 70 70 Rel. Hum., % 81 78 78 80 72 71 71 68 50 39 32 31 32 37 35 35 35 39 49 58 73 66 65 65 LOCATION: Lake Charles, La. DATE_______q /^a/iq C-2 VVC 0000X2^05 HOUR 00 01 02 03 04 05 06 07 08 09 10 11 12 13 14 15 16 17 18 19 20 21 22 23 M ETE0R0L0GICAL DATA | WI Speed, mph Direction, 6 5 1 020 3 020 5 , 020 5 | 020 5 020 4 020 5 020 6 010 4 020 7 020 5 030 4 040 6 040 5i 030 5 1 040 4 ,. 030 4 , 030 4 1 040 3 030 3 010 5 330 4 360 3 020 5 020 Temp., F 69 67 66 66 65 64 63 64 67 68 74 78 82 82 82 83 84 82 78 73 71 72 74 73 Rel. Hum., % 64 68 67 67 66 66 65 62 50 51 45 43 41 37 37 35 28 35 47 67 74 70 62 67 LOCATION: Lake Charles,! La. DATE 9/25/78 C-3 vvc 000012^8^ HOUR 00 01 02 03 04 05 06 07 08 09 10 11 12 13 14 15 16 17 18 19 20 21 22 23 METEOROLOGICAL DATA WIND Speed, n ph Direction, 4 020 4 020 5 010 4 020 4 010 4 020 5 020 6 020 4 020 4 020 6 050 5 040 4 050 4 090 3 030 3 020 2 030 2 010 003 020 5 020 5 020 4 020 Temp., F 73 71 71 68 67 67 67 67 69 74 78 81 83 84 85 85 85 83 79 77 76 77 76 75 Rel. Hum., % 67 60 60 64 68 68 68 68 64 55 57 52 50 48 43 40 43 50 60 68 71 68 71 70 LOCATION: Lake Charles, La. DATE 9/26/78 C-4 ooooiz^7 yVC HOUR 00 01 02 03 04 05 06 07 08 09 10 11 12 13 14 15 16 17 18 19 20 21 22 23 METEOROLOGICAL DATA WIK D Speed, mph | Direction, 3 010 1 360 2 010 2 340 3 020 03 010 5 350 7 010 6 010 7 020 7 010 10 020 7 030 7 020 8 350 8 350 5 350 7 350 6 340 6 340 7 350 7 360 5 010 Temp., F 74 73 69 69 69 70 69 69 72 74 77 81 81 81 81 81 80 79 77 74 73 72 72 72 Rel. Hum., % 62 61 76 76 76 73 76 76 66 62 64 56 56 56 56 56 54 50 55 59 54 58 58 58 LOCATION: Lake Chari 5S, La DATE 9/27/78 C-5 VVC 00001Z488 METEOROLOGICAL DATA HOUR 00 01 02 03 04 05 06 07 08 09 10 11 12 13 14 15 16 17 18 19 20 21 22 23 WIND Speed, m; oh Direction, 0 5 360 6 340 6 350 6 360 5 340 7 010 5 010 7 010 11 360 9 020 10 030 11 030 12 030 9 030 9 020 8 020 6 020 5 020 4 020 3 020 4 030 3 010 5 030 6 04 0 Temp., F 72 71 71 70 70 70 70 70 72 73 74 75 75 73 72 70 70 69 68 67 67 67 67 67 NOTE: 0 .02" rain fi om 0400 to 0600 hours. LOCATIC)N: Lake Ch irl -s. La. DATE Rel. Hum., % 58 66 66 70 70 70 73 78 70 67 66 60 55 70 62 73 80 85 80 85 85 85 85 85 9/28/78 C-6 VVC 0000124a9 HOUR 00 01 02 03 04 05 06 07 08 09 10 11 12 13 14 15 16 17 18 19 20 21 22 23 METEOROLOGICAL DATA Speed# mph 5 4 4 5 5 6 5 7 7 7 8 7 8 6 6 6 0 0 0 0 0 0 0 0 D Direction, 030 010 020 020 020 010 010 020 020 030 050 100 100 110 090 090 - Temp., F 67 67 67 67 67 67 67 67 69 73 76 78 80 80 81 81 81 80 75 71 70 69 69 69 Rel. Hum., % 85 85 85 85 85 85 85 80 72 63 53 50 45 39 37 40 40 41 55 68 72 76 76 80 LOCATION: Lake Chari ss, La. DATE 9/29/78 C-7 VVC 000012*' HOUR 00 01 02 03 04 05 06 07 08 09 10 11 12 13 14 15 16 17 18 19 20 21 22 23 METEOROLOGICAL DATA W IND Speed, mph Direction, 000003 020 04 020 5 020 5 020 5 040 6 030 5 030 2 030 2 360 3 030 4 030 2 030 000-- 0-- 00- Temp., F 68 68 70 70 70 69 68 67 72 75 79 81 83 84 84 85 85 84 78 74 72 69 69 68 Rel. Hum., % 87 87 78 78 78 80 87 85 67 55 43 44 39 37 32 29 29 30 46 59 73 80 85 87 LOCATION: Lake Cha rle s. La. DATE 9/30/78 C-8 vv c OOOOl**91 HOUR 00 01 02 03 04 05 06 07 08 09 10 11 12 13 14 15 16 17 18 19 20 21 22 23 METEOROLOGICAL DATA w IND Speed, mp 1 Direction, 0000000003 360 2 020 2 010 2 060 2 070 3 100 000000000- Temp., F 68 67 65 65 64 64 64 65 70 77 79 82 84 86 85 87 86 83 77 74 74 72 70 70 - Rel. Hum., % 87 85 90 90 90 90 90 85 80 64 50 40 33 29 28 25 26 31 64 74 74 83 90 90 LOCATION: Lake Chai *les , La DATE 10/1/78 C-9 VVC 000012492 HOUR 00 01 02 03 04 05 06 07 08 09 10 11 12 13 14 15 16 17 18 19 20 21 22 23 METEOROLOGICAL DATA WIND Speed, mi ih Direction, 000000000- 1- 3 340 2 240 1- 2 160 2 160 4 170 4 190 3 200 2 170 2 180 00- 00- Temp., F 69 69 67 67 67 67 67 67 70 76 81 82 83 85 85 85 83 80 76 72 71 70 70 69 Rel. Hum., % 94 90 95 95 90 90 90 85 86 63 52 50 44 36 34 34 41 55 68 83 85 90 86 90 LOCATION: Lake Cha rlc s , La. DATE 10/2/78 C-10 vvc ooooi^93 HOUR 00 01 02 03 04 05 06 07 08 09 10 11 12 13 14 15 16 17 18 19 20 21 22 23 METEOROLOGICAL DATA w IND Speed, mp! Direction, 0 000000000001112 140 103 170 000000- Temp., F 68 67 67 67 66 67 67 68 71 73 78 80 82 83 84 82 78 77 74 72 72 71 69 68 Rel. Hum., % 90 90 90 90 90 85 85 87 88 82 68 55 43 43 36 46 60 64 74 80 78 86 85 90 LOCATION: Lake Cha rle s , La. DATE 10/3/78 C-ll vvc 000012494 HOUR 00 01 02 03 04 05 06 07 08 09 10 11 12 13 14 15 16 17 18 19 20 21 22 23 METEOROLOGICAL DATA w IND Speed, mf h Direction, 03 340 003 020 2 020 3 030 3 030 4 060 6 050 5 050 5 050 2 090 4 100 13 090 00000000- Temp., F 68 68 68 67 66 67 67 66 67 72 74 77 80 82 83 84 84 83 78 76 74 72 71 69 Rel. Hum., % 90 87 87 90 90 90 85 90 85 61 55 44 41 40 40 39 36 34 52 68 74 83 88 90 LOCATION: Lake Chai lei3, La. DATE 10/4/78 C-12 VVC 000012^^5 HOUR 00 01 02 03 04 05 06 07 08 09 10 11 12 13 14 15 16 17 18 19 20 21 22 23 METEOROLOGICAL DATA W IND Speed, mp 1 Direction, 000_ 12 340 1102 350 3 030 12 130 4 060 12 320 3 180 1112 250 0000- Temp., F 69 68 67 67 67 67 67 67 70 76 81 82 84 84 87 87 84 82 77 75 75 73 72 72 Re1. Hum., % 90 90 90 90 90 90 90 85 86 70 55 50 39 36 30 30 41 49 70 79 79 86 86 86 LOCATION: Lake Charles, La. DATE 10/5/78 C-13 vvc ooooiz^6 HOUR 00 01 02 03 04 05 06 07 08 09 10 11 12 13 14 15 16 17 18 19 20 21 22 23 METEOROLOGICAL DATA V IND Speed, mph Direction, 00012 340 1102 350 3 030 12 130 4 060 1- 2 320 3 180 11- 12 250 0000- Temp., F 69 68 67 67 67 67 67 67 70 76 81 82 84 84 87 87 84 82 77 75 75 73 72 72 Rel. Hum., % 90 90 90 90 90 90 90 85 86 70 55 50 39 36 30 30 41 49 70 79 79 86 86 B6 LOCATION: Lake Cha :le s, La. DATE 10/5/78 C-14 VVC 000012497 APPENDIX D (METEOROLOGICAL DATA FROM NE^W dRLEANS , LOUISIANA, STUDY HOUR 00 01 02 03 04 05 06 07 08 09 10 11 12 13 14 15 16 17 18 19 20 21 22 23 METEOROLOGICAL DATA WIND Speed, mF h Direction, 3 080 05 360 5 020 6 020 6 020 8 020 4 010 6 030 7 030 8 030 7 040 5 020 7 030 8 030 8 030 8 060 7 110 3 110 2 120 2 120 000- Temp., F 64 63 62 62 63 63 65 65 68 69 71 73 75 77 78 78 77 76 74 73 71 70 69 69 Rel. Hum., % 83 80 74 67 63 59 64 49 46 45 48 51 56 59 65 67 72 75 78 80 83 85 87 88 LOCATION: New Orle ans , La DATE 10/10/78 D-2 VVC 000012*" HOUR 00 01 02 03 04 05 06 07 08 09 10 11 12 13 14 15 16 17 18 19 20 21 22 23 Meteorological data W][ND Speed, mpl Direction, 000002 360 103 030 7 030 6 030 6 030 6 030 6 030 5 040 5 010 4 110 5 120 5 120 5 120 4 120 4 120 3 120 2 120 Temp., F 68 68 67 66 66 66 66 67 68 68 68 75 85 87 88 88 87 86 83 82 80 79 78 78 Rel. Hum., % 88 89 89 89 89 89 89 88 87 86 84 81 76 72 66 64 66 69 75 81 83 84 85 86 LOCATION: New Orleans,. La. DATE 10/11/78 D-3 VVC 000012500 HOUR 00 01 02 03 04 05 06 07 08 09 10 11 12 13 14 15 16 17 18 19 20 21 22 23 METEOROLOGICAL DATA WIND Speed, mph Direction, 3 120 2 120 2 120 3 110 2 100 2 100 2 100 2 100 3 100 3 130 7 120 8 130 5 140 8 360 8 360 4 050 7 120 8 110 4 120 4 120 4 120 3 120 2 120 2 120 Temp., F 78 77 77 76 76 76 76 77 77 80 86 89 90 91 87 87 89 89 87 81 80 79 79 78 Rel. Hum., % 86 86 86 86 86 86 86 86 83 74 61 53 51 56 66 68 70 69 74 80 84 85 86 86 LOCATION: New Orleans,, La. D-4 DATE 10/12/78 ooooi^01 HOUR 00 01 02 03 04 05 06 07 08 09 10 11 12 13 14 15 16 17 18 19 20 21 22 23 METEOROLOGICAL DATA tfIND Speed, m ah Direction, 00000004 020 3 030 2 100 3 360 5 360 3 360 5 020 7 360 5 330 3 320 0000010 350 13 350 Temp., F 77 77 75 75 73 72 71 71 74 78 83 85 87 88 89 90 87 85 80 76 73 72 72 72 - Re1. Hum., % 86 87 87 87 87 87 87 87 87 84 75 69 64 57 54 48 48 60 72 73 76 78 78 76 LOCATION: New Orle ans , La. DATE 10/13/78 D-5 WC 000012502 METEOROLOGICAL DATA HOUR 00 01 02 03 04 05 06 07 08 09 10 11 12 13 14 15 16 17 18 19 20 21 22 23 blND Speed, nr Dh Direction, 0 14 13 15 15 14 16 16 -----------------1--6------ 1----17 ! 20 19 ' 17 14 ' 14 1 1 16 | 15 15 1 15 1 1 12 1 9 ,1 7 7 12 1 13 350 350 350 360 360 010 010 010 010 010 010 010 010 360 360 350 350 350 360 350 340 350 010 010 Temp., F 68 67 64 62 62 61 61 61 61 62 65 64 65 66 66 66 64 60 57 53 53 54 54 54 Rel. Hum., % 74 74 75 70 63 61 57 53 52 50 47 38 36 28 28 27 26 30 38 45 60 63 60 54 LOCATION: New Orle ans , La. DATE 10/14/78 D-6 cyQf'b 0ooov2 HOUR 00 01 02 03 04 05 06 07 08 09 10 11 12 13 14 15 16 17 18 19 20 21 22 23 C4ETEOROLOGICAL DATA w IND Speed, mp 1 Direction, 0 13 010 12 010 9 010 6 020 2 310 2 320 4 330 4 330 0- 7 030 9 040 7 060 7 060 5 050 4 030 2 330 0- 0- 0- 1 21 - 200 2 240 4 250 4 240 Temp., F 53 53 52 48 43 42 44 48 58 61 63 64 65 66 67 67 67 62 57 55 55 55 55 54 Rel. Hum., % 55 57 59 60 80 94 95 98 70 46 35 33 30 30 29 27 27 32 48 59 70 73 78 82 LOCATION: New Or leeins La. DATE 10/15/78 D-7 vvc 0000125^ HOUR 00 01 02 03 04 05 06 07 08 09 10 11 12 13 14 15 16 17 18 19 20 21 22 23 METEOROLOGICAL DATA l WIND Speed, mph Direction, 2i 2 i1 2i 0i 0 0, 0i 0, 9 11 91 7| 8| 91 9 ', 8' 6 7 3 3 4 7 12 13 12 220 250 240 290 290 310 270 290 290 290 300 320 330 330 340 350 360 010 010 Temp., F 53 52 51 49 48 48 49 52 60 63 70 72 75 77 78 78 77 74 66 61 61 61 60 58 Rel. Hum., % 87 89 93 95 97 97 97 96 92 80 57 44 33 27 27 28 29 35 57 70 75 64 50 52 LOCATION: New Orle ans La. DATE 10/16/78 D-B VVC 000012505 HOUR 00 01 02 03 04 05 06 07 08 09 10 11 12 13 14 15 16 17 18 19 20 21 22 23 METEOROLOGICAL DATA ;IND Speed, mp^l Direction, 11 010 12 020 11 030 11 030 11 040 10 040 10 050 10 060 11 060 11 050 11 050 10 050 10 030 10 040 8 050 8 040 5 350 4 310 000 0_ 0_ 0-- Temp., F 56 56 57 57 56 55 54 55 57 58 59 61 63 63 64 64 64 62 58 56 55 54 52 51 Rel. Hum., % 55 57 58 57 57 59 62 64 62 60 57 56 52 47 43 43 42 45 59 65 87 96 99 99 LOCATION: New Orlea ns, La. DATE 10/17/78 D-9 VVC 000012506 METEOROLOGICAL DATA _ . ------- -- -- - -- -- _ -- -- HOUR 1 WIND Speed, rr^ph i Direction, Temp., F 00 1 - 01 01 -- 02 11 - 03 5 020 04 6 010 05 5 010 06 5 020 07 6 010 08 6 020 09 8 030 10 8 040 11 8 030 12 9 040 13 9 040 14 8 050 15 9 060 16 8 070 17 61 100 18 41 110 19 31 120 20 i 0 21 0 22 1 _ 23 1 I - 50 52 50 53 57 55 54 55 56 60 65 67 69 71 74 75 75 75 75 74 71 70 68 67 Rel. Hum., % 100 94 93 95 89 79 87 85 88 81 72 69 68 67 65 65 68 66 65 67 71 75 80 85 'I LOCATION: New Orleans,, La. DATE 10/18/78 ------------------------- D-10 00001Z57 \fVC HOUR 00 01 02 03 04 05 06 07 08 09 10 11 12 13 14 15 16 17 18 19 20 21 22 23 METEOROLOGICAL DATA W] :nd Speed, mph Direction, 2 010 2 010 2 010 2 350 4 350 4 330 4 360 3 360 5 010 8 020 7 010 8 010 7 360 5 360 8 350 7 340 3 340 12 280 01110- Temp., F 65 64 64 66 66 66 67 67 69 70 73 75 76 77 78 79 79 77 70 66 63 61 60 59 Rel. Hum., % 94 98 96 92 95 98 99 99 99 99 98 55 46 46 46 43 43 49 70 81 94 93 95 95 LOCATION: New Orleans La. DATE 10/19/78 D-11 VVC 000012508 Lake Charles VCM Plant CERTIFIED MAIL #3156E6 October 29, 1979 (CC'fK Conoco Chemicals Company A Division of Conoco Inc. P 0. Box 605 Westlake. Louisiana 70669 (318) 491-521 1 Richard Goudeau Louisiana Wildlife and Fisheries 1213 Lakeshore Drive Lake Charles, LA 70605 Dear Mr. Goudeau, Attached is the info Ration you requested during your plant inspection on October 17, 1979. Tf e information includes three strip charts and integrator readings for the waste treatment system effluent flow. Chart 1 includes temp erafcure and flow information for the waste treatment system effluent, Tie waste treatment system effluent is sampled at discharge point 2C 1. Chart 2 includes pH and dissolved oxygen content information also gath erei at discharge point 201. Chart 3 contains acid neutralization pit effluent flow information and effluent temperature and pH information for th e combined waste streams. The neutralization pit effluent flow is meas ured at discharge point 101 and the combined waste streams information s collected at discharge point 001. During the duration of the plant inspection, there was no measurable acid neutralization pit effluent flow. The (discharge point identification numbers are per the discharge point identifiration numbers listed in the VCM Plant's NPDES Permit of August 26, 1979. Integrator readings were also recorded. The integrator reading for the waste treatment system at discharge point 201 was 569,393 x 100 gallons at 10:40 on October 18, 1979. Should any additional information be required, please advise. Sincerely, Gary Foshee Chief Process Engineer br cc: R. A. LaFleur bcc: REL,CRH,HJN,MAF,RLH,GLF,PLF,JOG,JWW (JCL. VVC 000012509 /$ -/<?- 79 UtL ->>r2,. L A VJ <. a. -g: rkiLg._____ _o______:_______ ^ / : II - - ros ! ' /? 5 ~ ' `i '' ' " I 3. <? 2 * j? " ! ,1 i ` 1j - 'i '( '- .-. :-v.'- .-* ' rtnnftl25X6 * Y V Q0 . ,[i . t - - - , j: ;' . v..- . -r ' V. * - ... .-4- i . - ` -- " '- .' "' ' ' * -' -V ?%'.. ^**'.S-- .4 c ; Jim DeEiern^rdi 3 'C. C (Conoco) yisjJldozu /,// 7/ 7 f rr ^*T_ pcs y {Jcw/tf: VVC 000012517 Interoffice Communication To J. A. DeBernardt Frorq mH.(/Garrison 6,6 Date September 18, 1379 Subject ERA Final Rule Regarding PCBs Cconoco) RECEIVED OCT 22 raTT The purpose of this letter is to summarize the ftnal EPA rule regarding PCBs and to document the VCM PI ant's current compliance position and policies to con- * trol compliance. The basi s for discussfon is the Final Rule for Polychlorinated Biphenyls [PCB's] Manufacturing, Processing, Distribution in Commerce, and Use Prohibitions published on May 31, 1979. in the Federal Register [44 FR 31514) by the U. S. Environmental Protection Agency. Also a publication of questions and answers to help meet the r equirements of the new rule which was recently prepared by the Industry Assistance Office and Office of Toxic Substances in the U. S. Environmental Protection Agency was used. Basically, the VCM Plant i s most affected with the rules governing transformers. The only PCB capacitor [BL -301 motor] was replaced during the last turnaround [February, 1979) and dispo sed in accordance with the EPA regulations in May, 1979, through Chemical Waste Man agement Incorporated. Transformers are categorized by the rule as PCB Transforme rs [contain greater than 500 ppm PCB), PCB-Contaminated Transformers [contain betw een 50 ppm and 500 ppm PCB), and Non-PCB Transformers (contain less than 50 ppm PCB). All of our transformers fall in the PCB-Contaminated category. __ Attached is an'up-to-date nsUliy ul tronsfennei s til the VCM Plant. This list should be updated if additions of transformers are made. The final rule appears to have been designated to include most transformers in the PCB-Contaminated Trans former category in order to minimize expenses and simplify requirements [and probably enforcement] for servicing, disposal, labeling, and use. Transformers can be reclassified as a Non-PCB Transformer if its dielectric fluid has been tested or dtherwise verified to contain less than 50 ppm PCB; however, there is very li ttle incentive to do so since actions required by the Rule are practically the same for PCB-Contaminated Transformers and for Non-PCB Transformers. A file has been set up to contain all documents related to the plant's compliance with the PCB regulations, This file will he kept with the other EPA files and will be maintained in a si milar manner. The following paragraphs Retail actions and responsibilities with regard to the servicing, disposal, spill s, testing, labeling, and recordkeeping requirements as it pertains to PCB-Contami nated Transformers in the VCM Plant: SERVICING: PCB-Contaminated Transformers are subject to no restrictions on servicing [.including rebut!di ng] or coil and casing disposal, except that after July 1, 1979, servicing of PCB-Contaminated Transformers must be performed either by the owner or operator c r by someone who has an exemption from the EPA, from VVC 000012518 J. A. DeBernardt Page 2 September 18, 1979 SERVICING fContinued) the processing and distribifcjtion bans. Routine servicing of transformers includes such activities as- tes1;ing the dielectric fluid, filtering the fluid, removal of some fluid and then returni ng or replacing it, replacing gaskets, etc. Prior to servicing of transformers or purchasing dielectric fluid, a copy of the EPA exemption must be presented to the Plant Superintendent or Plant Manager for approval of such work. DISPOSAL: Once the fldiid is drained, a PCB-Contaminated transformer can be scrapped or sold for scrap. The PCB-Contaminated fluid, however, must be disposed of in high efficiency boilers, in approved chemical waste landfills, or in Annex I incinerators. Non-liquid PCBs at any concentration such as contaminated rags, absorbent materials, contaminated soils and other solids must be disposed of in Annex II chemical waste landfills. Prior to d sposal of any PCB-Contaminated Transformer, Fluid, or Article, the Plant Superintendent o r Plant Manager's approval must be obtained to ensure that all applicable regulat ons Rave Been reviewed and are being fulfilled. SPILLS: Under the authori ty of TSCA, PCB spills have to be reported whenever the incident poses a substanti al rfsk to human health or the environment. In addition a spill should also be reported when the volume or extent of the spill is unknownsuch as spills that en*:er drainage systems or threaten water courses. As a general rule, spills involving a single capacitor do not have to be reported unless PCBs threaten or enter a wa*:er course. Because of the greater threat to health and the environment, transformer spills should be reported--unless only minor leaks, such as bushing leaks, are involved. Any spilling or leaking should be stopped, con tained and repaired as soon as possible. Reporting of a spill should follow the established policy and procedures outlined by the TSCA plan for the VCM plant. The first priority is :o dontrol the spread of any spill by damming or diking the leak and preventing the sp ill from entering any drainage systems or waterways. Clean-up should begin once the spill is contained. Retrieval of spilled liquid, removal of contaminatedo seilll or debris, and in some cases, special PreCtBs sorbents or special filtration/ carton absorption removal of PCBs from water may be required. TESTING: Testing of t *ans formers to classify them as PCB-Contaminated Transformers, is not necessary. If ?or one reason or another testing is needed, there are specific EPA approved test procbdur es that should Be followed to validate the testing. LABELING: PCB-Contaminated Transformers, containing between 50 and 500 ppm PCB, are not required to be labeled. An unmarked transformer is automatically assumed to be a PCB-Contaminated Transformer, however, if a transformer has no nameplate information and there is a reasonable suspicion that PCBs may be present above 500 ppm--the transformer phoqld be labeled as a PCB Transformer, until the PCB content can be verified. RECORDKEEPING; Other thark the documentation file the VCM Plant has adopted on the subject, recordkeeping is not required by the VCM Plant. Specifically, the Rule re quires that if you own or operate a facility which uses PCBs or PCB Items, or have either stored, you are to keep records of their disposition. This applies to facilities using or stori n? at least 99.4 pounds (45 kilograms] of PCBs in PCB Container(s) one or more PCB Transfb rmers; or 50 or more PCB High or Low Voltage Large Capacitors, These records shall be maintained for at least 5 years after the facility ceases using or storing PCBs or PCB Items in prescribed quantities. VVC 000012519 J. A. DeBernardi Page 3 September 18, 1979 Basically, any purchase Of t ransformer/capacitors, servicing of transformers, disposal of transformers an d/or fluids, or spills should be thoroughly documented in the official EPA PCB File an d approved if appropriate by the Plant Superintendent or Plant Manager. By cop y o this letter to all supervisors, their responsibilities with respect to PCB shoul a & a understood. If there are any questions or if clarification is needed now or in the future, please let me know. Also any differences of interpretation should be esolved as soon as possible. H. Garrison CC: Supervisors EPA PCB File yyC 000012520 VC A PLANT TRANSFORMERS As of: September 12, 1979 Transformer Serial Nj. ITE 14754 ITE 14757 ITE 14756 ITE 14755 ITE s 15408 UPTEGRAFF 84412 Westinghouse Westinghouse Westinghouse Westinghouse 71-C-6011 Westinghouse 78-C-68 7138 Westinghouse 78-C-687136 GE 1-2471L9 Service 13.2 KV/4160V Substation A Substation B Substation C Substation D Spare 13.2 KV/4160V Dock Vent Recovery Dock Vent Recovery Dock Vent Recovery Secondary Waste Treatment Incinerator Area Incinerator Area VCM Loading Exposure Reduction ooooi*5Zl b VCM Plant CERTIFIED MAIL #316097 RETURN RECEIPT REQUESTED jconozd) Formerly Conoco Chemicals CO . . Continental Oil Company P.0. Box 605 Westlake. Louisiana 70669 (318)491-5211 A Div. of CONOCO, Inc October 19, 1979 RECEIVED OCT 2 5 1$, 3 Paul D. Fahrenthold (WH-552) Organic Chemicals Branch Effluent Guidelines Division Environmental Protection Age ncy 401 M Street, S.W. Washington, DC 20460 Dear Mr. Fahrenthold: Attached is the completed q Jestionaire on the design factors and operating conditions of the steam stri pper in operation at CONOCO's VCM Plant in Westlake, Louisiana. We pr esently operate one steam stripper but are in the process of installing a spare steam stripper for use during downtime of the primary stripper. Dc ta has been enclosed only for the stripper we presently operate. Gperati on of the spare steam stripper should parallel that of the primary stripper presently in operation. If you should require further assistance, please dontact Gary L. Foshee, Chief Process Engineer, at 318/491-5062. Sincerely, 0. A. DeBernardi Plant Manager br cc: R. A. LaFleur BCC: REL-JCL-CRH-HJN-MAF-RLH-GLFfPLF-JOG-JWW 000^ z**1 Form Approved 0MB No. 158-R0160 COMPANY CONOCO , INC. LOCATION VCM PLANT, LAKE CHARLES DATE 10/19/79 STEAM STRIPPING Copy and answer Parts I throu oh I of this questionnaire for each steam stripper used to reduce the raw waste load ing prior to-direct discharge or discharge to an end-of-pipe treatment system (whether it be a publicly owned treatment works, a regional industrial treatment sys|t em, your own on-site treatment system, or other system such as a nearby refine ry 5 biological treatment system). PART I 1. List the names of all prodess (es) whose waste water discharges constitute a portion of the feed (charge) to the steam stripper. In the event more than one process waste water stream makes up the charge (feed) to the stripper, give the approximate percentage of each st ream on a flow or weight rate basis. Please place the percentages of each str earn in the table below. Wastewater streams from the ox.ychlorination, EDC wash, and EDC purification processes are combined in the ste am stripper feed drum, T-110, and discharged to the steam stripper.* 1 2 3 * Stripper Feed Source *Percentage of Feed 1. Ox.ychlorination 1. 52.4% (gpm) 2. EDC Wash 2. 31.1% (gpm) 3. EDC Purification 3. 16.5% (gpm) Total Feed flow (gpm) and/or weight (lb/hr) 80 *Indicate whether basis is weight (Ib/hr) or flow (gpm). VVC o 00012523 COMPANY CONOCO INC. LOCATION VCM PLANT> LAKE CHARLES DATE 10/19/79 _____ PART II This part of the survey reque its information adequate to assemble a trial material balance around the stripper, Operating data is the preferred source of information requested in this part. Flow or stream composition data gased on limited monitoring or calculations (eifi gineering estimates) is required as an alternative. 1. Please attach a process f ow diagram of the steam stripper. Kindly number and label all waste streams tHi at are associated with the operation of the stripper such as the charge ( feed), reflux, overhead product, decanter water, bottoms, etc. Indicate in yoi|i r drawing major equipment items such as pumps, heat exchangers, etc. A samp e sketch has been provided for reference. 2. Complete the attached Tab I with the information requested for each stream numbered in the sketch prepar ed in (1) above. Note that two sets of information are requested. One set consi Sts of general stream characterization parameters such as flow, temperature, pH BOD, TOC, etc. with spaces for additional or different characteristics, and organic or inorganic compounds known to be present, The second set labeled "compon ent" refers to priority pollutants identified or indicated to be present in thi waste waters associated with the stripper. vvc 000012524 BRUNING 40-534 38314 * y V) -r o v<t) < *4 ^ c* <0* N <Q s. (V tN. 'V > H< 8$ v) ^ .-> >^ \ Q 0 Vo <i > tn <5 14' (s <X .. ...Ui. v\ <j I $ V) ir M 51 \ 5> ^ ... .... <i f*i is * > V. 0 i'v T 4>'+'> /*v gr^5r c. a. -VX"Ns Vs. Vj 'Ui Vi \j __i. I Z3 c *& _o <v ac. S3 og O CJ 13 --r ...Q t CJ 03 CZ. --- --- VeI .o cc:i ua uu -o ________1 JCa->l 'cl cEo_> - VVC 000012526 NOTES 1) Flow, temperature, a nd composition data are from plant test run and plant operating data 2) COD, BOD, etc., has not been monitored. The steam stripper was designed for removal of EDO and fCM from plant wastewater streams. 3) A complete analysis of ^hese streams has not been conducted but the following priority pollutants have been identified as constituents of the streams. Concentration ranges are not indicated because the results presented below were obtained by analysis of a single sample and the concentration rangeS| haye not been defined. Priority Pollutant Vinyl Chloride C^loroethane 1,1 Dichloroethylene i 1]2-trans-dichloroethylene Chloroform 1.2-dichloroethane Carbon tetrachloride Trichloroethylene VVC 000012527 COMPANY LOCATION DATE CONOCO INC.___________ VCM PLANT, LAKE CHARLES 10/19/79 PART III This part of the survey reque sts information essential to evaluate the operating performance of the stripper and the energy consumption of the operation per unit of pollutant removed from the waste water. 1. Utility Requirements A. Steam Requirements Pressure 30 _psia Temperature RATE 250 6,000 _F 1bs/hr Is open steam used or doe^ thb column utilize a reboiler ? X Open Steam Reboiler B. Cooling Water Use Condenser Ir flu ant Temperature Condenser Ef flu ant Temperature Flow Rate Un known 83 F Unknown gal/hr. C. Other Energy Requirements Electricity 30,000/.yr. Compressed a|ir Inert gas kwh _scfm scfm 2. Column Specifics (The sketch called fo^ in II (1) above can be expanded upon to provide the following information). 5 vvc 0000X2528 COMPANY CONOCO, INC. LOCATION VCM PLANT - LAKE CHARLES DATE 10/19/79 Part III (Continued) A. Feed Rate 43,1 50 lb/hr B. Feed Temperature 30 C. Operating Pressure Top___________ Bottom 17 19 _psia psi a D. Operating Temperature Top______________ 216 Bottom 226 E. Column Diameter 4' - 0" I.D. ft. F. Number of Theoretical Trays (if known)______ No. G. Actual Number of Installed Trays or Packing Height 1 5* - 0" ft. No. or ft. (specify) H. Type of Trays or Packing Cascade Mini Rings I. Tray Spacing _____________ ft. J. Overall Column Height 26' - 0" ft. K. Reflux Ratio* (if any) L. Reflux Rate M. Reflux Temperature _1 b/hr Or- N. Bottoms Flow Rate 42,870 1 b/hr 0. Bottoms Temperature 226 P. Materials of Construction Trays __________ - Packing Polypropylene *Use overhead flow rate as the basis of this value VVC 0000 COMPANY CONOCO. INC. - LOCATION VCM PLANT, LAKE CHARLES DATE 10/19/79 Part III (Continued) Column or Ve? sel Column 3. Specify the ultimate dispcisition of column overheads (i.e., incineration, returned to process, etc.) foi' both the aqueous and the organic phases. The stripper column overhead s routed throuqh a condenser and knock out pot. The condensed liquids are retijrned to the steam stripper feed drum. The noncondensed is incinerated. 4. Specify the method of dis )osition of column bottoms, (i.e., discharged to biological treatment, dischar jed directly to surface waters, reused as cooling tower make-up, etc.) The steam stripper bottoms ar ; discharged to bioloqical treatment. 5. Are there any substances )resent in the influent stream to the steam stripper that interfere with the remov il of the pollutant(s) listed in (2) above.(i.e., maximum boiling azeotropes, p 1 adjustment, foaming, scaling, necessity to equalize flow or feed concent -ation, etc.). If so, please list and explain the nature of the interferences a id any methods devised to minimize or eliminate these interferences. Also explain low successful these methods have been. NO 6. Operating Specifics A. Is the steam stripper operated in a continuous or batch mode ? If batch, explain. Continuous B. Explain the method of treatment of the process wastewater that is normally discharged to the strippe r when the steam stripper is down for repair. Process wastewater will b e fed to the spare steam stripper after its completion. Wastewater i s presently by-passed durinq stripper down time. 7 vvc 0000X2530 COMPANY LOCATION DATE CONOCO INC.___________ VCM PLANT> LAKE CHARLES 10/19/79 PART IV Your responses to the folia wi ifig questions.will be used to determine the desireability of additional ff<b 1 low-up relating to capital and operating costs associated with the stei m stripper. A. Was the steam stri ppe - installed as a new piece of equipment ? Yes X No B. When was the steam stHpper installed ? December, 1967 Estimated spare stripper completion - January 1980 C. Do you have detai led tost information (both capital and operating) relating to the st earn stripper as a separate unit ? Yes NO D. Are you will ing tc share this cost information with EPA to be used to verify the cost of tha installation of steam strippers for the treatment of waste water. Yes X No E. Operating Labor Direct Operating 40 work-days/yr Maintenance 15 work-days/yr Supervisory work-days/yr F. Do you have V-L equil ibrium data which was used to design the stripper from your own experim ents, or Henry's Law Constants, or vapor pressure data, or activity coe fficient data, or other correlations? No Yes X_________ Identify which one Vapor pressure data used in conjunction with the Ideal Gas Law. G. Do you have informlation regarding the cost impacts of installing the stripper on the ftillcwing off-site activities ? (check either Yes or No, or indicate (a), b) or (c) as appropriate). Yes No a. Steam generatf on or a major revision in distributi on VVC 000012531 8 COMPANY CONOCO INC. LOCATION VCM PLANT> LAKE CHARLES DATE 10/19/79 Part IV (Continued) b. electrical sutsta bion capacity c. Instrument air cab aci ty d. Valve/Piping/Wiri ig systems to supply a, t, o r c Yes (a) (b) (c) No X_ X (a) (b) (c) XXX 9 vvc 000012532