Document N2Y6XjrRZ0oROey3wB4q99zoE

AR226-2681 Environmental Laboratory AR226-2681 Results from Analyses of Soil and Groundwater Samples From the E. I. DuPont de Nemours and Company Facility in Parkersburg, West Virginia STUDY COMPLETED: October 27,1997 FINAL REPORT COMPLETED: November 13,1997 Prepared by: j ^ 6 . & ^ Susan A. Beach Senior Environmental Biologist 3M Environmental Laboratory Building 2-3E-09 935 Bush Avenue St Paul. MN 55144 EID129573 3M Environmental Laboratory Table of Contents Summary of Results: 3 Project Description: 6 POAA Analyses in Groundwater and Soil (5/97 Samples): 7 POAA Analyses in Groundwater (6/97 Samples): 15 POAA Analyses in Soil (6/97 Samples): 22 Volatiles and Semi-volatiles in Groundwater by Purge and Trap Concentration with GC/MS Analysis (6/97 Samples): 30 Volatiles by AED (5/97 Samples): 38 Volatiles by AED (6/97 Samples): 45 Total Fluoride in Soil (6/97 Samples) 55 Total, Organic and Adsorbable Fluoride in Groundwater (6/97 Samples) 64 Soil Properties and Nutrient Concentrations (6/97 Samples) 79 Copies of Chain of Custody, Shipping Papers, Lab Requests 105 EID129574 Environrriental Laboratory HT Summary of Results . DuPont Washington Works Samples Sample Dates 5/8/97 (groundwater), 5/30/97 (soil) 3M LR No. R2008-1 R2008-2 R2008-3 R2008-4 R2008-5 R2008-6 DuPont Smpl. No. 1 2 3 4 5 none Matrix ground water ground water ground water ground water Dl blank soil POAA"', PPb 52 49 52 53 n.d-"' 364 Vol. & Semi Vol. F,CI. BrbyAED, Ppm <MQI.P> <MQL <MQL <MQL <MQL <MQL (1) POAA = Perfluorooctanoic acid anion (2) limit of detection/limit of quantitation a 650 ppt. (3) Minimum quantitation limits: Br -1.176 ppm in water, 1.187,1.220 ppm in soil 01=1.408 ppm in water, 1.253,1.461 ppm in soil F 0.280 ppm in water, 0.282 ppm in soil ASH010476 ._t_ 5 ^ au 71 ) il ."-^flUuOon'lOsct-- |io -- o QPfP)M <, i '301' ' ' 9M Environmental Laboratory \ ^^\ u-^^ -- ^ 5oi( "t/ Summary of Results \ -let ^ ?" ^ DuPont Washington Works Groundwater Samples i--"--tciO--^--wi^----------i----------i--_--_--__--_--_--S--am--ip--le----Da--te--6--/i2--6--/9--7--_i--__--_--_--_--_ Adsorb. DuPont 3M LR No. Smpl. No. POAA"' mg/L Total Fluorine mg/L Fluoride Ion Organic Organic F, mg/L F, mg/L'4' mg/L R2148-1 MW-1-1 5.64 8.0 0.20 7.8 4.5 R2148-2 MW-1-2 5.32 16 0.20 16 4.2 R2148-3 MW-2-1 0.234 3.3 0.16 3.1 0.28 R2148-4 MW-2-2 0.234 3.5 0.16 3.3 0.46 R2148-5 MW-3-1 0.487 4.2 0.14 4.1 1.1 R2148-6 MW-3-2 0.477 3.3 0.14 3.2 0.76 R2148-7 MW-4-1 0.0842 4.0 0.11 3.9 0.19 R2148-8 MW-4-2 0.0590 4.2 0.11 4.1 0.14 R2148-9 MW-5-1 < PQU2' 3.0 <0.10 2.9 0.11 R2148-10 MW-5-2 < PQU" 2.8 <0.10 2.7 0.14 R2148-11 MW-6-1 < MDU3' 2.3 0.10 2.2 <0.05 R2148-12 MW-6-2 < MDL" 4.2 0.10 4.1 <0.05 Vol. & SemiVol. F by AED, ppm 0.20 <[F]< 2.5 0.20 <(F|< 2.5 0.20 <[F]< 2.5 0.20 <|FI< 2.5 0.20 <IF1< 2.5 0.20 < [F]< 2.5 0.20 <[F]< 2.5 0.20 <[?]< 2.5 IF] < 0.05 0.05 <IF]< 0.20 IF] < 0.05 IF]<0.05 ' ASH01 Trichlorotri fluoroethan ng/L 820 730 1600 1500 2300 2400 760 670 130 140 tert-Butyl 3M LR No. R2148-1 R2148-2 DuPont Smpl. No. MW-1-1 MW-1-2 Alcohol ^ig/L 59 49 R2148-3 MW-2-1 R2148-4 MW-2-2 R2148-5 MW-3-1 R2148-6 MW-3-2 R2148-7 MW-4-1 R2148-8 MW-4-2 R2148-9 MW-5-1 R2148-10 MW-5-2 R2148-11 MW-6-1 R2148-12 MW-6-2 (1) POAA Pertluorooctanolc add anion Cis-1,2Dichloroethene ng/L Chloroform 49/L 5.5 5.9 5.8 37 5.9 39 13 16 (2) Practical quant, limit 0.0510 mg/j^y^p; 1.1,1trichloro- ethane H8/L Trichloroethene 49/L Tetrachloroethene ng/L Trichlorofluo methane 49/L 140 16 150 18 14 520 5 26 14 570 5.2 26 6.3 81 5.9 6.2 66 5.8 (3) U^ of detect. - 0.0255 mg/L (4) Total Fluorine Ftuorlde Ion - Organ 3M Environmental Laboratory Summary of Results DuPont Washington Works Soil Samples Sample Date 6/23/97 ASHO 1 3M LR No. R2382-1 DuPont Sample No. SS-1 0-2' R2382-2 SS-1 4-6' R2382-3 SS-1 8-10' R2382-4 SS-1 12-14' R2382-5 SS-1 16-18' R2382-6 SS-1 20-22' R2382-7 SS-1 24-26' R2382-8 SS-1 28-30' R2382-9 SS-1 32-34' R2382-10 SS-1 36-68' R2382-11 SS-1 38-40' Total Fluoride, mg/kg 21,300 20,100 61,200 78,300 106,300 82,700 59,100 37,600 33.500 41,200 30,300 POAA"'. mg/kg 0.119 0.17 614 207 219 39.8 24.6 29.3 13.1 6.78 2.11 Sulfate, mg/kg 98 99 73 54 43 70 220 150 100 63 46 Sulfite, mg/kg <2 <2 <2 <2 <2 <2 <2 <2 <2 <2 <2 Nitrite, mg/kg 0.41 0.41 0.36 0.14 <0.10 <0.10 <0.10 0.11 <0.10 <0.10 <0.10 pHin water 7.7 7.7 7.3 6.7 5.7 6.0 5.8 6.8 5.8 6.1 6.8 pHin CaCI, 7.2 7.3 7.0 6.3 5.3 5.5 5.3 6.3 5.2 5.4 6.2 CEC, Moisture, meq/100g % 15.8 12.3 18.4 12.7 17.5 15.5 17.5 18.9 18.4 18.3 19.3 19.2 17.5 20.0 11.4 18.1 13.1 , 13.6 9.6 17.9 6.3 22.2 (1) POAA = Perfluorooctanoic acid anion 3M Environmental Laboratory Project Description Three coolers were received from E.I. DuPont de Nemours and Company ("DuPont"), each containing samples for analyses by the 3M Environmental Laboratory. Each cooler-group was assigned an unique project number (Lab Request Number). Each sample was also given an unique number which was a sub-set of the project number. The project numbers are as follows: R2008, samples 1-6 Four groundwaters, one Dl water blank and one soil sample, with sample dates 5/8/97 (waters) and 5/30/97 (soil). R2148, samples 1-12 Twelve groundwater samples, with a sample date of 6/26/97* ' R2382, samples 1-11 Eleven soil samples, with a sample date of 6/23/97 Samples were stored at 4C, in the dark, until analyzed. Different groups within the 3M Environmental laboratory were responsible for various analyses. Attached are the summary reports for analysss^K^AA, B Total, free, organic and adsorbable fluoride, volatiles and semNft)laWs'|i nitrate," sulfate, ahd'sulfide, and soil pH,percent moisture and cationaefeNaftge^ capacity. "yv EID129578 Environmental Laboratory POAA Analyses in Groundwater and Soil (5/97 Samples) EID129579 3M Environmental Laboratory Data Transmittal Summary Fiaal (Date Received: Sponsor or Client: Representative Name Company Name DuPont Company Address Phone )DJ: QAU (Archives): LffiN System: Project Manager: Sue Beach Others (List Recipients^'Address/Phone/FAX) |T. DiPasquale, 22-11&03; 3-1891; 736-3257 Seotby:/Datggg| Igh on 11/10/97 -l^as-/ A copy of the report mdudrng this form Mdt&e client cover page it to Segiven to QAU, LIRN and to the Group Leader. 8 ^ S^S- EID129580 \ 3M Environmental Laboratory- Advanced KrisHansen-Sr. Analytical Chemist Advanced Method Development Team Building 2-3E-09 612-778-6018 kjhansen@miiim.coia Report - Analytical Study Determination ofPOAA in Sou and Water 1.0 Summary One soil sample and five water samples were subnutted by DuPont for quantitatwe analysis of perfluorooctanoic add anion (POAA). The soil sample was assigned number R2008-6; the water samples were given numbers R2008-1 through K2008-5. Analysis of the samples by negative ion electrospray mass spectrometiy(ES/MS)determmed that peraaoroo<aanoate add amon is present maUsansples except R2008-5. Specificresults axe listed in Table 1. Table 1. Concentration of POAA in R2808 aamntea. Sampled K2008-6 Matrix soil Dilution Factor Extractability n.a. n.a. Corrected concentration Owb) 0.364 mg/kg Average (ppb) Std.Dev. n.a. n.a. R2008-1-1 water 2 1.3 B2008-1-2 water 2 1.3 R2008-2-1 water 2 1.3 R2008-2-2 water 2 1.3 R20Q8-3-1 water 2 "K2008-3.2 water 2 R2008-4-1 water 2 1.3 R2008-4-2 water 2 1.3 R2008-5-1 water 2 1.3 K2008-5-2 water 2 1.3 * limit of detection/limit of quantitation is 650 ppt %.;.-.. *'%- 52 52 49 49 52 '-sT""1-57 49 n-d.* n.d. 52 0 49 0 i s l rm .;o' 53 6 n.a. n.a. 2.0 TEST MATERIALS One soil and five water samples were received fiomEhiPont on 06/10/97. The samples were stored at 4Cuntn extraction; extracts were stored at 4C until analysis. u. i-i ,,,,T "'t 3.0 EXPERIMENTAL-OVERVIEW AND METBOBS 3.1.1 Sample, soil I Because no HBPqirtifflimq^ mi1 wag avaitahTefnr blank analysis, the method af standard addition was used to deteniuTM the coiK^teaaoa ofPOAA m the soflreCTavedfiomD^ Aneight oo pomtstan<tori curve was prepare by spadng2._grasmamples of the soBwths^ M solution between 500 ppt and 1.0 ppm. The soil was mixed with approximately 1 gram of diatomaceous earth and loaded into a 10 mL stainless sted extraction cartndge. TBC spiked samples were extracted using high pressure solvent extraction (HPSE)withimethaaol; tne extracts were dried with nitrogen and reconstituted with ACN/water (1:1). After analysis by negative ion ES/MS, the data was subjected to Imear regression and the resulting prediction equation was used to determine the conceatratioa of anafyte Word Version 6.0 Lab Request #R2008 R2008JDOC <? ^^5- EID129581 in the unspiked material (see Figure 1, attached). Four unspiked soil samples were also extracted to confirm that the method reproducibility was better than 10%. The method of standaid addition assuna^ there are no mterferencesia the anatysis and that the extractionefficiencyoftlieaaalytefiomtheniatrixisnotdependentuponaaalytecoacentration. Thefast assumption is addressed by the selectmty of the both the extraction and the analysis; the latter has been verified in another study that focuses on a similar matrix. 3.1.2 Sample, water For method development, two series of samples -wass prepared for analysis by ES/MS- In series A, the target analyte was extracted fiom the samples with an ion pairing reagent and analyzed; in Series B, each sample was diluted (1:1) with acetonitrile (ACN). Both Series A and B consisted of 2 aliquots of water from two of the submitted samples (R2008-1 and R2008-3). The recovery of POAA resulting from Series A and Series B analysis were in close agreement - AU five water samples were prepared, in duplicate, for anafysisusing the Scries B protocol. The samples were analyzed by ES/MS between two unextracted curves ofPOAA in ACN/H20. The reproducibility of the carves was within 15%. 3.2 Calibration and controls, water A set of controls, including a miUi-Q water blank, nulli-Q water spiked with POAA, and four samples of matrix spiked with POAA, was prepared along with each sample series. The controls were used to evaluate extraction efficiency of the POAA fiom water and subsequentlydetermine an accurate extractability factor for final concentration calculations. A POAA standard curve from 50 ppt to 1.0 ppm in ACN/H20 (1:1) was prepared; all extracts and prepared samples were analyzed by negative ion ES/MS and quantitated relative So a standard curve. The unextracted standard curve was plotted according to linear regression with a ooe5cient of determination^ equal to 0.999. Two-1 mL aliquots of sample R2008-1 were spikedwith POAA. These samples were designated the matrix spike (MS) and the matrix spike duplicate (MSD) and were prepared for analysis by the same procedure as the samples. The final concentration of POAA in the MS and MSD-'wassexpected to be 52 ppb. The concentratioa of POAA recovered fiom the samples was evaluatedtrelative.toLthe standard curve, aim 3.3 Extraction specifics, Mil The soil samples were extracted with the ISCO 3560 Accelerated Extraction System, with ISCO 100DX high pressure syringepumps according to me following conditions: ',s-w Extraction sotveat: Extraction pressure: Extraction temperature: Restrictor temperature: Static extraction timc-1: Dynamic extraction vohime-1: Static extraction time-2: Dynamic extraction time-2: Restrictor flow rate: methanol, HPLC grade 2500psi 70 C 70 C 40 minutes 15 nT. 2 minutes 2 minutes 2.5 mL/min ^g Samples were reconstituted in glass autovials with HPLC-grade ACN aad milli-Q water. sh-* w vsc'- Word Version 6.0 Lab Request #B2008 R2008.DOC 2 \0 4 1^5' EID129582 3.4 ES/MS Analysis specifics, soB and water Negative ion ES/MS analysis was peifanned on a MicromassPlatfonnn atmospheric pressure ionization mass spectrometer runmag Mass Lynx 2.1. A Hewlett Packard 1100 was used for the autosampler and HPLC system. MobUe phase: ACN/H20 (1:1) Flow rate: 60 tiL/min Injection volume: 15pL Cone Voltage "-20 Capil2aiy voltage = -2.56 Source Temperature =80C Analyzer Vacuum Pressure =0.000079 mBar Quandtarive results were based on the instannental response generated by momtoriag a single ion characteristic of the analyte. This ^ype ofmonitoring minimizM interference by other iona in solution and increases system sensitivity to the target aoaiyte. 4.0 BATA ANALYSIS 4.1 Sample, sott By the memod of standaidaddidon,t2ic soil was detennmed to contain 0.364 mgPOAA/kg. This value was calculated usmg the prediction ecpationresulimg^m linear regression aaal^ eight point extracted curve. ThfieoeffidentofdeterDHBationforthecurveisO.990. Calculations used to detennine the concentration of POAA in the soil are shown in Appendix A. 4.2 Samples, water TheconcentradonofPOAAmeachwatersamplewasdetennmedbycomparison.ofidetected peak areas resulting firom analysis of the samples to the average ofthe two uaje^^^ using the following formula: ; s t<'t. C.=OP-9/S (4) Where, C,:ss Concentration ofPOAA ia sample (ug/mL) P = Peak area of sample (response) I = Intercept of the calibration curve (response) S== Slope of the caHbration curve (response/concentration) The concentradondctenmned to be mtSie extract was converted to ^ concentration m the water sai^ according to the following equation: i Cp=(C.*D)*E (5) Where, S Cp=Concentradon of POAA in actual sample (ug/mL) C, = Concentration ofPOAA ia prepared sample (pg/mL) sl-- D= Dilution Factor E = Extractability 00 IS>. Wold Version 6.0 Lab Request ffR2008 B2008J30C 3 (i 4 ia.ff' EID129583 ^..: ^i.;Mi-?1' 4.3 Determinxtion of percent recovery and estractability, water Matrix q)5ke sampleswere analyzed to detoinine the iecoveiy of POAAfiom the water. POAA recovery and the related extractability value are calculated as fellows: %R= [(Cf- cy / c,i*ioo% (6) where, %R = Percent recovery ofPOAA Ct= Concentration ofPOAA fouadmMS/MSD(}tg/BaL) Cn = Nadve concentration of POAA in sample before dilution adjustment (}ig/mL) C, = Concentration of POAA spiked in MS sample Qig/mL). As an example, the percent recovery for the R2008-1-1, MS sample is calculated as follows: therefore, Cr= 0.057 i^ftriL; C= 0.020 (ig/iaL; C," 0.052 p^mL; %B. (0.057-0.020)/0.052 x 100%= 74%. The extractabiliQr is equal tQ 100% dhddedby %EL The percent rccovedes of POAA m the MS aadMSD samples and tha correspondingextractabmty facto are presented in Table 2. Sample MS MSD Recovered Concentration (wfmL) 0.057 0.059 Spiked Concentration (neAnL) 0.052 0.052 Native ' CoBcentration (msftnL) 0.02 0.02 Avenge % Recovery 74 75 75 Extractxbilhy 1.3 1.3 L3 5.0 CONCLUSION High pressure solvent extcacdoo, ESAfS aaalysis aod liiKi detenmae&at 0.364 nag/Isgof POAA is present in the soil saniple received feomDuPont Waters R2008-1 through R2008-4 also contain about 50 ppb POAA. No POAA was detected inR2008-5. 6.0 MAINTENANCE OF RAW DATA AND KECOBBS Hard copies of these data are filed in the AMDT archive. Simple pftpiixlioa: GML/JJ AiMlyKO&flL4gh Report pccpftKXL kpi -t ' ^ - it. '!! "*ii. la thr w o i-- o 4^. 00 LX Word Version 6.0 Lab Request #R2008 B2008J>OC ^ ^ 13.S- EID129584 DATA TABLE 1.0 Spiked Standard Cone. of POAA in Extract (ug/mL) Blank 0.0005 0.005 0.050 0.100 0.250 0.500 0.750 1.000 Cone. of POAA m Soil Qig/kg) 0.00 0.50 5.00 49.22 99.63 248.97 493.88 748.39 995.17 FIGURE 1.0 R-2008 DoPoat Soil Data POAA Standard Curve and Data Table Volume of Extract (mL) 2.0 2.0 2.0 2.0 2.0 2.0 2.0 2.0 2.0 Peak Area of Estract-a 1822272 2076435 1967476 2129047 2457197 3249144 5136166 5879632 - 7704024 Spiked Amount of of POAA in Extract (pg) 0.00 0.001 0.01 0.10 0-20 0.50 1.00 1.50 2.00 Peak Area of Extract-b 141494 396700 475027 623624 225468 395568 666830 786883 842187 Mass of SoU (g) 2.0259 2.0032 2.0004 2.0319 2.0075 2.0083 2.0248 2.0043 2.0097 Total Peak Area(a+b) 1963766 2473135 2442503 2752671 2682665 3644712 5802996 6666515 8546211 Cone. of POAA in SoilOig/kg) 0.00 0.50 5.00 49.22 99.63 248.97 493.88 748.39 995.17 1 "WSCSis'' 13 4 US' EID129585 R-20Q8 DuPoBtSolS Data POAA Standard Cm-v aad Data Table CALCULATIONS In order to plot the Total Peak Area versus the Concentration of POAA in Soil, the following conversion calculations were performed: Cone. of POAA, fiom Volume Mass Convert spiked standards, x of X of X g to = in die extract Extract Sou kg Cone. of POAA in Soil US x mL X 1 x 1000 g = M mL I S kg kg To calculate total Peak Area, the area integrated for peak "a" for tee initial extraction of the soil and the area integrated for peak "b" for the second extraction of the same soil are summed. Using the Method of Standard Addition determine indigent anatyte concentration by solving for for me x-intercept where y ss 0, and equation of the slope of the line of Peak Area vs. Cone. of POAA in Soil is: y = 6248 x+2275109 x=-2275109/6248 x-364 concentration of indigent analyte POAA in soil determined to be 364 pg/kg EID129586 Environmental l-aboratory POAA Analyses in Groundwater (6/97 Samples) EID129587 3M Environmental Laboratory Data Transmittal Summary Final late Received: Sponsor or Client: Representative Name Company Name DuPont Company Address Phone Analyte(s) or Test Method ft POAA Sample Matrix: water Analysis Dates: 9/97-11/97 Analyses): LAC Author: LAC, Igh D] ata Reviewed by: PAR Project Lead (or designee):kjh "amesD. Johnson (or designee): Internal IDJ: QAU (Archives): LIRN System: Project Manager Sue Beach Others (List Recipients /Address /Phone /FAX) JT.DiPasquale, 22-11B.03; 3-1891; 736-3257 iWsSt:^''' Sent by./Date Sent by:/Date Igh on 11/10/97 ^ a 0 St--^ SO A copy of the report including this form and the client cover pige is to be given to QAU, URN and to tee Group Leader. /&. ^ l^ EID129588 3M Environmental Laboratory - Advanced Method Development Team Contact: Kris Hansen - Senior Analytical Chemist Building 2-3E-09 778-6018 Final Report - Lab Request R2148 Electrospray Mass Spectrometry Analysis of DuPont Water Samples Prepared 8126/97 1.0 SUMMARY Twelve samples from DuPont were submitted to the 3M Environmental Laboratory for the analysis of Surfactants. These samples were numbered R2148-1 through K2148-12 (MW-1 through MW-6) and analyzed with an Electrospray Mass Spectrometer. This analysis determined mat perfluorooctanoic acid anion is present in samples 1 through 10. Results are listed in table 1. Tablet Sample Results Sample ft Ion Count Dilution Concentration Average Std. Dev. Area Factor |jg/mL (ppm) R2148-1-1 (MW-1) 160473 20 5.71 K2148-1-2(MW-1) 157432 20 5.58 5.64 0.0872 R2148-2-1 (MW-1) 148341 20 Rawg-z^Q^.gllt^ 'fSip^ 20 R2148-3-1 (MW-2) 79430 2 5.21 5.42 0.242 ^.32 $ ftf 0.149(M --CT R2148-3-2(MW-2) 75610 2 0.226 0-234 0.0110 R2148-4-1 (MW-2) 80126 2 0.245 82148-4-2 (MW-2) 74915 2 0.224 0.234 0.0149 R2148-5-1 (MW-3) 135558 2 0.469 B2148-5-2(MW-3) 143990 2 0.504 0.487 0.0242 R2148-6-1 (MW-3) 135283 2 0.468 K2l48-6-2(MW-3) 139707 2 0.486 0.477 0.0127 B2148-7-1 (MW-4) 43324 2 0.0954 B2148-7-2(MW-4) 37814 2 0.0731 0.0842 0.0158 R2148-8-1 (MW-4) 35756 2 0.0647 R2148-8-2 (MW-4) 32916 2 0.0532 0.0590 0.00814 R2148-9-1 (MW-5) 24116 2 <PQL g R2148-9-2(MW-5) 23264 2 <PQL <PQL <PQL R2148-10-1 (MW-5) 21873 2 <PQL > 00 R2148-10-2(MW-5) 26025 2 <PQL <PQL <PQL R2148-ll-l(MW-6) 11696 2 <MDL B2148-11-2 (MW-6) 11932 2 <MDL <MDL <MDL \0 R2148-12-1 (MW-6) 9132 2 <MDL 0 R2148-12-2(MW-6) 10595 2 <MDL <MDL <MDL Word Version 6.0 B2148.DOC Page 1 of 5 17^ \3L5' EID129589 2.0 TEST MATERIALS Twelve water samples were received from DuPont on 07/02/97 (MW-l-1, MW-1- 2, MW-2-1, MW-2-2, MW-3-1, MW-3-2, MW-4-1, MW-4-2, MW-5-1, MW-5-2, MW-61, and MW-6-2). These samples were checked-in as R2148-1 through 12 and were analyzed for suriactants. The samples were stored at 40C until preparation and analysis. 3.0 EXPERIMENTAL-OVERVIEW AND METHODS 3.1 Investigative Samples One halfmL was removed from each sample and diluted with 0.5 mL of acetomtrile (ACN, TN-A-1504) for a final sample solvent composition of 1:1 ACNrWater. These samples were vortex mixed and ready for analysis by electrospray mass spectrometry (ES/MS). 3.2 Matrix Spike Samples Matrix spike (MS) and matrix spike duplicate (MSD) samples were each prepared diluting 0.5 mL fiom sample R2148-12-1 with 0.5 mL of ACN. The MS and MSD samples were each spiked with 0.005 mL of a 101.1 ug/mL (ppm) ammonium perfluorooctanoate standard solution (W397-741) for final concentrations of0.503(ig/mL. 3.3 Calibration Ammonium Perfluorooctanoate calibration standards, ranging in concentration '^'X.^.M^. from 0.0500-1.01 ug/mL, were analyzed bracketing the samples. The calibration curve w wa^yw was developed by plotting the|nean of two standard peak areas of ammonium <ng ass of r*? perfluorooctanoate versus the^concentranon of ammonium perfluorooctanoate standaBlsth using linear regression. 3.4 Instrumentation The following instrumental conditions were used to analyze these samples: Micromass Platform Electrospray Mass Spectrometer Hewlett Packard 1100 Pump and Autosampler MassLynx 2.1 software Cone Voltage = -14 Skimmer Lens Offset = 3 Source Temperature = 80C Analyzer Vacuum Pressure = 0.000079 mBar Injection/sample: 1 ^ Injection size: 10 uL w Flow Rate: 0.080 mL/min o g 3.5 Continuing Calibration Standards ^o Continuing calibration standards at 0.253 ppm ammonium perfluoroctanoate were analyzed bracketing every ten samples during sample analysis. Word Version 6.0 R2148.DOC Page 2 of 5 /a 4 \zsr EID129590 3.6 Detection Limits The method detection limit (MDL) is equal to approximately 3 times the baseline noise and half me practical quantitadon limit (PQL). The PQL coiresponds to the lowest point on the calibration curve. The PQL is 0.0510 jig/mL; the method detection limit is 0.0255 pg/mL. 4.0 DATA ANALYSIS 4.1 Calibration Curve Average peak areas from the initial curve were plotted against me concentration of ammommn perfluorooctanoate in the calibration standards. The standard curve was linear (R'S 0.99). 4.2 Continuing Calibration Standard Continuing calibration standards were analyzed before and after every 10 samples. The continuing calibration standards remained within 20% of the initial standard. This meets the criteria used to determine if the calibration curve has maintained linearity. The relative percent difference is calculated using me following equation: Equation 1 %D = -^--^xiooyo nj where, ' . r(e"":' %D= relative percent difference R, = area 0.253 ppm calibration standard from me initial calibration R, = area 0.253 ppm calibration standard from the continuing calibration a " $et & l l ;s ^ *sr' ?*;i"-ri; 4.3 Investigative Samples 4.3.1 Calculations Concentrations of ammonium perfluorooctanoate were determined by comparison of detected peak areas to the calibration curve using the following formula: vv* Equation 2 cessPp-I- > S *s o Where, S Cg = Concentration of ammonium perfluorooctanoate in extract (ug/mL) ^ Psa Peak area of sample I = Intercept of me calibration curve Word Version 6.0' R2148JDOC Page 3 of 5 /7 i us- EID129591 S = Slope of me calibration curve (mL/ug) The concentration of ammonium perfluorooctanoate in the extract was converted to the concentration in the water samples by using the following equation: Equation 3 Cp = CexjD Where, Cp= Concentration of ammonium perfluorooctanoate in water sample (u,g/mL) C, = Concentration of ammonium perfluorooctanoate in extract (pg/mL) D^ Dilution Factor As an example, ammonium perfluorooctanoate anion was detected in sample R2148-1, where P = 160473, S = 493135 mL/pg, I = 19797; therefore, using Equation (2), C, = ((l60473-19797)/493135) = 0.285 pg/mL. To determine the concentration in water, using Equation (3), C, = 0.285 ug/mL and D = 20; thus C,= 0285 pg/mL x 20 = 5.71 pg/mL (ppm). 4.4 Matrix Spike Samples Matrix spike samples were analyzed to determine the recovery of ammonium perfluorooctanoate. Recovery was calculated using the following equation: Equation 4 . . %R = ^--^xlOO'/o Cms ....t.w, where, %R sa Percent recovery of ammonium perfluorooctanoate Cg = Detected concentration of ammonium perfluorooctanoate in MS sample (pg/mL) ,,(., ,^^p,jgi, = Average background concentration of ammonium perfluorooctanoate in sample. (jug/mL) ipk ( U&T Cn,e = Expected concentration of ammonium perfluorooctanoate in MS sample (pg/mL). As an example, the percent recovery for me R2148-12-1, MS sample is calculated as > follows: - gj o On = 0.404 pg/mL; I Cb^O.OOug/mL; u> C^ 0.503 pg/mL; therefore, %R = (0.404-0.00yo.503 x 100% = 80%. Worf Version 6.0 B2148.DOC Page 4 of 5 <%) ^ W EID129592 The percent recoveries of ammonium perfluorooctanoate in the MS and MSD samples are presented in Table 2. Table! Matrix Spike Results Recovered Expected Sample Type DuPont Water Sample ID R2148-12-1.MS R2148-l2-l,MSD Concentration (ug/mL) 0.404 0.401 Concentration1 (ug/mL) 0.503 0.503 Average % Recovery 80 ' 80 80 Notes: 1 Recovered concentration is equal to the concentration detected in tile spiked safflple minus the average concentration detected in associated unspiked samples. 5.0 CONCLUSION The results ofES/MS analysis determined that the ammonium perfluorooctanoate anion is present in DuPont water samples R2148-1 through R2148-10 at average concentrations of 5.64 ppm, 5.32 ppm, 0.234 ppm, 0.234 ppm, 0.487 ppm, 0.477 ppm, 0.0842 ppm, and 0.0590 ppm respectively. The results have been presented in table 1. 6.0 MAINTENANCE OF RAW DATA AND RECORDS Hard copies of these data are filed in the AMDT archive. ' "'^ 7.0 APPENDICES The appendices are not included with these data. archive. 7.1 Extraction Logbook ------- 7.2"Instrument 'Rontog"--------- 73 Curve and Cbromatograms 7.4 Results They are filed in the AMDT LAC 8/29/97 Word Version 6.0 R2148.DOC Page 5 of 5 ^l ^ \^ EID129593 3M Environmental Laboratory POAA Analyses in Soil (6/97 Samples) EID129594 3M Environmental Laboratory Data Transmittal Summary Final >ate Received: Sponsor or Client: Representative Name Company Name DuPont Company Address Phone 'reject Lead: KrisHansen (8-6018) Group Leader: Jim Johnson (8-5294) Analyte(s) or Test Method fr. POAA Sample Matrix: water $o i L Analysis Dates: 9/97-11/97 Author: kjh Analyses): GML, JJ, Igh i Data Reviewed by. MEE |ProjectLead (or designee):kjh ames D. Johnson (or designee): ____ pDJ: QAU (Archives): JLIBNSystem: jprojectManager: Sue Beach Others (List Recipients /Address /Phone /FA3Q IT. DiPasquale, 22-11E-03; 3-1891; 736-3257 Sent by./Date Igh on 11/10/97 I --* o 4s> so o\ Acopyoftheraportmdudmgtlusformadthedieffltc<verpayi8toteg^entoQAU,LIRNandtothe Group Leader. A3 4 /^ EID129595 3M Environmental Laboratory- Advanced Methc- - KrisHaasen-Sr. Analytical Chemist Advanced Method Development Team BuHding 2-3E-09 612-778-6018 kjhansen@mram.com -_____ 'Report - Analytical Study Betenmnatum offOAA in Soil and Water Lab request-B2382 1.0 Summary Eleven soU sampleswere aibnuttedl^DuPont&rquaitdtaavcajaalysis of peifluoro^^ amon(POAA). The sou samples were assigned nmi^S2382-l through-11. Extraction of the soils usmglMghpiessurasolveM extraction (CTSE)fbUowed by analy^ of die eittracts by Mga^ electtospray mass spectroisietly (BS/MS) detennined that POAA is present maH samples.^ concentration ofPOAA mK2382-l was detenmiiediisingfbe meOod ofstandaxd additions, ;A^other soils |were evaluated relative to the curve generated ia the standard additions anai^s^aif^^^es^tsjae listed in table 1. Table 1. CttpcentratinB rfPOAA m W3S1 ssaaAsa. Sampled mgPOAA/kgsoil R2382-1 0.119 R2382-2 B2382-3 0.170 748 ^ B2382-6 272 (ftt '. 280- 52J& B2382.7 373 B2382-8 39.7 K2382-9 18.0 R2382-10 12.7 B2382-11 2.27 * limit of detection/limit ofquantitation is 0.100 ing (100 ppb). 2.0 TEST MATERIALS Eleven soil samples were received ftomIhiPont oa 06/10/97. until extraction; extracts were stored at 4C until aaatysis. iu>.. ,wess stored at4CC 3.0 EXPEKIMENTAL-OVERVIEW AMD METHODS 3.1.1 Sample, soil Because no mKontaininatedsoa was availabtefca blank aaaty^ the inctn^ addition wasissedtodetcmmetlweon<antrafionofPOAAmthesonreceivedfiomDuPonL Afivepoint standard curve was prepand by spads^ 2 gram saa^Ics ofthe sdlQE^824) with some a^ solution between 500 ppt and 1.0 ppm. Two-gram samplesofthe teffirensainiog soils, and the sp&ed soils were each nuxed with approximatdy I gnttacrfcnatomacewu earth aad loaded mtoa 10 inLstaa^ extraction cartridge. TIM sables were extracted usiag high pressure solvent extraction (HPSE) with methaaol. Each samplewas extracted mto an a'(prunar^c!xttact)aBdV(secondaiyextra^^ The Word Version 6.0 Lab Request #K2382 K2382J30C 21 4 l^ EID129596 with nitrogen and reconstituted with acetonitrile (ACN), filtered, and diluted with water (1:1)- After analysis by negative ion ES/MS, the data from the spiked samples was subjected to linear regression and the resulting prediction equation was used to determine tile concentration ofanalyte in the unspiked sample R2382-6 (see Figure 1, attached). The remaining soils were evaluated relative to this curve. Soil from samples B2382-2 through-11 was prepared m the same way. For most samples, dilutions of Ac extracts in 'a' and *b' vials were necessary. It was also necessary to dilute and reanalyze four samples on 11/04/97. The POAA concentrations of these samples were determined by me same method, using a standard curve generated that day (see Figure 2, attached). The method of standard addition assumes there are no interferences in me analysis and mat me extraction efficiency of me analyte from me matrix is not dependent upon analyte concentration. The first assumption is addressed by me selectivity of both the extraction and me analysis; me latter has been verified in another study mat focuses on a similar matrix. 3.1 Extraction specifics The soil samples were extracted with me ISCO 3560 Accelerated Extraction System equipped with ISCO 100DX high pressure syringe pumps according to the following conditions: Extraction solvent: Extraction pressure: Extraction temperature: Restrictor temperature: Static extraction time-1: Dynamic extraction vohune-1: Static extraction time-2: Dynamic extraction time-2: Restrictor flow-rate: methanol, HPLC grade 2500 psi 70 C 70 C 40 minutes 15 mL 2 minutes 2 minutes 2.5 mL/min Samples were reconstituted in glass autovials with HPLC-grade ACN and milli-Q water. 3.4 ES/MS Analysis specifics W.GW Negative ion ES/MS analysis was performed on a Micromass Platform n atmospheric pressure , ionization mass spectrometer running Mass Lynx 2.1 operating system. A Hewlett Packard(|yLflpaWas,we(L^ -^ for the autosampler and HPLC system. . Mobile phase: ACN/H20 (1:1) Flow rate: 60 pL/min Injection volume: 15uL Cone Voltage =-20 Capillary voltage" -2.56 Source Temperature = 80C Analyzer Vacuum Pressure = 0.000079 mBar Quantitative results were based on the instrumental response generated by monitoring a single ion characteristic of the analyte. This type of monitoring minimizes interference by other ions in me extract and increases system sensitivity to the target analyte. 4.0 DATA ANALYSIS ^ CO By the method of standard addition, sample R2382-1 was determined to contain 0.119mg/kg of POAA. This value was calculated using me prediction equation resulting from linear regression analysis of ^ the five-point extracted curve. The coefficient of determination for the curve is 0.999. Calculations used ^ to determine the concentration of POAA in the soil are shown in Appendix A. The concentration of POAA in samples R2382-2 throughB2382-11 was determined by evaluation of ES/MS response relative to the curve generated for sample R2382-1. Calculations are detailed in Appendix A. Word Version 6.0 Lab Request SR2382 R2382JDOC 2 S5' ^ l^ EID129597 5.0 CONCLUSION High pressure solvent extraction, ES/MS analysis, and linear regression analysis were used to determine that between 0.119 and 614 mg/kg ofPOAA is present in me eleven soil samples received from DuPont 6.0 MAINTENANCE OF RAW DATA AND RECORDS " Hard copies of these data are filed in me AMDT archive. Sample preparation: GML/JI Analysis: GMLflJflgh Report preparation: kjh/JJ eslljjy was usad Word Version 6.0 Lab Request ?2382 R2382.DOC ^ >--> I W -?& ^ /.PA-" EID129598 R-2382- DoPont Soil Data Appendix A R-2382 POAA Determination Calculations For Detennination of "indigent" amount in Standard Additions Carve for R2382-1 Step 1: From Plot of Peak Area vs Spiked POAA Standard Concentration determine equation of the linear regressionby least squares analysis, for y =' mx + b Example: y = 126000 x+15000 Step 2: Solve linear equation for x, where y = 0, for the x-intercept of the line. Example: 0 = 126000 x +15000 x = -15000/126000 Step 3: Indigent amount will equal absolute value of x. Par Soil R-2382 Soils 2-11 Step 1: (Peak Area - Y intercept)/ Response == Diluted Cone. of POAA (ug/ml) Peak Area, intercept, and response fiom std.additions curve calculated ia ugtal Example: (31000 - 15000yi26000 " 0.127 ug/ml Step 2: Example: (Diluted Cone. of POAA ug/ml * Dilution Factor ) + Indigent Cone. ugtaL'= Adjusted Cone. of POAA ug/ml (0.127 ug/ml 50) +.119 ug/ml = 6.47 ug/ml Step 3: Example: Adjusted Cone. (ug/ml) * 2ml extract/mass (g) * 1000 g/kg * 1 mg/1000 ug -Total Cone. of POAA (ing/kg) 6.47 ug/ml * 2ml extract/1.9999 g * 1000 g/kg * Img/1000 ug 6.47 mg/kg POAA Step 4: Example: Add Total Cone. of POAA detennined for Peaks "a" and "b"ss Total determined POAA (mg/kg) 6.47 mgflkg+0.43 mg/kg =6.90 mg/kg .,sKi OWH... 1 Y;- CIWK QS!^ TOB Mcsar > ^ o i-- s 0 0 Calculations R2382 103097 8:59 PM11/4/97 .?? ^ /a5" EID129599 R-2382-DuPontSoill Figure 1 R.2382-1 Soil- Standard Addition Curve fay/ml extract^ Cone. ofPOAA Spiked into Soil (ugfal) 0.05 0.10 0.25 0.50 0.75 FileD102897B Peak Area of Extracts-a 20000 25000 40000 71000 96000 FileD102897B Peak Area of Extracts-b 1000 3000 4000 9000 14000 FBe DI02897B File DI02897D Tola] Peak Area|Total Peak Area (a^b) frH>) 21000 28000 44000 80000 110000 Average of Initial & Final Curve 0.05 0.10 0.25 0.50 0.75 FileD102897D Peak-a 20000 27000 44000 71000 94000 FileD102897D Peak-b 1000 3000 4000 9000 14000 Extracted POAA Standard Curve iao - 0.00 0.10 0.20 OJO 0.40 0.50 POAA Cone. (ng/ml) 0.60 0.70 O.OT Curve Equation: Y-intereept 15000 Slope (m) 126000 X-mtercept -0.119 Indigent POAA analyte (Absolute value of X-intercept): 0.119 tig/mi ^ --* o <- 0 Soil 1 Curve ugml R2382 103097 9:00 PM11/4/97 SB 4 l^ EID129600 R-2382- DuPont Soil Data Figure! R.2382-1 Soil- Standard Addition Carve Analyzed bv ESMS nn 11/04/97 Cone. ofPOAA Spiked into Soil (ug/ml) 0.05 0.10 0.25 - 0.50 - - 0.75 FileDI10497B Peak Area of Extracts-a 21000 26000 41000 67000 94000 FileDI10497B Peak Area of Extracts-b 1700 3200 4400 ~~SEW~ 13700 FaeD110497B Total Peak Area (^b) 22700 29200 45400 -- 752001 " 107700 Curve Equadon: Y-intereept 16000 Slope (m) 120000 Indigent POAA analyte (Absolute value ofX-intercept): X-intercept -9.133 0.133 ll.04Curveugml R2382 103097 > ^ s hk 0 m o t0 8:58 PM11/4/97 ;n ^ U5' EID129601 3M Environmental Laboratory Volatiles and Seml-volatiles in Groundwater by Purge Trap Concentration with GC/MS Analyses (6/97 Sample^oR A" > ^ 0 S 30 4 \^ EID129602 ANALYTICAL SUMMARY Department: 3048 Lab Request: R2148 Project Description: DuPont Water Summary Prepared by: Dennis Seeger, Pace-1 Contract Lab: Pace-1 Project Lead: Dennis R. Seeger Sample Matrix: Water Date: 10/7/97 Analytical Tests Requested Twelve water samples were submitted for identification and quantitation of volatile organic sample components by purge and trap sample concentration with gas chromatography/mass spectrometry (GC/MS) analysis. Analytical Results The results of me GC/MS analyses are reported in Appendix A. After an- initial analysis of the undiluted samples, appropriate dilutions were analyzed for quantitative determinations of trichlorotrifluoroethane and trichloroethene. Where the calculated concentrations were below me practical quantitation limit (J footnote), me reported values should be considered as estimates. wyy-w^ ui, far q; wacssv. e awsktored a Analytical Summary nrw Gas Chromatography Methods Summary The samples were analyzed using the GC/MS instrument and sample concentrator conditions listed below. Procedure GC/MSParameters (Instrument ID "Alphie") Sample Concentrator: Tekmar model 2000 sample concentrator and model 2050 vial autosampler. Trap: Carbopack B/Carboxen 1000 & 1001 (Vocarb 3000) ^ Purge time: llnun. W Purge gas flow: 40mLAnin. 2 Desorbtime: 0.5 min. S Desorbtemp.: 270 "C S Desorb flow: 30 mL/min GC column: Restek RTx-624,60 m x 032 mm I.D., 1.8 urn fitel thickness. nft$ 3\ ^ US' EID129603 GC conditions and oven temperature program: Initial temp.: Oven temp. ramp: Injection, port temp.: Interface temp.: Purge B: Head pressure: Split flow: 40''C; 2.0 min. hold ll-C/min. to 220C; 250C 250C Initial value ON 19.6 psig 30 mL/min. 1.0 min. hold Mass spectrometer: Solvent delay: Electron multiplier Scan range: Scans per second: Scan threshold: 2.2 min. 2053 volts 35to260amu 2.17 soo Instrument Calibration *' "- Prior to sample analyses, the analysis of 50 ng ofbromofluorobenzene (BFB) demonstrated the accuracy and resolution of the mass spectrometer. A calibration check standard containing each of the target analytes at me midpoint concentration of me most recent five level calibration curve was analyzed to demonstrate acceptable instrument response for target analyte quantitation. A blank water sample water sample was analyzed to demonstrate analytical system cleanliness. All quality control analyses satisfied me criteria specified for analyzing samples by EPA method 8260. J Closing <;; ,..: . -^sf-^: ^'1' This analytical summary and associated analytical results have been reviewed Wdiaretapproved for release. Dennis R. Seeger, Project (612)778-6093 3^. < /^5" EID129604 Appendix A: Report of Laboratory Analysis < ^ <" > en a 0 t--t 0 v 0 0\ 33^ ^5' EID129605 Method 8260 Results for R2148 Compound Dichtorodifluoromethane Chloromethane Vinyl Chloride Bromomethane Chloroethane Trichtorofluoromethane Ethyl Ether Trichlorotrifiuoroethane Acrolein 1,1-Dichloroethene Acetone Isopropy! Alcohol Carbon Disulfide Allyl Chloride Methylene Chloride tert-Butyl Alcohol tert-Methyl Butyl Ether trans-1,2-Dichloroethene Acrylonitrile IsopropyI Ether 1,1-Dichloroethane 2.2-DichIoropropane Ethyl Acetate cis-1,2-Dichloroethene 2-Butanone 2-Butanol Bromochloromethane Tetrahydroftiran Chloroform 1.1,1-Trichloroethane Carbon Tetrachloride 1,1 -Dichloropropene Isobutanol Benzene 1,2-Dichloroethane n-Butanol Trichloroethene 1,2-Dichloropropane Dibromomethane Bromodichloromethane 2-Chtoroethyl Vinyl Ether 2-Nitropropane cis-1.3-Dichtoropropene 4-Methyl-2-penlanone Toluene 4-Methyl-2-Pentanol PRL Sample Concentrations (ug/L) (ugfl.) R2148-1 R2148-2 R2148-3 R2148-4 R2148-5 R2148-6 10 - - - - - 10 10 10 10 - 10 -->- 5 5 820 - - - - - - 40 5 10 60 ----------- 5 - ------- 5 - - 730 10 - - 16 1600 - - - 18 1500 3.7J - - - 26 2300 7.8 J - 26 2400 8.0 J 5 2.7J 2.9J - - 2.3J 2.7J 20 59 49 - ------ 5 5 2.911 3.0 J 40 - - - - - 5 - - 5 - 5 - - - - - 10 - - - - - 5 3.3 J 3.5 J 10 - - - - - 60' 5 10 5 5.5 5.9 5 14 14 5 ----------- 5 - - - - - 100 - 5 .- - - - - 5 - - - - - ------------ 100 - - - - - 5 1.8 J 1.5 J 140 150 520 570 5 - - 5 - - - - - 5 - - - - - 10 - - - 10 - - ^ 5 - - - - - 10 - . - 5 - - - - - 60 - PRL -- Practical Quantitafion Limit J - The concentration is below the practical quantisation limit EID129606 Method 8260 Results for R2148 PRL Compound trans-1,3-Dichloropropene 1,1,2-Trichloroethane Tetrachloroethene 1,3-Dichtoropropane 2-Hexanone Dibromochloromethane 1,2-Dibromoethane Chlorobenzene Ethylbenzene 1,1,1,2-Tetrachloroethane m & p-Xytene o-Xylene Styrene Bromoform IsopropyI benzene Cyclohexanone 1,1,2,2-Tetrachloroethane Bromobenzene n-PropyI benzene 1,2,3-Tricnloropropane 2-Chlorotoluene 1,3,5-Trimethylbenzene 4-Chlorotoluene tert-Butyl benzene 1,2,4-Trimethylbenzene sec-Buty (benzene p-lsopropyitoluene 1.3-Dtehlorobenzene 1.4-Dichlorobenzene n-Butyl benzene 1,2-DichIorobenzene 1,2-Dibromo-3"Chtoropropane 1,2,4-Trichlorobenzene Hexachlorobutadiene Naphthalene 1,2,3-Trichlorobenzene ;ug/L) "5" 5 5 5 10 5 5 5 5 5 5 5 5 5 5 60 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 R2148-1 3.6 J Sample Concentrations (ug/L) R2148-2 R2148-3 R2148-4 R2148-5 1.1 J 5 1.7 J 1.8 J R2148-6 5.2 > w a 0 I--t 0 u 0 00 PRL ~ Practical Quantitation Limit J - The concentration is below the practical quantitation limit Page5 3^4 /AfT EID129607 Method 8260 Result-3 for R2148 PRL Sample Concentrations (ug/L) Compound (uga.) R2148-7 R2148-8 R2148-9 R2148-10 R2148-11 R2148-12 Dichlorodifluoromethane Chtoromethane Vinyl Chloride Bromomethane Chloroethane Trichiorofluoromethane Ethyl Ether Trichlorotrifluoroethane Acroiein 1,1-Dichloroethene Acetone IsopropyI Alcohol Carbon Disulfide Ally! Chloride Methylene Chloride tert-Butyl Alcohol tert-Methyl Butyl Ether trans-1,2-DichIoroethene Acrylonitrile IsopropyI Ether 1,1-Dichtoroethane 10 10 10 10 10 - 10 5.9 ----------- 5 5 760 670 - 40 5 - - - - - 10 6.7,1 10 60 5 5 ------ 5 20 5 -----.-?-'"---- 5 40 5 - - ------.------ 5 - 130 - 140 - - 32 J - 1.8 J 5.6J - " '- "'"' :.,ft^.- -,-;;.; :.;<- - - 2,2-Dtehloropropane 5 Ethyl Acetate 10 cis-1,2-Dichloroethene 5 2-Butanone 10 2-Butanol 60 Bromochloromethane 5 Tetrahydrofuran 10 Chloroform 5 1,1.1-Trichloroethane 5 Carbon Tetrachloride 5 1,1 -Dichtoropropene 5 Isobutanol 100 Benzene 5 1,2-Dichloroethane 5 n-Butanol 100 Trichloroettiene 5 1,2-Dichloropropane 5 Dibromomethane 5 Bromodichioromethane 5 2-Chloroethyl Vinyl Ether 10 2-Nitropropane 10 cis-1,3-Dichioropropene 5 4-Methyl-2-pentanone 10 Toluene 5 4-Methyl-2-Pentanol 60 PRL - Practical Quantitation Limit - - -Ss - 5.8 5.9 2.7 J 2.6 T0^"' - - - - -atanong -~,f^: 37 39 13 16 6.3 6.2 - 5.8 - ------... - - - - >wtimv- ------- 81 66 - - ------ . - - - ------ , - - - - ------------------------ - - - - J - The concentration is below the practical quantitation limit EID129608 Method 8260 Results for R2143 PRL Compound trans-1,3-Dichtoropropene 1.1,2-Trichloroethane Tetrachloroethene 1,3-Dichloropropane 2-Hexanone Dibromochloromethane 1,2-Dibromoethane Chlorobenzene Ethyibenzene 1,1,1,2-Tetrachloroethane m & p-Xylene o-Xylene Styrene Brornofonn Isopropyi benzene Cyclohexanone 1,1,2,2-Tetrachloroethane Bromobenzene n-PropyI benzene 1,2,3-Trichtoropropane ;"8fl-) 5 5 5 5 10 5 5 5 5 5 5 5 5 5 5 60 5 5 5 5 2-ChIorotoluene 5 1,3,5-Trimethylbenzene 5 4-Chlorotoluene 5 tert-Butyl benzene 5 1,2,4-Trimethylbenzene 5 sec-Butylbenzene 5 p-lsopropyitoluene 5 1.3-Dichlorobenzene 5 1.4-Dichlorobenzene 5 n-Butyl benzene 5 1,2-Dichlorobenzene 5 1,2-Dibromo-3-Chloropropane 5 1,2,4-Trichlorobenzene 5 Hexachlorobutadiene 5 Naphthalene 5 1,2,3-Trichtorobenzene 5 R2148-7 4.8 J Sample Concentrations (ug/L) R2148-8 R2148-9 R2148-10 R2148-11 R2148-12 5.8 W'W'Bft"t''^! mz'3 ^ s I--t o m i-- 0 PRL - Practical Quantftation Limit J - The concentration is below flie practical quantitation limit Page 7 37 ^ US- EID129609 3M Environmental Laboratory Volatiles by AED (5/97 Samples) w 38 ^ W EID129610 3M Environmental Laboratory Data Transmittsil Summary Preliminary ^va^ (circle one) Lab Request #: 3M Study #: R?.<iW_____^'ysi^^S g^ne-yii/^ iDate Received: |Spons6orr Client: Representative Name Company Name Company Address Phone PtA^O/l^ oject Lead: Name / Phone hWl ^vi i'Sio^l^ roup Leader: Name/Phone JDJohnson/85294 .yte(s) or Test Method #: p0 A A [SampleMatrix: \^i \^r\ So 11 Analysis Dates: (M^tT- iJ>WC^ Analyst(s): Author: SFMi'll^.^ S Ml 11^ Data Reviewed by: Project Lead (or designee): James D. Johnson (or designee): Contract Laboratory! JDJ: QAU (Archives): LIRN System: Project Manager: ^ufc 8^^.&h Others (List Recipients /Address /Phone /FAX) Sent by:/Date A copy of the report including this form and the client cover page is to be given to QAU, URN and to the Group Leader. 31 ^ US' EID129611 3M Environmental Laboratory - Advanced Method Development Team Contact: KrisHaasen Bilildmg 02-3E-09 612-778-6018 kjhansen@mmm.com Final Report - Lab Request R2008 DuPont Water and Soil Samples 07 November 1997 1.0 SUMMARY Five water samples and eigteNl^lw%>l^fi^ DuPont wire analyzed fo^heia: presence of fluorine, chlorine, bromine, carbon, and hydrogen using headspace samplings and gas chromatography coupled with an atomic emission detector (GC/AED). The samples were analyzed on two different columns, a DB-5 and a DB-624. Standard curves were generated during each analysis. Very little was seen in the samples and the compounds that were detected existed at levels below the lowest standard. wa'Wft; '">a tevt-;i 2.0 INTRODUCTION ^ff' .-Five water8 samples and ei^^^^^ft^te&Werereceived <3|QBiiDuPont under . request #2008. The samples were to^be analyzed for the presence of perfluorooctanoic i,"'p acid anion (POAA). However, since it is not volatile, POAA was not detected using GC/AED. A headspace sampler was used to introduce any volatile or semi-volatile components of&e samples into the GC/AED. The samples were monitored for fluorine (F690), bromine (Br478), chlorine (C1479), hydrogen (H486), and carbon (C496). ae 3.0 TEST MATERIALS The five water samples were labeled on large amber glass bottles as follows: Lab Request ff # of Bottles Sample Description R2008-1 1 DuPont Wash. Works RanneyWell FC143 1:48 pm R2008-2 1 DuPont Wash. Works Ranney Well FC143 1:48 pm R2008-3 R2008-4 R2008-5 1 DuPont Wash. Works RanneyWell FC143 l:50pm > 1 DuPont wllftrWiltks RanneyWetI FC143 l:50pm CO 1 DI Water h--t 0 Ul I--A lA> 3M Environmental Laboratory, Lab Request 82008 Page 1 of 5 yo ^ ^sr EID129612 The eight soil samples were labeled on 1L plastic containers as follows: Lab Request # R2008-6 # of Containers_____________Sample Description____________ 8 DuPont Washington Dirt 5/30/97 11:00 All samples were refrigerated at approximately 4C until sample preparation and analysis. 4.0 EXPERIMENTAL-OVERVIEW Sample Preparation The water samples were prepared by pipetting lOmL of each sample into 20mL glass headspace vials. Each sample was "salted" by adding approximately 2 to 3 grams of sodium chloride (this was done to increase me ionic strength of the solution). The soil samples were prepared by transferring 10 0.5 grams of soil (weight recorded) into headspace vials. The soil samples were not salted. . av.sp^^ - The standard curves were prepared using two differenfflatandards, para- bromolhiorobenzene (p-BFB) and ortho-dichlorobenzene (o-DCB).' u'Fhe-p-BFB was prepared in acetone and the o-DCB was prepared in methanol. The standardsavere spiked into lOroL Milli-Q water at levels of 25pl, 50ul, and lOOul. Acetone arid methanol spikes (lOOp! each) in lOmL Milli-Q as well as a lOmL WM-Q blank were also analyzed, "rt Since all eight containers of soil were me same, three of the eight samples were used to make a standard curve. These were spiked exactly as me watetswere. One soil sample was spiked with acetone and methanol, leaving fouriiCon^iDap ,ofi.soil to be treated as "samples." '* r * - Because two different columns were used and all five elements could not be monitored simultaneously, the water and soil samples were prepared four separate times. Each time a standard curve was generated. When just F690 was monitored, the standard curve was generated based on p-BFB. When all other elements were monitored, two standard curves were generated, using p-BFB and o-DCB. SSrn ti-.ir Instrumentation and Operating Conditions Headspace Sampler. Hewlett Packard 19395A Settings: Bath Temperature 85C Valve/Loop Temperature 140C Probe in, tas 1 second Vial Pressurized, t = 3 seconds to 13 seconds Vent/Fill Loop, t = 14 seconds to 19 seconds Inject into GC, t = 20 seconds to 50 seconds Probe out, t = 51 seconds Packed column on vent 3M Environmental Laboratory, Lab Request R2008 Page 2 of 5 ^i i i^~ EID129613 Gas Chromatograph: Hewlett Packard 5890 Series n Column: DB-5 (J&W Scientific) 30 x .25 x .25, serial # 2633586 Oven Program: 1 min @ 60, 10/nun to 300 for 5 min (F690) 1 min @ 40, 10/min to 300 for 5 min Column: DB-624 (J&W Scientific) 30 x .32 x 1.8, serial # 5812142 Oven Program: 1 min @ 40, l0fvaa to 200 for 5 min Injection Port: 225C, split Atomic Emission Detector: Hewlett Packard 5921A "Flo" GC Block/Transfer Line Temp 275 Cavity Block Temp 275 5.0 DATA ANALYSIS SAMPLE SESULTS: Lab Request # Column R2008-1 DB-5 R2008-2 DB-5 R2008-3 DB-5 R2008-4 DB-5 R2008-5 DB-5 R2008-6 DB-5 'minimum quanritatioc limit Element F _____ _____Results*.^ no peaks detected F no peaks detected F no peaks detected F no peaks detected F no peaks detected F no peaks detected 0.280 ppm F in water, 0.282 ppm F in soil Lab Request # R2008-1 Column____Elements______________Results*__________ DB-5 H,C,Br,Cl no peaks detected R2008-2 DB-5 H,C,Br,Cl no peaks detected R2008-3 DB-5 H,C,Br,Cl no peaks detected R2008-4 DB-5 H.C.Br.Cl no peaks detected R2008-5 DB-5 H,C,Br,Cl no peaks detected R2008-6 DB-5 H,C.Br,Cl________no peaks detected_____ *minimum quantitation limits: 1.176 ppm Br in water, 1.220 ppm Br in soil .inuMw 'nmwsf 1.408 ppm Cl in water, 1.461 ppm Cl in soil Lab Request ft R2008-1 DCBo-6lu2m4 n____ElFement__________n_o_p_eRakessduelttesc*te_d________ R2008-2 DB-624 F no peaks detected R2008-3 DB-624 F no peaks detected R2008-4 DB-624 F no peaks detected R2008-5 DB-624 F no peaks detected ._________no R2008-6 DB-624_____F peaks detected minimum quantitation Kmit: 0.280 ppm F in water, 0.282 ppm F in soil 3M Environmental Laboratory, Lab Request R2008 Page 3 of 5 EID129614 Lab Request # R2008-1 Column DB-624 R2008-2 DB-624 R2008-3 DB-624 R2008-4 DB-624 R2008-5 DB-624 R2008-6 DB-624 minimum quantitation limits: Elements Results* H,C,Br,Cl peaks detected on Cl channel (below mql), no peaks on other channeb H,C,Br,Cl H,C,Br,Cl H,C,Br,Cl peaks detected on Cl channel (below mql), no peaks on other channels peaks detected on Cl channel (below mql), no peaks on other channels peaks detected on Cl channel (below mql), no peaks on other channels H,C,Br,Cl no peaks detected H,C,Br,Cl no peaks detected 1.176 ppm Br in water, 1.187 ppm Br in soil 1.408 ppm Cl in water, 1-253 ppm Cl in soil STANDARD CURVES: The following are examples of standard curves taken from the analyses: F Curve for DuPont Soil (OB-5) 200 Cl Curve for DuPont Water (DB-624) 15000. 3M Environmental Laboratory, Lab Request R2Q08 Page 4 of 5 EID129615 6.0 CONCLUSION Qualitative analysis of DuPont water and soil revealed very little was present in any ofstahme pslaems pBle2s0.0C8l--1cotnhtraoiunginhgRc2o0m0p8o-u4n. dsTwheerleevfoeulsndofutshinegsethceoDmBpo-6u2n4dscowleurme nniont standard. water quantitated because they were present in levels below the lowest 7.0 MAINTENANCE OF RAW DATA Hard copies of the data are filed in the AMDT archive. SB Miller 110797 3M Environmental Laboratory, Lab Request R2008 Page 5 of 5 EID129616 Environmental Laboratory Volatiles by AED (6/97 Samples) ys-^ /a5- EID129617 3M environmental T.aboratorv Data Transmittal Summary Preliminary \inal^cfrcte one) Lab Request #: PO.I1^ JDateReceived: (^-^S/H- |SponsoorrClient: Representative Name Company Name pu-Powt- Company Address Phone project Lead: Name/Phone KHo^^M/ ^b^ Group Leader: Name / Phone JDJohnson/85294 _ . , , , . . , , ^ ^ " ^ l l l B H " B " " i ! i l ! " " " " l ^ Sample Matrix: Wd.+&r j C^iCL-hliS. +suni-wil<!t-^ie Analysis Dates: ^dc^-li^^f Author: S^MiIkv Analyst(s): SCMl'1^ Data Reviewed by: PA ^t.+^W)i? lv><f~h^~f Project Lead (or designee): : James D. Johnson (or designee): .'siasot, JDJ: QAU (Archives): JLIRN System: project Manager: S(AtB<Ac4^ Others (List Recipients /Address /Phone / FAX) Sent by:/Date > S w 0 1^1 I--* SO A copy of the report including this tonn and the client cover page is to be given to QAU, URN and to the Group Leader. Hh 4 ^-5- EID129618 3M Environmental Laboratory-Advanced Method Development Team Contact: KrisHansen Building 02-3E-09 612-778-6018 kjhansen@nuam.com Final Report - Lab Request R2148 DuPont Water Samples 07 November 1997 1.0 SUMMARY Twelve water samples were received &om DuPont on July 2,1997. The sami^a, were %||^|fcfi)rithe jsresence of;,flu@rine, chlorine, bromine, cai^^g|in^ihi^r<peae,-^;. itefiS^&e sampling and gas-chrbmatography coupled wifli%|a|^cg^B^sg^riB^ . ,,, using ,. ,,s detector (GC/AED). The samples were analyzed on two different columnsyaggB-5 aadsftnpiK DB-624. Standard curves of no less than R^^ were generated during each analysis- if Column DB-5 Samples 1-8 Results Description halogenated organics low levels of halogenated organics C only detected DB-624 1-8 halogenated organics DB-624 9-10 low levels of halogenated organics DB-624 11-12 C and F only detected *reported as total ppm per sample '' _0_.2_3-1_.3_p_p_m_P,_0_.29_-0_.8_6_pp_m_C_, _^w;i;:t;.s:, 0.39-2.5 ppm Cl ^,^ 0.32-0^3.5ppm C, F and^l areas Igss. ^ ^ than low standard response C area less than low standard response 0.23-1.1 ppm F, O^'M.50 ppm C, 0.45-3.6 ppm Cl 0.082 ppm F (#10), F, C, and Cl areas less than low standard response .. ,,,,,, C and F areas less than low standard response Bromine was not detected in any of the samples on either column. Hydrogen was detected in four samples on me DB-5 and in one sample on the DB-624. > gCO ^--t 0 Ln to 0 3M Environmental Laboratory, Lab Request R2148 Page 1 of 8 H7 4 l^S' EID129619 S IWB C <(B?Si:;BW ^S^ess te ..taaww 5KM 2.0 INTRODUCTION Twelve monitoring well water samples were received from DuPont under lab request R2148. The samples were to be analyzed for the presence of organofluorines. A headspace sampler was used to introduce any volatile or semi-volatile components of the samples into a GC/AED. The samples were monitored for fluorine (F690), bromine (Br478), chlorine (C1479), carbon (C496), and hydrogen (H486). 3.0 TEST MATERIALS The water samples were received in amber glass bottles and labeled as follows: 3M Lab Request # B2148-1 R2148-2 R2148-3 R2148-4 R2148-5 R2148-6 R2148-7 R2148-8 R2148-9 R2148-10 R2148-11 R2148-12 Sample Description MW-1 lof2 MW-1 2 of 2 MW-2 lof2 MW-2 2 of 2 MW-3 lof2 MW-3 2 of 2 MW-4 1 of 2 MW-4 2 of 2 MW-5 lof2 MW-5 2 of 2 MW-6 1 of 2 MW-6 2 of 2 All samples were refrigerated at approximately 4C until sample preparation and "we v.n analysis. 4.0 EXPERIMENTAL-OVERVIEW Sample Preparation The water samples were prepared by transferring approximately lOmL of each sample into tared headspace vials containing approximately 4 0.1 grams of sodium chloride. The vials were rewieghed to get the weight of the water. This was done instead of pipetting an exact volume so that exposure to air was kept to a minimum, and the possibility of losing volatile components reduced. S Standard curves were prepared using two different standards, para- > bromofluorobenzene (p-BFB) and ortho-dichlorobenzene (o-DCB). Two standard curves CO were necessary so calibration curves could be generated for all elements of interest t-^ fluorine, carbon, hydrogen, and bromine from p-BFB; carbon, hydrogen, and chlorine gi ^- from o-DCB. The p-BFB was prepared in acetone and the o-DCB was prepared in mefhanol. The standards were spiked into lOmL Milli-Q water (salted) at levels of5uL, 3M Environmental Laboratory, Lab Request R2148 Page 2 of 8 48 ^ IAS' EID129620 25uL, 50uL, 75uL, and lOOpL. Acetone and methanol spikes (lOOuL each) in lOmL Milli-Q as well as a lOmL Mflli-Q blank were also analyzed. The combination of two columns (the DB-5 is good for late eluting compounds and the DB-624 is used to separate compounds that elute relatively quickly) yielded a thorough analysis for each sample. Because two different columns were used and all five elements could not be monitored simultaneously, the samples were prepared four separate times. When just F690 was monitored, me standard curve was generated based on pBFB. When all other elements were monitored, two standard curves were generated, using both p-BFB and o-DCB. The final results for fluorine, carbon, hydrogen, and bormine were based on p-BFB. The chlorine curve was based on o-DCB. Instrumentation and Operating Conditions Headspace Sampler: Hewlett Packard 19395A Settings: Bath Temperature 85C Valve/Loop Temperature 140C Probe in, t = 1 second Vial Pressurized, t = 3 seconds to 13 seconds Vent/Fill Loop, t = 14 seconds to 19 seconds Inject into GC, t = 20 seconds to 50 seconds Probe out, t == 51 seconds Packed column on vent Gas Chromatograph: Hewlett Packard 5890 Series H Column: DB-5 (J&W Scientific) 30m x .25mm x .25vm, serial #2633586 Oven Program: 1 min @ 40, 10/nun to 300 for 3 min Column: DB-624 (J&W Scientific) 30m x .32mm x 1.8(im, serial # 5812142 Oven Program: 1 min @ 40, l0/minto 240 for 5 min Injection Port: 225C, split Atomic Emission Detector: Hewlett Packard 5921A "Flo" tss. t-ssxasat la.eatifcl Mtel l Ww w 3M Environmental Laboratory, Lab Request R2148 > I to to Page 3 of 8 ^ ^ ^- EID129621 5.0 DATA ANALYSIS SAMPLE ANALYSIS: Column: DB-5 Lab Requests________________F690* R2148-1 0.23 ppm, 1 peak < low std. response R2148-2 0.23 ppm, I peak < tow ad. response R2148-3 0.079 ppm, 0.55 ppm R2148-4 0.34 ppm, 1 peak < low std. response R2148-5 0.26 ppm, 0.57 ppm R2148-6 0.39 ppm, 0.90 ppm R2148-7 0.066 ppm, 0-21 ppm R2148-8 0-075 PP"i> 0-22 ppm R2148-9 2 peaks < tow std. response R2148-10 2 peaks < low std. response R2148-11 none detected R2148-12 none detected *low standard concentration: 0.056 ppm F Column: DB-624 Lab Request R2148-1 #_____________0-2_6_pp_m_F_, 3Fp6ea9ksB< *low std. response R2148-2 0-23 ppm P, 3 peaks < low std. response-s-..,, R2148-3 0.075 ppm, 0.44 ppm F, 2 peaks < low std. response R2148-4 0.074 ppm, 0.42 ppm F, 2 peaks< low std. response R2148-5 0.086 ppm, 0.27 ppm, 0.70 ppm F, 3 peaks < low std. response R2148-6 0.080 ppm, 0.23 ppm, 0.59 ppm F, 3 peaks < tow std. response R2148-7 0.087 ppm, 0-20 ppm F, 2 peaks < tow std response R2148-8 0.083 ppm, 0.16 ppm F, 2 peaks< tow std. response R2148-9 5 peaks < tow std. response R2148-10 R2148-11 R2148-12 0.082 ppm F. 4 peaks < tow std response 1 peak < tow std. response none detected "same low standard concentration as above 3M Environmental Laboratory, Lab Request R2148 Page 4 of 8 EID129622 Column: DB-5 Lab Request # R2148-1 R2148-2 R2148-3 C496* 1 peak-slow std. response 1 peak < low std. response 0.43 ppm H486* none detected none detected none detected R2148-4 R2148-5 0.39 ppm, 3 peaks < low std. response 0.32 ppm, 0.42 ppm, 2 peaks < tow std. response 1 peak < low std. response 0.13 ppm, 2 peaks < low std. response C1479* 0.39 ppm 0.46 ppm 1.2 ppm, 2 peaks < low std. response 1.0 ppm, 2 peaks < low std. response 0.43 ppm, 1.2 ppm, 031 ppm R2148-6 0.36 ppm, 0.50 ppm, 2 peaks < low std. response 0.078 ppm, 2 peaks < low std. response 0.54 ppm, 1.6 ppm, 0.40 ppm R2148-7 0.29 ppm, 2 peaks < low std. response 1 peak < low std. response 0.46 ppm, 2 peaks < low std. response R2148-8 2 peaks < low std. response none detected 0.46 ppm, 2 peaks < low std response R2148-9 0.32 ppm, 2 peaks < low std. response none detected 2 peaks < low std. response R2148-10 035 ppm. 2 peaks < low std. response none detected 2 peaks < tow std. response R2148-11 1 peak < low std. response. none detected none detected R2148-12 I peak < low std. none detected none detected response *low standard concentrations: 0-21 ppm C, 0.060 ppm H, 03,3 ppm Cl, 0.24 ppm Br Br478* none detected none detected none detected none detected none detected none detected none detected none detected none detected none detected^--' ^TiChi nonedete'Btea'-aw .'i'- none detected 3M Environmental Laboratory, Lab Request R2148 Page 5 of 8 5-1 4 /^ EID129623 >: < me.i.-'!!d s, twitesetwa. Column: DB-624 Lab Request # R2148-1 C496* 1 peak < low std. response R2148-2 1 peak < low std. response R2148-3 0.24 ppm. 1 peak < low std. response R2148-4 Ipeak < low std. response R2148-5 0.34 ppra, 3 peaks < low std. response R2148-6 0.50 ppm, 3 peaks < low std. response H486* none detected none detected none detected none detected none detected lpeak<low std. response R2148-7 2 peaks < low std. response R2148-8 2 peaks < low std. response R2148-9 1 peak < low std. response R2148-10 1 peak < low std. response R2148-11 1 peak < low std. response R2148-12 1 peak<Iowstd- response *same low standard concentrations as above none detected none detected none detected none detected none detected none detected C1479* 0.57 ppm Br478* none detected 0.45 ppm none detected 12 ppm none detected 1.0 ppm none detected 0.40 ppm, 1.6 ppm, 0.42 ppm 0.57 ppm, 2.4 ppm, 0.58 ppm, 1 peak < low std. response 0.45 ppm, 1 peak < low std. response 0.66 ppm, 2 peaks < tow std. response 3 peaks < low std. response 3 peaks< low std. response none detected none detected none detected none detected none detected none detected none detected none detected none detected none detected All results were normalized, assuming the density of water = Ig/mL. 3M Environmental Laboratory, Lab Request R2148 Page 6 of 8 Ss. 4 l^S~ EID129624 STANDARD CURVES: Example of a standard curve from the analysis (all standard curves had R2 of 0.99 or greater): 3000 F Curve for R214S (DB-624) 0.2 0.4 0.6 0.8 ppmF 6.0 CONCLUSIONS Twelve water samples were analyzed on two different columns with a GC/AED. More fluorine was detected using the DB-624 than the DB-5; in the DB-5 analysis, more carbon, hydrogen, and chlorine were detected. All of me samples evidence of at least one of the elements targeted. Many peaks were detected but not quantitated because the peak ; area was less than the low standard response for that element. :'e aeoacp;a were ;ia% "ssiMss';: fo 7.0 MAINTENANCE OF RAW DATA ( W (MM Copies of all data will be filed in the AMDT archive. "A 8.0 APPENDICES . Appendix A: Chromatogram of sample 6 (MW-3 2 of 2) F690 DB-624 SEMiller 110797 3M Environmental Laboratory, Lab Request R2148 > I o >-n ts) o\ Page 7 of 8 S3 ^ U5" EID129625 Appendix A: Chromatogram of sample 6 (MW-3 2 of2) F690 DB-624 F G90 of 1300T:F021R13R.D 40- 30^ 2010- 6 3 10 20 . Ti me (in in. ) - FB90ofl300T:F02lR13R.D 40- 30 ''S6S c!{ ''';r t 30- 2010- A 1 2 3Time (min.) 3M Environmental Laboratory, Lab Request R2148 Page8of8 ^ - > S 2 5 u> fro ^ ^/^5- EID129626 Environmental Laboratory Total Fluorlde in Soil (6/97 Samples) S5' ^ l^ EID129627 3M Environmental Laboratory Data Transmittal Summary Preliminary / Final (circle one) pate Received: 06/06/97 Sponsor or Client: Roger Zipfel Dupont Washington Works Plant 'reject Lead: Name / Phone Kris Hansen / (612) 778-6018 (s) or Test Method #: Total Fluoride .ample Matrix: Soil Analysis Dates: 9/29/97 through 10/01/97 Analyses): Daniel Howman SAuthor: Daniel Howman Data Reviewed by: Kris Hansen ;'rms.es ' Internal Reviewer: James D. Johnson QAU (Archives): Rich Youngblom LIRN System: Denise Appleton Project Manager: Sue Beach Others (List Recipients /Address / Phone / FAX) jProjectLead: Kris Hansen Sent by: / Date DRH/11-07-97 Sent by:/Date DRH/11-07-97 A copy of the report including this form and the client cover page is to be given to QAU, LIRN and to the Group Leader. JT4 ^ l^S- EID129628 : / Pate 3M Environmental Laboratory - Kris Hansen - ST. Analytical Chemist Advanced Method Development Team Building 2-3H-09 612-778-6018 kjhansen@mnun.com Advanced Method Development Team Final Report Determination of Total Fluoride in Soil Laboratory Request R2382 1.0 SUMMARY Eleven soil samples from Dupont, Washington Works Plant were submitted to the Environmental Laboratory for analysis of total fluoride. The samples were submitted under Lab Request No. R2382, samples 1 ttaough 11. The samples were analyzed using an Orion EA 940 Expandable Ion Analyzer after combustion using a Dohrmann DX2000 Organic Halide Analyzer modified for fluoride analysis. H sums -aaiysis o' s & The following table contains a summary of the results. The Total Fluoride values are the average of three replicates of the same sample, and are given in the table along with the "sae <sa"nD1- standard deviation of the three replicates. Total fluoride is defined as me concentration of ^)iU:%(&S- (t.- F- measured following complete e^^^^oiofthesample. l - net Wit-steals ^ Summary Table: Soil Samples from Diupont W ashingtonR2M12 S Nuoride^^weRQ^myKg): Standard Deviation: 2800 2400 4200 6000 2100 1400 Fluoncte^^werag^myKg): Standard Deviation: 4900 3600 1400 2200 1600 1 "'"tlw '.'y, > 2.0 TEST MATERIALS W The soil samples were sent from Dupont, Washington Works Plant, and received at me o i/i m Environmental Laboratory in St. Paul on 6/6/97. The samples were logged in under Lab 0 Request R2382, samples 1 through 11. Samples were refrigerated at 4C undl analysis. Analyst/Date Daniel Howman /10-1-97 Page 1 of 7 S? ^ ^5" EID129629 3.0 INSTRUMENTATION A. Dohrmann DX2000 Organic Halide Analyzer modified for fluoride analysis OPERATING CONDITIONS Combustion tube temperature= 950" C Oxygen and Helium flow = 50 cc/minute - ,;yr " di Vaporization/Drying time = 240 seconds Bahe time = 300 seconds Collection fluid = 3.0 mL of 1:1 TISAB/Mffli-Q H^O B. Orion EA940 Expandable Ion Analyzer with Orion 9609BN Combination Fluoride Electrode 4.0 EXPERIMENTAL OVERVIEW: Total Fluoride Determination 4.1 Standards A standard curve was prepared from Amonium Perfluorooctanoate (POAA) stock solution (S397-420) at the following concentrations: 25,50, 250,500,1000 ppm POAA in MeOH. For each sample, 0.2mL of soil was extracted thermally with the Dohrmann DX2000 Organic Halide Analyzer. The EOX-Liquids computer program was used for the standard extraction. Standards were prepared and analyzed in triplicate. The extraction products of the standards were collected in 3 mL of 1:1 TISAB II/H^O. The collection vial was placed so that the tip of the combustion tube was in me collection fluid. Gases released during pyrolysis bubble through the collection fluid; the F- partitions into the collection fluid. :'i :._ , The concentration of fluoride in the collection vial was determined by direct measurement with the Orion EA940 Expandable Ion Analyzer with Orion 9609BN Combination BRulaaaaeeteode. The Orion E&940 was ^ calibrated by direct measurement with no blank correction, using standards with a concentration of 0.1,0.5,1.0,1.5,5.0 ppm P. Standards were prepared using Coming SodiutEeStearide?^TN-A-0572) and diluted in 1:1 TISAB BE/HA ----------- * w. ' - 4.2 Blanks Prior to analysis of the samples and standards, O.lmL ofMilli-Q was S extracted on the Dohrmann DX2000 Halide Analyzer in the same way as ^ the standards to insure the system was free of any fluoride contamination. 5 Total fluoride was then measured on me Orion EA940. Analyst/Date Daniel Howman /10-1-97 Page 2 of 7 S-8 ^ )^S~ EID129630 4.3 Samples For sample analysis, 0.02 gram samples of soil were extracted in triplicate on the Dohrmann DX-2000 in fbe same way as the standards. The EOXSolids computer program was used for sample extraction. The concentration offluoride extracted was determined by direct measurement with me Orion EA940. 5.0 DATA ANALYSIS: Total Fluoride determination 5.1 Standards A standard curve was developed using the POAA standard solutions (see appendix). The fluoride content of POAA is 66.10%, thus, the concentration offluoride in me standards was determined by multiplying the concentration of POAA by 66.10%. Concentration ofF- = (Standard concentration) * (0.661) Concentration ofF- = (25ppm POAA) * (0.661) Concentration ofF- in 25ppm POAA = 16.5ppm These calculated values were plotted and a standard curve calculated using linear regression. The equation of the regression is y = 0.0067x - 0.1061. A linear correlation coefficient of 0.9962 was obtained for the standard range of 25 -1000 ppm APO. 5.2 Blanks No further analysis was done on the blanks, siwias n ft. 53 Samples The Total Fluoride in me samples is reported as me average of triplicate sample analysis using the linear regression equation to correct for extraction efficiency (see appendix). Calculated F- (mg/L) = (Meter Reading + Intercept) / Slope Calculated F- (mg/L) = (Meter Reading ofR2382-l-l + 0.1061) / (0.0067) Calculated F- (mg/L) = (0.8047 + 0.1061) / (0.0067) Calculated F- ofR2382-l-l = 136mg/L Calculated F- (mg/Kg) = (Calculated F- (mg/L)) * (Collection Volume) / (Sample Weight) Calculated F- (mg/Kg) = (136mg/L) * (3ml) / (0.0203grams) Calculated F- (mg/Kg) = 20100mg/Kg Analysis blanks and calibration check standards were analyzed periodicallyto verify mat the system continued to operate properly. Analyst / Date Daniel Howman /10-1-97 Page 3 of 7 EID129631 6.0 CONCLUSIONS Triplicate analysis of the pyrolysrisproducts ofK2382-l to R2382-11 determined that fluorine is present in all samples. Total fluoride concentration varies fiom 20100ppm to 106,300ppm; data are summarized in the Summary Table (section 1.0). The highest levels of fluoride were found in R2382-5 and K2382-6 and the lowest levels^ in samples R2382-1 and R2382-2. Analyst/Date Daniel Howman /10-1-97 Page 4 of 7 (.0 ^ l^S~ EID129632 ASH01053 Standard Curve POAA 5.00000 4.50000 4.00000 3.50000 ,, 3.00000 - 1 &.wUUUU 1 A.UUUvU 1.50000 1.00000 y a O.OOt }7w , o j|o 61------ ^ R^ 0.9962 ^ " ^4------- ^^ Z ' 0.50000 n nnnnn . 0.0 100.0 200.0 300.0 400.0 Standard Concentration in F- (ug/L) ^ ^--- ^-- 500.0 600.0 Analyst / Date Daniel Howman /10-1-97 Page 5 of 7 Project R2382 Dupont Washington Soil Samples Calculations for Standard Curve Calculated F-(mg/L) Meter Reacftig Oldeefcn Vohime J Sampte Volume Sample ID DBulion Sample Volume (RiL^ Analysis: DRH 9-29-37 3C 4.33PPM ERA CHECK 2 3LANK-1 1 0.01 OLANK-2 BLANK-3 1 0.01 1 001 2SPPMW397-919 25PPM W397-919 25PPM W397-919 2SPPMW397-919 0.01 1 0.01 1 001 1 0.01 X31.0PPM CHECK 0.01 50PPMW397-92d' 0.01 50PPMW397-920 5UPPMW397-820 250PPM W397-821 1 1 0.01 aoi 001 250PPM W397-921 0.01 aCI.OPPM CHECK 1 BLANK-1 I BLANK-2 1 BUWK-3 1 25PPM W397-819 1 25PPM W397-919 1 25PPM W397-919 1 50PPMW397-920 1 50PPMW397.920 1 50PPMW397-920 1 QC1.0PPM CHECK 1 250PPM W397-821 1 250PPM W397-921 1 2SOPPMW397-S21 1 500PPMW3S7-922 1 500PPMW397-S22 1 SOOPPMW397-922 1 1000PPMW397-923 1 1000PPMW397-823 1 1000PPMW397-a23 1 QC1.0PPM CHECK 1 i NotebooK Reference: Cartton-SA-2. 0.20-21 0.02 0.02 0.02 0.02 002 002 002 002 0.02 0.02 0.02 002 0.02 002 0.02 002 002 0.02 Collection Volume (WLI 3.0 3.0 3.0 3.0 3.0 3.0 3.0 3.0 3.0 3.0 3.0 3.0 3.0 3.0 3.0 3.0 3.0 3.0 3.0 3.0 3.0 3.0 3.0 3.0 3.0 3.0 3.0 3.0 3.0 3.0 3.0 Calculated F.(>nsft.) Standcad FConcentration (mg/L) Meter Reacftig % Rec. Comments iaS 16.5 12.8 13.9 305 2S.2 21.7 111.7 128.4 ""i&5 16.S 165 165 33.1 33.1 33.1 165.3 165.3 13.7 17.2 16.0 26.5 28.S 2S.5 1306 148.5 144.1 301.8 3006 314.4 645.2 672.1 858.5 16.5 16.5 16.5 33.1 33.1 33.1 165.3 . 165.3 165.3 330.5 330.5 330.5 661.0 661.0 661.0 2.062 0.05653 003691 002618 0.06097 0.055(16 0.04256 0.04638 0.9685 01016 DJ38735 0.07239 ~i'y- 03724 ?->. 0.4279 '% 0.9845 0.07984 0.02783 0.02634 0.09136 0.1149 0.1067 0.1764 01906 0.1764 0.9725 0.8710 0.9765 0.9607 "?, 2.012 2.004 2.096 4.301 4.481 4.390 0.9646 95.25 110.69 99.96 77.26 84.20 96.85 92.22 79.29 65.71 87.61 77.68 98.45 Due to tow metereaiSngsandlow ecoNerKdeclded to renjn using 20ut-as samplevnlumeslll 8Z93 104.2S 96.86 80.04 86.50 B0.04 97.25 79.06 88.64 87.20 91.32 90.95 95.13 97.61 101.68 99.63 96.46 Analyst/Date Danial Howman; 10-1-37 P*g*8or7 > m i--i o Ul t*> L> ^ ^ l^ EID129634 ^ mss^ .^is^ . "eiMsaS; Project: R2382 Soil Samples from Dupont Washington ' Calculations for Total Fluoride in Soil CalculatadF-(mgA-)(Melw Reading <-lnlenpl)/Slope Calculated F- (ing/Kg) Calculated F- (mgA.) Collection Voluma / Sample Weight Sampla Dilution Sonpto Collection CalculalBd ID Weight (g) Volume (mL) Reading F-(msfl.) Analysis: DRM 9-30-97 QC 4.33PPMERA CHECK 2 BLANK-1 --- 1 2.079 . 3.0 007719 BLANK-2 1 3.0 0.05811 BLANK-3 1 3.0 0.05168 R2382-1-1 0.0203 3.0 08047 136 R2382-1-2 0.0231 3.0 0.9870 148 R23B2-1-3 0023 3.0 1.155 188 R2382-2-1 R2332-2-2 0.0236 00215 3.0 0.8080 138 3.0 05163 153 R2382-2-3 0.0213 3.0 0.9542 158 OC1.0PPM CHECK 1 0.9698 R2382-3-1 R2382-3-2 0.0204 3.0 2.485 387 0.0225 3.0 2583 461 R 2382-3-3 0.0202 3.0 Z841 440 R2382-4-1 0.0235 3.0 3.668 563 R2382-4-2 0.0227 3.0 3.838 598 R2382-4-3 0.0225 3.0 4.109 629 R2382-4-4 w/IOuL spike of 0.023 3.0 8.189 940 IQ.OOOppm POAA R2382-5-1 R2382-5-2 0.0228 0.023 3.0 5.349 814 3.0 5.436 827 R2382-5-3 O.D226 3.0 5.136 782 aC1.0PPM CHECK 1 0.9856 R2382-6-1 0021 3.0 3.835 588 R2382-6-2 R23B2-6-3 0.021 3.0 3.789 581 0.0214 3.0 3.774 579 R2382-7-1 0.0218 3.0 2.383 461 R2382-7.2 0.0201 3.0 2.S88 402. R2382-7-3 0.021 3.0 2.415 378 R2382-8-1 0.022 3.0 1.811 286 R2382-S-2 0-0216 3.0 1.841 291 R2382-8-3 0.0215 3.0 1.503 240 aC1.0PPM'CHECK 1 0.9777 R2382-9-1 0.0209 3.0 1.485 237 R2382-9-2 0.021 3.0 1.509 241 R2382-9-3 0.0203 3.0 1.342 216 aC1.0PPM CHECK 1 0.9737 Analysis: ORH 1<M-97 aC 4.33PPM ERA CHECK 2 2.019 BLANK-1 t 3.0 01319 BLANK-2 1 3.0 0.06430 BLANK-3 1 3.0 0.05910 R2382-10-1 R2382-10-2 R2382-10-3 0.0203 3.0 1.665 264 00201 3.0 1.741 276 0.0208 3.0 1509 301 R2382-H-1 R2382-11-2 R2382-11-3 0.0218 3.0 1.288 208 0.0223 3.0 1.471 235 0.022 3.0 1.402 225 QC1.0PPM CHECK 1 0.9420 Notebook Refefanca: Cartlon-SA-2. p.21-23 Calculated Statisfes % F-(mg)KB) (mafKBl Recovery 98.0 20.100 19.200 AVE 21300 STD 2800 24.500 17.300 21.300 21.700 CV 13 AVE 20100 STD 2400 CV 12 ----^------ 56,900 AVE 61200 61,500 STD 4200 65.300 CV 7 71^00" AVE 78300 79.000 83.900 STD CV 6000 8 122,600 107,100 107.SOO 103.800 AVE STD CV 106300 2100 2 84,000 83,000 81.200 63,400 60,000 53,800 39,000 40,400 335006^: --------3P 34.100t34.400 31.900 AVE 82700 STD 1400 CV 2 AVE 59100 STD 4900 CV 8 AVE 37500 STD CV 3800 10 a.tes AVE .33500 STD 1400 CV 4 97.0 51.4 SB.B 97.8 97.4 933 39,100 41.100 AVE 41200 STD 2200 43.400 CV 5 28:600' AVE 30300 31.700 30.700 STD CV 1600 5 94.2 Comments ffl 0 i--* 0 m u> 0\ Analyst/Date Daniel Howman/10-1-97 Paga7of7 63 ^ W EID129635 3M Environmental Laboratory, Total, Organic and Adsorbable Fluoride in Groundwater (6/97 Samples) EID129636 3M Environmental Laboratory Data Transmittal Summary Preliminaiy / Final (circle one) Lab Request #: R-2148 IjDate Received: Sponsor or Client: Representative Name Dale Bacon/Robert Howell Company Name 3M Company Address 935 Bush Ave., St Paul, MN Phone 778-4736/778-7540 ojectLead: Name/Phone KrisHansen roup Leader: Name/Phone 612-778-6018 Analyte(s) or Test Method #: Total Fluorine, Fluoride Ion, Adsorbable Organic Fluoride Sample Matrix: Dupont Waters Analysis Dates: 8/15/97-8/25/97 Analyst(s): Jan Schutz, Nancy Bergman Author: Jan Schutz [ProjecLtead (or designee): Data Reviewed by: PatRethwill 10/03/97 ames D. Johnson (or designee): Internal JDJ: KrisHansen QAU (Archives): Rich Youngblom LIRN System: Denise Appleton Project Manager: Sue Beach Others (List Recipients /'Address /Phone /FAX) Sent by:/Date JGS/11/07/97 JGS/11/07/97 JGS/11/07/97 JGS/11/07/97 Sent by: / Date A copy of the report including this form and the client cover page is to be given to QAU, LIRN and to the Group Leader. ^ 13.5- EID129637 3M Environmental Laboratory - Advanced Methpd Development Team Contact: Kris Hansen Building 02-3E-09 778-6018 kjhaasea @ mmin.com Sr. Analytical Chemist Final Report - Lab Request R2148 Total Fluoride Analysis - DaPont 30 September 1997 1.0 SUMMARY Twelve water samples from DuPont were submitted to the 3M Environmental Laboratory for organic fluorine analysis. The samples were submitted under Lab Request R2148, samples 1 through 12. Samples were tested for fluoride ions, total fluorine, and adsorbable organic fluorine (AOF). A modified version of DIN method 38 402 H29 was used to measure the AOF. The following table contains a summary of the results. Sample ID Sample Request Fluoride Ion Oig/mLF-) Total Fluorine (ug/mLF-) Total FluorineFluoride Ion (pg/mL) Adsorbable Organic Fluorine (tig/mL F-) itt'-'.y^ MW.1-1 R2148-1 7.8 MW-1-2 R2148-2 S'yfj^.sS'S.'.i.... ^ 16 MW-2-1 R2148-3 0.16 33 3.1 MW-2-2 R2148-4 0.16 3.5 3.3 MW-3-1 R2I48-5 0.14 4.2 4.1 MW-3-2 R2148.6 0.14 33 3.2 MW-4-1 R2148-7 0.11 4.0 3.9 MW-4-2 R2148-8 0.11 43. 4.1 MW-5-1 R2148-9 <0.10 3.0 2.9 MW.5-2 R2148-10 0.10 2.8 2.7 MW-6-1 B2148-11 0.10 2.3 13. MW-6-2 B2I48-12 0.10 43, 4.1 2.0 INTRODUCTION 4.5 4-2 0.28 0.46 1.1 0.76 0.19 0.14 0.11 0.14 0.05 0.05 A request was made of the 3M Environmental Laboratory to determine the ^ amount of fluoride and organic fluorine in twelve monitoring well water samples, using a modified Dohrmann Organic Halide Analyzer and the Orion EA940 Meter with a fluoride specific electrode. i--i o 3.0 TEST MATERIALS <j\ w w Twelve monitoring well water samples were received from DuPont. The samples were labeled as having been collected on 6/26/97. The samples were logged in as Lab 3M Environmental Laboratory, Lab Request R2148 ^ ^ ^s~ EID129638 Request R2148, samples 1 through 12. Samples were kept refrigerated until they were analyzed. A standard curve was prepared, from an ammonium perfluorooctanoate (POAA) standard (S397-386) for total fluoride plus organic fluorine analysis and from an ammonium perfluorooctanoate (POAA) standard (S397-383) for adsorbable organic fluorine. The Orion meter was calibrated daily with standards prepared from a Coming fluoride stock standard in 50% TISAB W50% Milli-Q water 4.0 EXPERIMEP<TAL-OVERVIEW 4.1 Fluoride Ion Analysis This analysis measured the amount of fluoride ion in me sample without combusting me sample. For measurement of fluoride ion, an Orion EA940 meter was calibrated daily, using Coming standards over me range of 0.05 - 1.5 ppm fluoride. One milliliter of unfiltered sample was diluted with one milliliter of TISAB II and analyzed on the Orion meter. A mid-range calibration standard was analyzed periodically to verify that the system continued to operate properly. 4.2 Adsorbable Organic Fluorine (AOF) This analysis measures the amount of adsorbable organic fluorine as fluoride in the sample by passing the filtered sample through two carbon columns and then combusting the carbon. For measurement of AOF, a modified version of the German wastewater analysis method, DIN method 38 402 H29 (column method), was followed. The POAA standard curve and samples were prepared by running 100.0 roL of standard or sample (or an aliquot of sample^ffiluted to 100 mL) through two carbon columns using a Dohrmann AD-2000 Adsorption Module. The carbon columns were burned in a modified Dohrmann DX2000 Organic Halide Analyzer, collecting the off-gases in 3.0 mL of 1:1 TISAB II/Milli-Q water and analyzing on an Orion EA940 meter with a fluoride specific electrode. The Orion meter calibrated from 0.5 - 25.0 ppm fluoride. 43 Total Fluorine Analysis This analysis measured the amount of total fluorine by combusting an aliquot of unfiltered sample, collecting the off-gasses, and analyzing me collection solution for fluoride. For this measurement a modified Dohrmann Organic Halide Analyzer and an Orion EA940 meter (calibrated from 0.1 - 5.0 ppm F-) were used. An POAA standard curve was generated by burning 0.10 mL standard and collecting me off-gasses in 3.0 mL 1:1 TISAB n/Milli-Q water for analysis on the Orion EA940 meter. The water samples were analyzed following me same > method as the standards, ffi o INSTRUMENTATION s Dohrmann DX2000 Organic Halide Analyzer modified for fluoride analysis Dohrmann Adsorption Module AD2000 3M Environmental Laboratory, Lab Request R2148 4.7 ^ W EID129639 INSTRUMENTATION Orion EA940 Expandable Ion Analyzer with Orion 9609BN Combination Fluoride Electrode DX2000 software, version 1.00, modified for fluoride extraction DX2000 software, version 2.00, modified for fluoride extraction (AOF analysis) Microsoft Excel OPERATING CONDITIONS Combustion tube temperature == 950 C Oxygen and Helium flow = 50 cc/minute VPOAArization/Drying time = 240 seconds Bake time = 300 seconds Collection fluid = 3.0 mL 1:1 TISAB II/Milli-Q water REAGENTS Fluoride Standard 100 ppm, purchased from Coming (part #478170, lot #1113022) Total Ionic Strength Adjustment Buffer (TISAB II), Orion (part #940909, lot AR1) 5.0 DATA ANALYSIS The Orion Meter, serial # 4202, was calibrated each morning prior to any samples being run. Calibration was based on direct measurement of calibration standards made from Corning fluoride stock standard. An acceptable correlation coefficient is = 0.9950. d a t e a n a lysis donecorrelation Total Fluorine Analysis / coefficient (R2) 18 - 21 August 1997 POAA standard curve 0.9993 18 August 1997 Fluoride ion analysis .0.9998 15 - 25 August 1997 AOF Analysis / POAA standard curve______0.9999_____ A standard curve for total fluorine was generated by combusting 0.1 mL aliquots of 2.0, 5.0, 20, 50, and 100 ug/mL POAA standard (POAA is 66.1% fluoride) in the Dohnnann DX2000 Modified Organic Halide Analyzer. The off-gasses were collected in 3 mL of 1:1TISAB W Muli-Q water and analyzed wilh the Orion meter. Using least squares linear regression, plotting the fluoride concentration of the standard on me x-axis, and the Orion meter response on the y-axis, the following curve was generated: Y - 0.0341x 0.0157 and R2 = 0.9988. A standard curve for adsorbable organic fluorine (AOF) was generated by pushing 100 mLs each of 5 standards containing 4.9,14.4,23.6,33.5, and 43.1 ug/mL fluorine as POAA through two carbon columns. The carbon columns were combusted in me > Modified Dohrmann DX2000 Organic Halide Analyzer. The effluent was collected in 3 g o mL of 1:1 TISAB II / Milli-Q water and analyzed with me Orion meter. Using least ^--* 0 squares linear regression, plotting the fluoride concentration of the standard on me x axis, ^ and the Orion meter response on the y axis, the following curve was generated: Y 1-A =0.2894x + 0.0196 and R2 = 0.9949. 3M Environmental Laboratory, Lab Request R2148 fc8 ^ /-?5- EID129640 SAMPLE ANALYSIS; Fluoride IOB Analysis Sampieff Meter Reading Dilution Factor Quantity of Sample (mL) Fluoride Ion iB Sample (tig/mL) R2148-1 0.1005 R2148-2 0.1017 R2148-3 0.0813 R2148-4 0.0801 82148-5 0.0701 R2148-6 0.0696 R2148-7 0.0567 R2148-8 0.0556 R2148-9 0.0465 R2148-10 0.0463 B2148-H 0.0491 R2148-12 0.0497 *Method detection limit (MDL) = 1.0 0.20 1.0 0.20 1.0 0.16 1.0 0.16 1.0 0.14 1.0 0.14 1.0 0.11 1.0 0.11 1.0 0.10* 1.0 0.10 * 1.0 0.10 * 1.0 0.10* 0.100 ppm (lowest calibration standard x dilution factor) AOF Standard Curve Total Ammonium PerQuorooetanoate Standard in Columns (top + bottom) Sample ID POAA Standard 1 0.072 ppm POAA Standard 2 0.217 ppm POAA Standard 3 0362 ppm POAA Standard 4 0.507 ppm POAA Standard 5 0.652 ppm *POAA Standard is 66.1% Fluoride Quantity Combined Spiked Sample Orion Meter ugtaL F- (mL) Readmg (pg/mLF-) ia Sample * 100 1.62 0.05 100 4.18 0.14 100 6.75 0.24 100 9.31 0.34 100 12.9 0.43 Y==0.2894x+0.0196 V1 ='93949 AOF Sample Analysis Sample ID Combined Meter Reading Quantity of Sample (mL) Adsorbabte Organic Fluorine in Sample (pg/mL) R2148-1 (top+bottom) R2148-2 (top + bottom) R2148-3 (top+bottom) R2148-4 (top + bottom) R2148-5 (top+bottom) R2148-6 (top+bottom) R2148-7 (top+bottom) R2148-8 (top+bottom) R2148-9 (top + bottom) R2148-10 (top+bottom) R2148-11 (top+bottom) R2148-12 (top+bottom) *MDL=0.05ugftnL. 6.544 6.063 6.776 11.30 3.235 2^29 2.696 2.024 1.556 1.937 0.537 0.536 3M Environmental Laboratory, Lab Request R2148 5.0 5.0 85.0 85.0 10.0 10.0 50.0 50.0 50.0 50.0 100.0 100.0 4.5 4.2 0.28 0.46 1.1 0.76 0.19 0.14 0.11 0.13 0.05* 0.05* EID129641 Total Fluorine Standard Curve Ammonium Perfluorooctanoate in MilIi-Q water Sample m POAA standard 1 -2.00ppm POAA standard 2 - 5.00 ppm POAA standard 3 - 20.0 ppm POAA standard 4 - 50.0 ppm POAA standard 5- 100 ppm Quantity Sample (nL) 0.100 0.100 0.100 0.100 0.100 Orion Meter Reading Oig/mLF-)' 0.048 0.100 0.421 1.089 2.248 Spiked ug/aiL F- in Sample 1.32 3.31 13 3. 33.1 66.1 'Based on the average of three replicates. Y 0.0341x - 0.0157 *ammonium perfluorooctanoate standard is 66.1 % Fluoride R* 0.9988 Total Fluorine Sample Analysis Sample ID Meter * Reading MW-1-1 R2148-1 03568 MW-1-2 R2148-2 0.5217 MW-2-1 R2148-3 0.0964 MW-2-2 R2148-4 0.1051 MW-3-1 R2148-5 0.1279 MW-3-2 R2148-6 0.0963 MW-4-1 R2148-7 0.1199 MW-4-2 R2148-8 0.1260 MW-5-1 R2148-9 0.0960 MW-5-2 R2148-10 0.0802 MW-6-1 R2148-11 0.0636 MW-6-2 R2148-12 0.1286 * Based on average of three replicates. Quantity of Sample (mL) 0-1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 Total jtg/mL * F-in Sample 8.0 16 3.3 3.5 4.2 3.3 4.0 4.2 3.0 2.8 23 4.2 6.0 CONCLUSION Fluoride ion concentrations range from <0.10 to 0.20 ug/mL, <0.05 to 4.5 ug/mL F- for adsorbable organic fluorine analysis, and 2.3 to 16 ug/mL F- for total fluorine analysis. The large difference in concentration of total fluorine for samples, R2148-1 and R2148-2 (duplicate samples) may have been caused by differences in the amount of solid particulate matter in me sample aliquots. The results for the adsorbable organic fluorine analysis may be lower than expected, due to me Sact that me solid particulate matter was filtered from me AOF samples, and some polymers may not adsorb on to me charcoal columns. 7.0 MAINTENANCE OF RAW DATA Hard copies of the data are filed in the AMDT archive. m yaactffl.xraaren g fr. Lk> JG Schutz 09-30-97 3M Environmental Laboratory, Lab Request R2148 70 ^ /^S~ EID129642 Cu(ve F- Cone. Meter In Standard -4:9 1.6156 14 14.4i 4.1827 Perfluorooctanoate AOF Curve 23.9 6.7477 33.5 9.3122 43.1 12.8872 12 y0.2894x+0.0196 l^" 0.9949 10 ASH010544 0-0 SO 10.0 16.0 20.0 25.0 30.0 38.0 40.0 45.0 FlUOridi Spiled (iigftnL) s- Vs '- Orion Data ASH0 DATA FOR AMMONIUM PERFLUOROC3CTANOATE AOF STANDARD CURV E Sample ID Actual Meter reading (PpmF-) Collect Dilution Vol (mL) Factor Sample Volume (mL) CaIcAOF <rf . column Total of Orion read top&bottom Calc. TOTAL AOF (Top& Bottom) blank bottom Std#1 bottom Std# 2 bottom S(d# 3 bottom Std# 4 bottom Std# 5 bottom blank top Std#1top Std#2top Std#3top Std#4top Sld#5top QG check 5.0 FLUORIDE 0.1522 3.0 0.4536 3.0 0.3701 3.0 0.3643 3.0 0.1815 3.0 0.1232 3.0 0.0544 3.0 1.1620 3.0 3.8126 3.0 6.3834 3.0 9.1307 3.0 12.764 3.0 5.098 1.0 1C3NANALY SIS 1 1 1 100 1 100 1 100 1 100 1 100 1 100 1 100 1 100 1 100 . 1 100 1 100 1 1 0,4565 0.0136,1 0.01 tfQ 0.0109296 0.00544 0.00370 0.00163 0.03486 0.1144 0.1915 0.2739 0.3829 5.098 Total Fluorida 1.616 4.183 6.748 9.312 12.887 0.048 0.125 0.202 0.279 0.387 Sample ID QC check 0.50 pp R2148-1 R2148.2 R2148-3 R2148-4 R2148-S R2148-6 R2148.7 R2148-8 R2148-9 R2148-10 R2148-11 R2148-12 QCchack0.50.pp Meter Read 0.5018 0.1005 0.1017 0.0813 0.0801 0.0701 0.0696 0.0567 0.0556 0.0465 0.0463 0.0491 0.0497 0.5039 TISABVol 1.0 1.0 1.0 1.0 1.0 1.0 1.0 1.0 1.0 1.0 1.0 1.0 1.0 1.0 Dilution Sample Vol 1 1.0 2 1.0 2 .1.0 2 1.0 2 1.0 2 1.0 2 1.0 2 1.0 2 1.0 2 1.0 2 1.0 2 1.0 2 1.0 1 1.0 (^g/mL) 0.502 0.201 0.203 0.163 0.160 0.140 0.139 0.113 0.111 0.093 0.093 0.098 0.099 0.504 F-Cone. in Standard (no/mi.) % Recovery -------- 0.049 0.144 0.239 0.335 0.431 100% 87% 85% 83% 90% 100% 101% Page1 Orion Data ASHO 1054 AOF ANALYSIS Sample ID QC check 5.0 ppm AOFhntr blank Bottom R2148-1 bottom R2148-2 bottom R214B-3 bottom R2146-4 bottom R214B-5 bottom R2148-6 bottom QC check 5.0 ppm R2148-1 Top R2146-2Top R2148-3Top ^2148-4 Top W48-BTOP US148-6Top QC check 5.0 ppm jlllllQBlk Bottom 12148-1 bottom 12148-2 bottom 1214S-5 bottom WWSi bottom R2148-7 bottom R2148-8 bottom Mini Qblk Top R2148-1 top R2148-2 top R2148-5top R214B-6top R2148-7top R2148-8 top QC cai check 4.33 ppm AOF Calc. ([ig/mL) = ((total meter reading - Meter Reading Collect Vol(mL) Dilution Factor Sample Vol(mL) intercept)/ slope) / sample volume Calc. Adsorbable Meter Reading Organic Fluorine Total (top&bottom) (ng/mL) Comments y=0.2894+0.01 % Recovery 5.039 1.0 1 1 0.0280 3.0 1 1 0.3019 3.0 1 85 0.2972 3.0 1 70 0.1222 3.0 1 85 0.1358 3.0 1 85 0.2881 3.0 1 90 0.2803 3.0 1 85 4.903 1.0 1 1 124.9 3.0 1 85 102.7 3.0 1 70 6.654 3.0 1 85 11.16 3.0 1 85 30.15 3.0 1 90 25.09 3.0 1 85 4.955 1.6 1 1 0.0565 3.0 1 100 0.1633 3.0 1 5 0.1910 3.0 1 5 0.1423 3.0 1 10 0.1128 3.0 1 10 0.2298 3.0 1 50 0.1881 3.0 1 50 0.0531 3.0 1 100 6.381 3.0 1 5 5.899 3.0 1 5 3.093 3.0 1 10 2.116 3.0 1 10 2.466 3.0 1 50 1.836 3.0 1 50 2.04 1.0 2 1 :j ;1Q .--.SN '; ae '<"' 125.2 103.0 6.776 11.29 . 30.44 26.37 0.110 6.544 6.090 3.236 2.228 2.696 2.024 101% 5.089 5.083 0.275 0.458 1.168 1.030 98% Read above top std, re-run Read above top std, re-run 99% Read above top std, re-run Read above top std, re-run 99% 0.0031 4.5091 4.1951 1.1113 0.7632 0.1849 0.1386 4.072 94% Page 2 ^ii^S^ AOF ANALYSIS Sample ID R2148-9 bottom R2148-10 bottom R214a-11 bottom R214S-12 bottom R214B-910P R2148-10 top R2143-11 top R2148-12top R2148-7 MS Bottom R2148-7 MS Top QCcal check 4.33 ppm R 2148-11 bottom R 2148-12 bottom R 2148.11 Top R2148-12TOP QC check 0.050 ppm ^^g;^ Orion Data ASHO 1 AOF Gale. Meter Reading (ug/mL)= {(total meter reading Collect Vol(mL) Dilution Factor Sample Vol(mL) intercept)/ slope) / sample volume Calc. Adsorbable Meter Reading Organic Fluorine Total (top&bottom) (top&bottom) Comments y=0.2894+0.01 % Recovery 0.2705 3.0 1 50 0.2784 3.0 1 50 0.1188 3.0 1 50 0.0713 3.0 1 50 1.2856 3,0 1 50 1.6588 3.0 1 50 0.3520 3.0 1 50 0.2683 3.0 1 50 0.1134 3.0 1 100 3.0297 3.0 1 100 2.228 1.0 2 1 0.0760 3.0 1 100 0.0839 3.0 1 100 0.4608 3.0 1 100 0.4518 3.0 1 100 0.4988 1.0 1 1 1.5561 1,9372 0.4707 0.3396 3.143 0.5368 0.5357 0.1062 0.1325 0.0312 0.0221 0.1079 4.456 mad below low ltd, re-run read below low ltd, re-run 103% 0.0176 0.0175 98% Page 3 POM CURVE ASH010548 Thermally Extracted Perfluorooctanoate Curve 11 jf.auuuu y=0, Q. 0341x - ( .0157 a 8 ^ 2.00000 --------F 12 E--=-- 0U<Q99Q<f -------- 0 ^ a W 1-50000 ^ 0 - ^ 2 1.00000 IS 0 "s S"0 0.50000 ^ 1 ^ 0 0.00000 c o 10 20 30 40 50 60 STANDARD CONCENTRATION (PPM F-) Pager- 'V-iit.' DUPONTI.xte 11/7/97 3:30 PM ASH01 Perfluorooctanoate Standard Curve 1 FACTOR | SAMPLE | COLLECT CALC. POAA Actual %REC COMMENTS iilHMffiSK wSsyl(iifflilww%%! lwS'IS^Bp^'l'sf l^y"P' '}lw^1MB)^ ERA4.33PPMSTD 2 QC1.0PPMSTD CHECK BLK-1 1 0.1 3 BLK-2 1 0.1 3 BLK-3 1 0.1 3 POAA1.0PPMW397-795 1 0.1 3 POAA 1.0 PPMW397-795 1 0.1 3 POAA1.0PPMW397-795 1 0.1 3 ERA4.33PPMSTD QC1.0PPMSTO CHECK BLK.1 1 0.1 3 BLK-2 . 1 0.1 3 BLK-3 1 0.1 3 POAA 2.0PPM W397-801 1 0.1 3 POAA 2.0PPM W397-801 1 0.1 3 POAA 2.0PPM W397-801 1 0.1 3 POAA 5.0 PPMW397-796 1 0.1 3 POAA 5.0 PPMW397-796 1 0.1 3 POAA 5.0 PPMW397-796 1 0.1 3 QC 1.0 PPM CHECK POAA20PPMW397-797 1 0.1 3 POAA20PPMW397-797 1 0.1 3 POAA20PPMW397-797 1 0.1 3 POAA50PPMW397-798 1 0.1 3 POAA50PPMW397-798 1 0.1 3 POAA50PPMW397-798 1 0.1 3 POAA100PPMW397-799 1 0.1 3 POAA100PPMW397-799 1 0.1 3 POAA100PPMW397-799 1 0.1 3 QG 1.0 PPM CHECK i: '(I^CM^ ^..47 ih02 0.48 1,16 0.97 1.40 ti^'wiBMJ^ff 0.661 0.661 0.661 iippnw)* 2.200 0.9652 0.0491 0.0340 0.0161 0.0388 0.0323 0.0467 yjy,'s^w 101.6 96.52 176 147 212 's-wps ^ww il ya-^ BELOW DETECTIO USE 2.0PPM STD D NOT INCLUDED IN 2.162 99.8 0.9864 98.6 0.01599 0.01455 0.01491 1.473 1.322 0.04911 111 1- 1.473 1.322 0.04911 111 11 1.397 1.322 0.04685 106 10 2.82 3.31 0.0939 85.2 3.22 2.99 12.10 3.31 3.31 13.22 0,1074 0.0998 0.9691 0.4033 97.5 90.6 96.9 91.6 12.80 12.96 31.92 33.12 32.97 66.54 69.60 66.27 13.22 13.22 33.05 33.05 33.05 66.10 66.10 66.10 0.4268 0.4321 1.064 1.104 1.099 2.218 2.320 2.209 0.9930 96.9 98.1 96.6 100 99.8 101 105 100 99.3 Pagel DUPONT1.X18 11/7/97 3:17 PM TABLE ; R2148 F- DETERMINATION: SAMPLES DUPONT INC. ICALCULAT(EPPDM F-) = (meter reading i|i|Broept)/slope) SEE STANDARD CURVB'POREQUATION; Y " 0.0341X - O.M57 ASH010 QC1.0PPM CHECK R2148-11-1 0.1 R2148-11-2 0.1 R2148-11-3 0.1 R2148-12-1 0.1 |R2148-12-2 0.1 R2148-12-3 0.1 R2148-10-1 0.1 R2148-10-2 0.1 R2148-10-3 0.1 IQC 1.0 PPM CHECK R2148-9-1 0.1 R2148-9-2 0.1 R2148-9-3 0.1 R2148-8-1 0.1 R2148-8-2 0.1 R2148-8-3 0.1 QC 1.0PPM STD CHECK 0.9743 0.05555 0.06031 0.07499 0.1699 0.1233 0.09247 0.08379 0.06284 0.09400 0.9663 0.1042 0.07910 0.07286 0.1361 0.1279 0.1131 0.9624 2.09 2.23 2.66 5.44 4.08 3.17 2.92 2.30 3.22 3.52 2.78 2.60 4.45 4.21 3.78 AVE 8TD CV AVE 8TD CV AVE STD CV 2.33 0.30 12.8 4.23 1.14 27.0 2.81 0.47 16.6 AVE STD CV AVE STD CV 2.96 0.49 16.4 4.15 0.34 8.24 96.24 DUPONT1 .xls 11/7/97 3:17 PM Environmental Laboratory Soil Properties and Nutrient Concentration Analyses (6/97 Samples) ..urner > w 5 <-> t/ ts 7^ ^ 1^ EID129651 3M Ecotoxicology and Environmental Fate Laboratory Soil Properties and Nutrient Concentration Analyses of Samples Received From the E. 1. DuPont de Nemours and Company Facility in Parkersburg, West Virginia STUDY COMPLETED: August 27,1997 FINAL REPORT COMPLETED: October 31.1997 Lab Request No. R2382 Prepared by: Susan A. Beach Senior Environmental Biologist 3M Environmental Laboratory Building 2-3E-09 935 Bush Avenue St Paul. MN 55144 EID129652 3M Ecotoxicoldgyand Environmental Fate Laboratory 1.0 Introduction Eleven soil samples were received from E.I. DuPont de Nemours and Company for preparation and analyses by the Ecotoxicology and Environmental Fate Testing Group of the 3M Environmental Laboratory. These samples were assigned a Lab Request number (LR No.) of R2382. The sample date was 6/23/97. Samples were numbered R2382-1 through R2382-11 as follows: 3M LRNo. R2382-1 R2382-2 R2382-3 R2382-4 R2382-5 R2382-6 R2382-7 R2382-8 R2382-9 R2382-10 R2382-11 DuPont COC Description SS-1 0-2' SS-1 4-6' SS-1 8-10' SS-1 12-14" SS-1 16-18' SS-1 20-22' SS-1 24-26' SS-1 28-30' SS-1 32-34' SS-1 36-38' SS-1 38-40' 2.0 Results A summary of the results obtained is presented below. Copies of methods, raw data sheets, and contract laboratory reports are attached to this summary report. DuPont Sample No. Sulfate. SuHita. mg/kg mg/L R2382-1 SS.1 0-2- 98 <2 R2382-2 SS-1 4-6' 99 <2 R2382-3 SS.1 8-10- 73 <2 R2382-4 SS-1 12-14- 54 <2 R2382-5 SS-1 16-18- 43 <2 R2382-6 SS.1 20-22- 70 <2 R2382-7 SS-1 24-26- 220 <2 R2382-8 SS-1 28-30- 150 <2 R2382-9 SS.1 32-34- 100 <2 R2382-K SS-1 36-38- 63 <2 R2382-11 SS.1 38-40- 46 <2 Nitrite Nitrogen, mg/kg 0.41 0.41 0.36 0.14 <0.10 <0.10 <0.10 0.11 <0.10 <0.10 <0.10 pHin CaCIZ 7.2 7.3 7.0 6.3 5.3 5.5 5.3 6.3 5.2 5.4 6.2 pHin water 7.7 7.7 7.3 6.7 5.7 6.0 5.8 . 6.8 5.8 6.1 6.8 CEC, meq/100g -?-' -15.8' 18.4 17.5 17.5 18.4 19.3 17.5 11.4 13.1 9.6 6.3 % Moisture. (as-rec'd) 12.3 12.7 15.5 18.9 18.3 19.2 20.0 18.1 13.6 17.9 22.2 2 3} ^ ^5- EID129653 3M Ecotoxicology and Environmental Fate Laboratory 3.0 Initial Observations 3.1 Sample R2382-1 Half of the two foot column not filled. Only one foot of soil present. 3.2 Samples R2382-2 through R2382-11 Had an unusual odor, possibly hydrocarbons. 3.3 Samples R2382-1 through R2382-6 Appear to be clay/silt. 3.4 Samples R2382-7 and R2382-8 Appear to be clay/sift/sand, more silt/sand. 3.5 Sample R2382-9 Appears to be sand/sift. 3.6 Sample R2382-10 Appears to be sand/silt with free-flowing water in column. 3.7 Sample R2382-11 Appears to be coarse sand. '< ^" 4.0 Sub sampling A one-foot core from the top of each column through the center was removed. The sample was thoroughly mixed then split for inorganic and organic analyses. The remaining intact cores were refrigerated at 4C in the dark. 5.0 Sample Preparation Aliquots of well-mixed wet soil (as received) were prepared as necessary for soil properties testing, nutrient analyses, CEC, and total fluoride analyses. After preparation, aliquots were provided to the proper laboratory personnel for testing. 5.1 Air-Dried Soil - 2.00 mm . > Soil samples were air-dried at ambient room temperature to constant weight. 2 Soil was crushed, as necessary with a mortar and pestle, and passed through a g 2.00 mm stainless steel sieve. Soil prepared this way was used for pH g analyses. ^ 3 8a. 4 /^ EID129654 Ecotoxicolbgy and Environmental Fate Laboratory 5.2 Air-Dried Soil - 0.500 mm Aliquots of air-dried 2.00 mm soil were crushed with a mortar and pestle until the entire sample passed through a 0.500 mm stainless steel sieve. Soil prepared this way was used for CEC and nutrient analyses. 5.3 Oven-Dried Soil - 0.063 mm Aliquots of the 2.00 mm air-dried soil were finely ground with a mortar and pestle until the entire sample passed through a 0.063 mm stainless steel sieve. The samples were then oven-dried (105C) to constant weight. Soil prepared this way was used for total fluoride analyses (results presented in a separate report by 3M AMDT Laboratory). 6.0 Analytical Methodology 6.1 Soil Water Content Aluminum pans were oven-dried to constant weight. Twenty-three to thirty-five gram aliquots of well-mixed wet soil (as-received) were weighed in the aluminum pans. The pans and soil were then oven-dried at 105C to constant weight. The soil water content was determined by the following equation: Weight of Wet Soil - Weight of Dry Soil Weight of Dry Soil X 100 6.2 Soil pH 6.2.1 pH in Water Ten grams of 2.00 mm-sieved soil and 10 mL Milli-Q water were placed into 50 mL conical centrifuge tubes. The tubes were then capped and shaken for one hour. After shaking, the tubes were allowed to stand for one hour. A Cole-Parmer Model 5992-60 soil electrode was used to measure the pH. 6.2.2 pH in 0.01 M CaCl2 After pH in water was determined, 0.10 mL of 1.0 M CaCl2 was added to each tube. The tubes were shaken for 30-minutes then allowed to stand for 30-minutes. A Cole-Parmer Model 5992-60 soil electrode was used to measure the pH. 6.3 Cation Exchange Capacity (CEC) by Sodium Saturation 6.3.1 Adsorption Step Five grams of 0.500 mm-sieved soil and 132 mL of 1.0N pH 8.2 NaOAG were placed into 250 mL conical polypropylene centrifuge tubes. The ^sa-aufc.,... ^.a SiftV&i';. "O" s >--t s Ul 0\ 4 83 ^ I^S- EID129655 3M Ecotoxicotogy and Environmental Fate Laboratory tubes were then capped and shaken overnight at 300-400 rpm. After shaking, the tubes were centrifuged for 10 minutes at 3000 rpm. The supernatant was then decanted and discarded. 6.3.2 Washing Step Fifty mL of 2-propanol was then added to each soil. Tubes were capped and shaken for 30-minutes. After shaking, they were centrifuged as in 6.3.1 and the supernatant discarded. This step was then repeated with another 50 mL aliquot of 2-propanol. 6.3.3 Desorption Step One hundred mL of 1.0 N, pH 7.0 NH40Ac was added to each sample. The tubes were stoppered and shaken over-night. After shaking, they were centrifuged for 10-minutes at 3000 rpm. The supernatants were decanted for sodium analyses. The supernatants were then submitted to the Inorganic Analysis Group of the 3M Environmental Laboratory for analysis of sodium by ICP (SW-846, Method 6010). 6.3.4 Calculation of Cation Exchange Capacity 0.1 x (cone. of Na. ma/LV23 oven-dried weight of soil, g* x100 = meq/IOOgsoil Sub-samples of 0.500 mm air-dried soil were oven-dried to constant weight and the moisture content was determined. The values obtained were used to calculate the final CEC value of soil on an oven- dried weight basis. 6.4 Nutrient Analyses Aliquots of the 0.500 mm-sieved soil were submitted to Minnesota Valley Testing Laboratories, Inc. (MVTL) for analysis of nitrite, sulfate and sulfite. The following methods were employed: 6.4.1 Nitrite Nitrogen Methods of Soil Analysis, 2nd Edition, 33-8. 6.4.2 Sulfate SW-846, Method 9088. 6.4.3 Sulfite EPA Method 377.1. ^ ^ -^ 5 EID129656 3M Ecotoxicology and Environmental Fate Laboratory Copies of Raw Data and Contract Laboratory Reports EID129657 ENVIRONMENTAL LABORATORY WORKSHEET LR 7?^38Z. PAGE / OF / DATE 8/5/?y ANAt^^y*3 ^^^( fWf^ynjdwriffwAj^f u^^^frr^ty^oef^ff--g^/--/ ------^ --n--n--iA---^--/i--^^--^--/^.i--f r--ti-a--ff--^ -7W--.c---=----------------------. ^/ //^ ^ ^A^yf/^ / /(a^ nf ^ ^ofu^ M^f ^^P . ^/y // ^sw/^w^ -tf-\ / ^ _fg^^W>yaf^f/v-t^-R^cWtW^ffOc^f^f^r"'^J^ ^f^Cf ff//f^iM/^/Sfit'ff_________, (f/ii^lSi/^-^ui/f ^^< fJ^Asatf// _^71^3/f^ S^Jl/'A^'/O ^^^/^/S/'//- ^.^it/^./.O. tA^lUrMr^-Hi--^I .li-/^ .-^i;-3u^y//^-/-'-/t ,f--l)/-^--^r^-,^--^-(-i-f-W^ (^(fffi^ I ft S^/6t^fj^ ^-t^c^,^_> <sf _<fl^yf^/7' //"y/^if^f^^' ^> ^ ^^T^W-" ^^ ---' !.^Bi.i,^--... -..- ^^ /^-^' -/^^m>f^^^^/>/^^^^U^r^J7^T/?^^yj^^^yt^t^/f7^W?^/^^(/^,^>^^0^h^y/u/n'^^-^f,-.f^^rft^ri-/^7r^^j^p/^fof/w<f^i^f^^^^ t"/vw^'w. i^fWf^g.u^-f' {j^a.^fi^Crf'f 7 / ^ y " ' - ^r^^T^^'Ky- Jf W' .f^^_'/^f^ J^^^^/y^g^y^ > M g t--t 0 (-^ Ul VO 8h if /^S' EID129658 ENVIRONMENTAL LABORATORY SOIL WATER CONTENT PERCENTAGE OF WATER IN THE SAMPLE ON A DRY-MASS BASIS Gardner. Walter. 1986. Water Content, p. 493-544. In Arnold Klute (Ed.). Methods of Soil Analysis. Part 1. Physical and Mineratogical Methods. Agronomy Monograph No. 9 (2nd Edition). % Water Content Weight of Wel Soil . Weight of Dry Soil x 100 Weight of Dry Soil SAMPLE DESCRIPTION -^Z-S^-l ^ ^ 4 --------6h---------- / <5? ^ 10 11 Wet Soil g4f'ahJ "'d^ill--5ki)^4 ?>%.-? l z.-s.^z- ^Afill ^.s<& 2-2^10 ?^-iqL 2l.L(<lK ^1.'80L>. ^z-sdi's 2<1.<KJ^ ^t-. Z.2?( Dry Soil g (oven 'dried) ^n.iZA ZjO.SSO Z.^.tSq 2-2.,UflO ^.1L,1 M.%S<1. Aft.O^ 2,1^19 l^.fti^ 2>l.l^ 2Ct.l^4 NET LOSSg 3.1^5 2L.KIZ. S.4S& ^,?3. S.Si^ 5,W/ <?.5<?^ -f,^^ , J?.^<?1 -A a/w<e/ ^ " ^.^7^ ,,^,.. .,, M^ /^-? <1ft 1/9^^ 2^-/9 ^^ S,!h!Si.USMy~ ^ t " &44'w~----- '"r"^^""" ^/..^^'E;'";^ .. y ^ ANAE DATE:) -f^Pf -------- > - CO s. o ^ 87 ^ /a5" EID129659 ...^tf.'^f.ftf,. ENVIRONMENTAL LABORATORY SOlLpH and LIME REQUIREMENT(LR) McLean, E. 0.1982. Soil pH and Lime Requirement, p. 199-224. In A. L. Page, R. H. Miller & 0. R. Keeney (Eds.) Methods of Soil Analysis, Part 2. Chemical and Microbiological Properties. Agronomy Monograph No. 9 (2nd Edition). 2.00 mm air-dried soil used. Soil - to - Millipore MilIi-QTM Water Ratio 1:1.10 g plus 10 mL For LR, SMP single-buffer method used. Soil - to - SMP Buffer Ratio 1:2.10 g plus 20 mL SAMPLE DESCRIPTION l^ffiZ-t L A 4 5 // 1 < c? 10 " pHw (pH In water) W 7.V 7.% f/.i. .<.-/ ^0 ^ Lft.^ ^ -4^4.8---- pHs(pHin0.01MCaC12) W ^ i,n (e^ ^2S <..<; ^s,^s ^^.^^ ff.y) Soil-Buffer pH LRfTA), , ANALYSI .fS^y^ PATE/7:^"/^/'^/ ' -------- > CO 0 o <j\ <3\ 8S ^ J^A" EID129660 EID129661 ENVIRONMENTAL LABORATORY SOIL WATER CONTENT PERCENTAGE OP WATER IN THE SAMPLE ON A DRY-MASS BASIS Gardner. Walter. 1986. Water Content, p. 493-544. In Arnold Klute (Ed.). Methods of Soil Analysis, Part 1. Physical and Mineratogfcal Methods. Agronomy Monograph No. 9 (2nd Edition). % Water Content = Weight of Wet Soil . Weight of Dry Soil x 100 Weight of Dry Soil SAMPLE DESCRIPTION F^ftZ-1 Z. ^ ^ ^ ^ T < ^ in 11 Wat Soil g (air-dried) ^Wm1 -f.M l.a^ If.^lQ b.f^l -f./A< 7.0^ ^h.iw^S (..6^ Dry Soil g (oven-dried) , ^IslETLOSSg l.^a? ^,o$<r -i.-m 1,<?U 1-.452- ^.L,OZ- 1.010 I.OL?^-]Z2/ (^(^^ (-.O^.S- O.Olel O.fl^ 0,0f/ 0,6'53 (^.O*??? ^<?f9 0-0S5' 0,<W o.W fi.f)2.1 d.O/^ % n^ n.w fi.^i O.K^ a. 90 o.f^ fil^ Q^ 0^ 0^...^^ -----------------------------------. ANA D A T E-/:-^// ///y^ > \ ... - ^. 8 S TO ^ /,?A' EID129662 ENVIRONMENTAL LABORATORY CATION EXCHANGE CAPACITY (CEC) BY SODIUM SATURATION Rhoades, J. D. 1982. Cation Exchange Capac'ity- p. 149-157. In A. L Page, R. H. Miller & D. R. Keeney (Eds.) Methods of Soil Analysis. Part 2. Chemical and Microbiological Properties. Agronomy Monograph No. 9 (2nd Edition). Extracts prepared using 0.500 mm air-dried soil. Cation Exchange Capacity by Sodium Saturation; modification of method is as follows: 'ADSORPTION Batch equilibrium method (over-night) with 1.0 N NaOAc pH 8.2 as saturation solution. "WASHED Two washings with 2-Propanol. DESORPTION Batch equaibrium method (over-night) with 1 .ON NH40Ac pH 7.0 as extraction solution, CEC EQUATION: (0.1 Na ppm/23/oven-dried wt. of soil g) x 100 = meq/100 g soil SAMPLE DESCRIPTION KZ^ft^-l Z. ^ ----------------^-------- .^ fc 1 < ^ 10 l AIR-DRIED WT.g 5.000 <000 C.OOO .<;.rtft0 .<nW) -?,00fl .<.ooo .*?.rtr>P> v*S OoO sffloo 6.00Q OVEN-DRIED WT.g -fr.qtol 4.<^5l1 4flSS' ^ S t <l.,q&< 4..llo& ^fll.1 ^ait^ ^.lio 4..^^ 4.q6R nig Na:(;l.;-,n,,! IW "~~ no 200 fan 3JO 27 f) fjao /SO ISO 110 72- maq /100 g soil ^a /S^ /^.<? /7.^ /fl.< /<?.& /7.^ //.<? ^./ -:: ^ :- ^.S DATE^-^^ ANAIJggT?^^^. . . . CO ,,,,,,,,,,,,,,,,,, ,, g ^l ^ ^^" EID129663 IABORATORIES, Inc. P.O. BOX 249, 1126 N. FRONT STREET NEW ULM, MN 56073-0249 PHONE (507 354-8517 WATS (800) 782-3557 FAX (507) 359-2890 WE ARE AN EQUAL OPPORTUNITY EMPLOYER MEMBER AC1L Report To; RocbdbRoindeau 3M Environmental Lab 935BushAvc.,Bldg.20 St. Paul, MN 55106 Date: Work Order: DBteltocdvd: 27 August 1997 10-0447 25 August 1997 Page 1 of4 InofgarncslabNo. SoilLabNo. ..... Sample ID. ..... Analyte NttritcNitrogea(mg/Kg'N) Sulfate(mg/Kg) ......... Sulfite(n^/L)........... S4352 W-547 R2382-1 S4353 W-548 R2382-2 S4354 W-549 R2382-3 S4355 W-550 02382-4 S4356 W-551 112382-5 S4357 W-552 R2382-6 0.41 0.41 036 0.14 <0.1 ... ^0.1 jiM 98.4 98.6 73.3 53.9 43.4 70.4 <2 <2 <2 <2 <2 <2 Report approved by: Anthony ILKochele By aad for MincMota Valley Te8tiBgLabo(3tories,6ic. MTLiMiMMttccuniq<tWMih<laM<^MtlnliaaMfclMllBtfchiiott<Maifalttlo^^ M^touiildl.^lfaMril.>attfM.Mfl..aiMBM.Ma^.Min^MVTI.aataJ>Bc(lBdl^l^>^ rfdtoi,^tt<llliBlbrtiiMtiii^rf<iiiit.aBd<itMa iitt^ tMiaagijiuiiiiuiiMiiiiI>^a^ ^ S yw i Ln __ ./ I } ~~ EID129664 LABORATORIES, Inc. P.O. BOX 248. 1126 N. FRONT STREET NEW ULM. MN 56073-0249 PHONE (507) 354-8517 WATS (800) 782-3557 FAX (507) 359-2890 WE ARE AN EQUAL OPPOBTUNITT EMPLOYER AOL Report To: RocheDeRdbideaa 3MEamroamenlalLab 935 Busk Aw., BIdg. 20 StPaid,MN 55106 Dite: Work Order: DateRecdred: Page 2 of4 27 August 1997 10-0447 25Angnstl997 Inot-samcsLabNo., SoflLabNo. ..... Sample LD. ..... S4358 W-553 K2382-7 34359 W-554 R2382-8 3*369 84361 84362 W-555 W-556 W-557 R2382-9 K2382-SO R2382-11 Aodyte Nitrite Nitrogen (ing/Kg^O .. <0.1 0.11 <0.1 '^rate^q[ <0.1 Sulfate(mg/Kg) ........... 217 153 102 63.3 46.2 SvSte(ma/L)............. <2 <2 <2 <2 <2 Report approved by: (i ^<J1A AnthoayILKoebcle > By a^ for MumesotaV^ey Testing I^bccatories,!oc. 03 ffi 0 --* 0 \<f3\ \ <3\ MTI,ciiuulmdMiKiii^<^lteuIf&fa<ltai<q^>dai<Mkltli|.nhMp(riU>feMV11.U^ itatslMlnaltatulDrfiafiiliailii .anptojiiUMUcoa<Hliaa^l.cUatth.Mn^Mlb.uu^.iJi^ntia<.pHntbTtVTl.a.aala^plol.tlu><ii^^^Fti^^<^ rfdlal.i^OThnrilaoa^pubUt>i<noflteau.rnnfh.lMlOfactt&larn<nlii^ifrepcrtL>lM^ i^abl&ua*aim70lliu _-- J I ^1 ~~ EID129665 LABORATORIES, Inc. P.O. BOX 249. 1126 N. FRONT STREET NEW ULM, MN 56073-0249 PHONE (507) 3544517 WATS (800) 782-3557 FAX (507} 359-2890 WE ASEANEQUAL OPPORTUNITY EMPLOYER ACH Andzte Nitrite Nitrogen Analysis of3M Samples Page 1 of 1 Detection Lerd O.lmg/KgN MytfeojRgf?rgflw Methods of Soil Analysis, 2ad Edition, 33-8 Suffitte 40mg/Kgoaa5g sample SW-846, Method 9038 Sulfite 2.00 mg/L EPAMeflK)d377.1 s 5 Lft S ltTLtB.<rt^ll<CT^rflk.riirtaM<a<h.^<a-ln>i*>lli^n!>ld^ ttBipUai>l~^taiUricii^I.rtltl^w.p^rat^uriiia^"pBag!^r<TLA.niutoripBlcUolocai^lli^^ Tf[^llllH.^lll^^1l1^T^-J--'-I-JJ'-^-^lllll '. l.^-'i-i^m.^m^...^.l.,-irii..dhiiianllamBi. Q (J yf i /[C" EID129666 DATE: 08/21/1997 3M ENVIRONMENTAL LABORATORY CONTRACT LABORATORY i;ORK GRCER BY PARAMETER LAB REQUEST NO. RB332 (XNTPACT LAB : hVTL PROJECT NUrfSER ; BIOENSWIR SHIP DATE : ^T^py CoBp-.ter Cade Test Nane PROJECT LEAD; RD HOhiELL TELEPHONE : FAX S 612-778-6176 Sample Nainbars Sample Available Date Result Due Date N02-N 03 NITRITE NITR03E?i - as M 1, 2., 3, "!., 5, 6, 7, 3, 9, 10i 11 SULFITE 1, 2, 3, ^ 6,, 7/,, 80, 97, 1J.0V, 11 SUi-FATE - as S04- 1., , 3, 4, 5, A, 7, 8, 1.1 03/13/1997 OS/a7/19?7 08/13/1997 08/27/1997 08/13/1997 08/27/1997 ?5-^ ^^- EID129667 Ecotoxicotogy and Environmental Fate Laboratory Copies of Soil Methods EID129668 3M ENVIRONMENTAL LABORATORY PRELIMINARY PREPARATION OF SOIL SAMPLES FOR LABORATORY ANALYSIS 2.00 mm Air-Dry Soil Air-dry (ambient room temperature) soil samples on flat trays for 24 to 48 hours or (Kid thoroughly dry (constant weight). If desired, samples can be oven-driBd at 35C overnight (18 4 hours)." Pass air-dried soil (cnished and mixed via mortar and pestfe) through a. 2.00 mm (10 mesh) stainless steel sieve. This removes large . - - -.,--,__ ___.,,, ,,,,, ,., etnnoa oraval and IIMQS. bI^eO&fuUrMthWeur idwhwriud.e..d^.iiwnto--js--m.a_llef--r p- ortions, . The soil sample is now ready for laboratory analysis. . Use the 2.00 mm ailrt-dry sooul (lor ssooni reactaion te5sitas a01nxd1 fiwoir physical characteristic analysis. soluble salts analysis or store In a cool. dart room. This soil is also used tor ffl31LREACTION TESTS pH SOLUBLE SALTS ANALYSIS BectricalConduaivity PffifaCftt CHARACTERISTICS Soa texture and ciassiBcation Urno Requirement Gypsum Requirement CI'.S04 Alkalinity 0.500 mm Air-Dry Soil Obtain about 20 to 40 g of a rapresentativs portion of (he 2.00 mm soil and grindin an agate mortar and peste until the entire sampte passes through a 0.500 mm (35 mesh) sieve. Use this soil for exchange activity tests {Cation Exchange Capacity, Base Saturation. SAR, ESP) and (or nutrient analysis (N.P.S). 0.063 mm Oven-Dry Soil Obtain about 10 to 20 g of a representative portion ot the 2.00 mm the entire sample passes through a 0.063 mm (250 mesh) sieve. Oven-Ay (105-110C) the above sample (placed in a tared abmir Use this flnety ground (ball milled) oven-dry soil tor total elemental analysis (1CP.AA). total fluoride and TOC analysis. SPECIAL NOTE All dried soil samples are placed in impermeable, polypropylenebottles. They are stored in 619 soil cabinet (dark and at ambient room temperature) (or one year after testing. Disposal (or afl soils and Iheir extracts is by incineration. REFERENCES > -~ Page, A. L.. MBter R. H. & Keeney D. R. (Eds.) 1982. Methods ot son Analysis, rare c. uiniw ----.--,,--. - -.-- --. 0^ 3 ^ Agronomy Monograph No. 9 (2nd Edition). S B<, K. and R. H. Geldarman,l988. SoB Sample Preparation, p. 2-4. In: Recommeandead Chemical Sotl Test Procedures (or the ---- S North Central Region. North Central Regional Publication No. 221 (Revised). NOTE. I! nitrate analyses are to be detenninad. the soil should ba.dried within twelve hows of sampling to prevent changes in the nitrate content. (Revised 12/94 RRR) f? 4 ^s- EID129669 3M ENVIRONMENTAL LABORATORY SOIL WATER CONTENT PERCENTAGE OF WATER IN THE SAMPLE ON A DRY-MASS BASIS PRINCIPLE OF THE SOIL WATER CONTENT METHOD The amount of water in a soil affects directly the growth of crops, microbes, and insects. The strength of the soil, which determines root penetration and the energy requirements for Ullage are dependent on the water content, however, me amount of plant available water in the soil is dependant on the soil water potential. Since the water potential is more difficult to determine, the water content is used as the indicator of the state of water in the soil (In laboratory terms, practically every type of soil analysis requires that the results be reported on a dry mass basis.) Traditionally, the water content has bean expressed as the ratio of the mass of wate.(,prassinUn|ha sample to the mass of the sample after it has been dried at 1C6C to a constant mass. Thus, thawa|9j^ntent as usually used in soil studies is a dimensionless ratio of two masses or is expressed as a paccenlago resulting from multiplyingthe dimensionless ratio by 100. Tha laboratory procedure employed here is water content measurements by the gravimetric method. It involves weighing the wet sample, removing the water, and reweighing Ins sample to determine the amount of water removed. Water content is determined by dividingthe difference between wet and dry masses by the mass of the dry sample to obtain the ratio of the water mass to the mass of the d>y soil, then multiplied by 100. This is now the percentage of the water in the sample on a dry-mass or dry-weight basis. ;.,i i' ,,a aa. vw r. - . ; as i s,g c (& T- ff -if- RANGE AND SENSITIVITY Tha range and sensitivity will depend on the time necessary to reach constant weight and. tha analytical balance used. -.-swfici INTERFERENCES Factors that may influence the results include: Failure of temperature control. The drying oven used must maintain a temperature in die range of 105 to 110'0. Sample matrix. Organic soils may have mass losses arising from oxidation and volatilization of organic components, also stony and gravelly soils, both on a mass and volume baste, can be grossly misleading. PRECISION AND ACCURACY Accuracy and reproducibility of water content measurements, assuming that tha weighing precision is consistent with the desired precision of tha water content measurements, depend upon tha drying technique and how used (whether 24 hours is adequate in obtaining a constant weight). o u> -~i ^ ^ l^ EID129670 EQUIPMENT AND REAGENTS 1). Analytical balance accurate to 0.001 g. 2). Ovan-driad aluminum weighing dishas. 3). Drying oven with temperature control device that will maintain a temperature between 1s0u5f-f1ic1i0entC. Forced -air circulating ovens will dry samples more rapidly, but convection ovens are " 4). Desiccators containing active dasiccant 5) No reagents are required. 1). 2). 3). 4). 5). 6). 7). WATER CONTENT PROCEDURE Obtain at a minimum 10 to 40 g representative portion of either a ball milted (air-d' ried) sample or as received (wet) sample. .;'^l.^.. Place in oven-dried aluminum weighing dish. Weigh the sample to the nearest 0.001 g as soon as possible. ...,,,.,. Place the sample in the drying oven and dry it to a constant weight (at a minimum 24 hours)., Remove the sample from the oven and place it in a desiccator until cooled to ambient room temperature. Rewaigh the sample to the nearest 0.001 g. ^ y^-s^mpw Calculate the water content as percentage of water in the sample on a dry-mass^basis^ .^^. ^^ % Water Content - (Weight of Wet Soil * Pan . Weight of Pro Soil Part x 100 Weight of Diy Soil ,, """'' REFERENCES Gardner. W. 1986. Water Content p. 493-544. In: Arnold Klute (Ed.). Methods of Soil Analysis, Part 1. Physical and Mineratogical Methods. Agronomy Monograph No. 9 (2nd Edition). I s 1*1 (^ 135' EID129671 3M ENVIRONMENTAL LABORATORY SOIL pH METHOD PRINCIPLE OF THE SOIL pH METHOD Soil pH is ona of the most indicative measurements of tha chemical properties of a soil. Whether a soil Is acidic, neutral, or basic has much to do with tha solubility of various compounds, tha relative bonding of ions to exchange sites, and tha activity of various microorganisms. Three soil pH ranges are particularly informative: a pH <4 indicates the presence of free acids generally from oxidation of suHides; a pH <5.5 suggests the likely occurrence of exchangeable Al; and a pH from 7.8 to 8.2 indicates the presence of CaC03. Soil pH is a measure of the activity of H-1- in the soil solution. Ionized H is in equilibrium with the adsorbed nonionized H but usually is a small fraction of it Much of tha nonionized acidity is exchangeable only at higher pH. Although other criteria are sometimes used as indices of One needs of acid soils, tha lime requirement is generally a measure of the base (lime) required to neutralize that fraction of the total acidity that must be neutralized to attain a desired soil pH that is favorable for crop growth. Hence the activity of H+- in the soil solutions is the intensity factor (index), whereas exchange acidity and lime requirement are the capacity factors of soil acidity. , ,.,.3 RANGE AND SENSITIVITY The range and sensitivity of the method will depend on the pH meter used. In routine soil testing, it is only necessary to read the pH to 0.1 units. INTERFERENCES rw Factors that may influence the measured pH include: ,ie, ma. w.e,.,sr(.,-: T(hHeyndartougreenainodnstympeayofdiinssoorgcaiantiecfaronmd othrgeaenxicchcaonngsetistuiteenstsorthmataycobnetrdibisuptelatcoedsobiyl ahcyiddterso^aa\.wTs^iy(if&bgwa.Swat;- fweswi <' The soil/solution ratio (1:1 is the most commonly used), nisiar'aia^- " The salt or electrolyte content (H+ are displaced by the cations of salts contained in the soils, in addition, the salts also displace exchangeable Al, which upon hydrolysis increases the H+ in solution. , The C02 content (COg from the atmosphere or soil air) dissolves HI water forming carbonic acid (HzCQa) which can tower the pH. In tha actual measurement of soil pH. the soil and water are shaken so they coma to equilibrium with the COa in the air. there is no effect on the pH measurement Only in soils of very low [H+] where the pH is considerably above 7.0 and particularly in soils containing tree CaC03 does the COz concentration of the air has any appreciable measurement effect on pH. Errors associated with equipment standardization and liquid junction potential. The use of 001 M CaClz is recommended to minimize differences caused by some of the above factors. This dilute salt solution masks small differences in salt contents without displacing a large fraction of tha H+ or Al34'. In addition, errors due to the liquidjunction potential are decreased. PRECISION AND ACCURACY S Random variation of 0.1 to 0.2 pH units is allowable in replicate determinations and can be expected from s, one laboratory to another. Dehydrated and scratched electrodes will give erratic values. % tTM-* o ^n a l&O ^ l^S~ Eini29672 EQUIPMENT AND REAGENTS 1). pH meter equipped with a combination electrode ( or soil pH electrode, Coie-Pannar Model ?5992-60) and automatic temperature compensation (ATC) probe. 2). Standard butters, pH 7.0 and pH 4.0. 3). 50 mL conical, polypropylenecentrifuge tubes. 4). Automatic pipets. 5). Gyratory shaker. 6). MilliporeMiUi-QTMwater. 7). Calcium chloride (CaCIa) solution. 1 M or 0.01 M. pHw AND pHs PROCEDURES 1). C^I&ratepH meter wim commercially prepared buffer solutions o(pH 7.0 and 4.0 according to the instrument Instruction manual 2). Weigh 10.000 g of 2.00 mm air-dried soil into a 50 mL conical centrifuge tuba. 3). With automatic pipat. add 10 mLotMnri-Q'TM water to each tube. 4). Mix thoroughly tor 5 minutes, preferably on a gyratory shaker. (Option: mix for one hour.) .*>ii-0* *, iy>.' w- n <w 5). 6). 7). 8). 9). 10). 11) Let stand for 10 minutes. (Option: let stand for one hour.) Insert the electrodes into the container. layer) Note; tee test mixture after settling will have an upper, lower layer of opaque soil suspension. Immersg the relatively clear layer (supernatant this mixture until the pH and a sensitive bulb Is covered by the opaque soil , sussppansiw,4,^"""^,. ewlehctHroedeleinato^U^referencecontad'inthesupema.antlayer.^ Allow time for the electrode to reach equilibrium(-1 to 3 irin.) and record as soil pH in water, pHw To detenrine the soil pH in 0.01 M CaCIa, add 0.10 roL of 1M Cads solution to the son water suspension. Mix intermittently tor 30 minutes. (Option: m'K 30 minutes, let aland 30 minutes.) Insert electrodes, and record as soi pH in 0.01 M CaCtz. pHs- Alternatively, the soil pH in 0.01 M CaCIa may be determined directly by substituting0.01 M CaC<2for lha water In step 2. H tha lima requirement is to be detemuned on the samples (pH < 6.9), save them for this purpose after reading the pHw or pHg. ,,.,, ,,,,,, ,, REFERENCES McLean, E. 0.1902. Sol pH and Ume Requirement, p. 199-224. Irc A. L Page. R. H. Miner & D. R. Koeney Microbiological Properties. Agronomy Monograph No. > (Eds.) Methods of Soil Analysis, Part 2. Cheiricai and w 9 (2nd Edition), fr--i Eckert. D. J. 1988. Recommended pH and Uma Requirement Tests, p. 6-8. In: Recommended Chemical Publication 221 (Revised). Soil g ^ Test Procedures for the North Central Region. North Central Regional No. 2 loi 4 /a-5" EID129673 CATION 3M ENVIRONMENTAL LABORATORY EXCHANGE CAPACITY (CEC) BY SODIUM BATCH EQUILIBRIUM METHOD SATURATION PRINCIPLE OF THE CEC METHOD electrostatic charge as a result of the atomic substitution in the lattices of the soil surfaces of the oxides, Soils possess an ol hydrolysisreactions on broken edges of (he lattices and exchangeable ions and form the attract minerals and as a result hydroxides, hydrous oxides and organic matter. These charges exchange complex. reversibly adsorbed per unit capacity (CEC) is the measure of the quantity of cations (An equivalent weight is The cation exchange weight of soil. It is expressed in milliaquiva!ants par 100 grams of oven-dried soil. hydrogen.) The principle of the method described here that is chemically equal to one gram of sites in the soil with a specific cation, sodium; removal of that quantity CEC by saturating the cation exchange adsorbed cation, sodium with the measures (washing);and finally replacing the tahmemeoxcneiusms sioantu(rdaetisnogrpsotilounti)ownhich is measured by an appropriate method (e.g. ICP). RANGE AND SENSITIVITY sensitivity of the method are dependent on the complicating interactions between saturating, The range and extracting solutions and the soil constituents. washing, and INTERFERENCES of the CEC method use. The three steps are saturation of the cation replacement of the Potential errors exist in each step specific cation; the removal of the excess saturating solution; and exchange sites with a Possible factors of error influencing these steps are: . .,, the-saturating cation due to saturating cation. Saturation Step. Exchange sites may not be completely saturated with adsorption sites or i-naysbssdua to the saturating other cations in the saturating solution competing for replace tha more strongly adsorbad'cations, such as replacing power is insufficient to (Exchangeablealuminum andifts hydroxy forms are not cation's exchangeable aluminum and its hydroxy forms. saturating solutions.) This effect causes an underestimate readily exchanged with monovalent cation problem associated with this step could be the presence of other cations In the of the CEC. Another saturating solution (dissolutionof calcium carbonate, gypsum and silicate minerals). The adsorbed cation may be Washing Step. This step has the most potential sources replaced by a hydrogen ion. of It errors. may also be replaced by cations brought into Rna removed by hydrolysisand solution in the washing solvent from the dissolution of calcium carbonate, decanting (these gypsum and silicates. exchangers have a tendency day particles and organic matter may be lost during the during washing). Some of the saturating solution may to disperse as the excess electrolyte is removed exchangeable cation it the washing is incomplete or if be retained in the soTilhaenmd alajoterirtyexotfrtahcetesde aesrroarns causa the CEC to be underestimated. of expandable the salt is retained. Adsorbed cation could be trapped between interiayers by contraction preventing its Replacement Step. silicates (this is especially true in vermiculitas and weathered micas) thus, of tha CEC. The second factor 2:1 layer replacement during extraction. The end result is an underestimate cations may be extracted from zeolites, teldspathoid, potential error is that nonexchangaable extracting solution. The error gives high CEC values. causing feldspar, ai nd mafic minerals by the PRECISION AND ACCURACY by using a method of CEC determination that employs reagents of similar Errors can boe concentration redou - and ceda uy p.H..t-o .t huo--asue.^.j_o-fn.ti.h,.e--esno--iilnt-oo- . be analyzed. H>SL a^/,1^' EID129674 EQUIPMENT AND" REAGENTS " i 1). 250 mL conical, polypropylene cantriluge tubas. 2). Automatic pipels. 3). Gyratory shaker. 4). Programmable centrifuge. 5). 1.0 N. pH 8.2 NaOAc (Sodium acetate). identHied as Reagent 81: For each liter of solution, dissolve 82.03 g of NaCaHaOz in MillieTM water. Measure the pH. The pH of this solution should be 8.2. If necessary, adjust the pH with either a few drop of acetic add (CHaCOOH) or sodium hydroxide (NaOH) to bring the reaction of the solution to pH 8.2. 6). 1.0 N, pH 7.0 NH40Ac (Ammonium acetate), identHied as Reagent S3.: For each liter of solution, add 58 mL of glacial acetic add (CHgCOOH)to approximately 600 mL of Milli-QTM water and then add 70 mL of concentrated ammonium hydroxide (NI^OH, specific gravity 0.90). It is best to add the NH40H under a fume hood through a long-stemmed glass funnel so that it is introduced into the bottom of the acid solution. Cool the solution to room temperature (-20 to 25 C) and adjust the pH to 7.0 with either CHsCOOH or NH^OH. Dilute the solution to volume, mix it and store until ready for use. Recheck the pH prior to using the solution. 7). Reagent grade, 2-propanol (99% isopropyi alcohol). PROCEDURE FOR CEC BY SODIUM SATURATION 1). Weigh 5.000 g of a 0.500 mm air-dried soil sample and transfer the sample to a 250 mL conical, polypropylene centrifuge tube. 2). Add 132 mL of 1.0 N. pH 8.2 NaOAG solution (Reagent 1). stopper the tube and shake on the gyratory shaker over-night ('18 hours) at 300 to 400 rpm. This is the saturation step. 3). Remove the sample from the shaker and place it in the centrifuge. Centrifuge 10 minutes at 3000 rpm. This recommended time and speed will be sufficient; a clear supernatant will be obtained. 4). Decant the supernatant and discard the liquid. NOTE: Careful decanting is vary important. Panicles of soil tost during the decanting steps will effect the final CEC result; a tower CEC value is the and result of this which leads to a falsa interpretation: poor soil quality. 5). Washing the sample is the next step. This eliminates the excess sodium. Add 50 mL of 2-propanol to the sample, stopper the tube and shake it on the gyratory shaker tor 30 minutes. Centrifuge as before. Decant the supernatant and discard the liquid. Repeat this step once more. Shaker speed should be the same as used in the saturation step. (Total wash time 60 minutes using 100 mL of 2-propanol.) 6). Add lOOmLof 1.0 N.pH 7.0 NH40Ac (ReagenHK) to the sample, stopper (he tube and shake it on the gyratory shaker over-night (-18 hours). This is the replacement step. NOTE: Make sure the Identical shaker speed and time are used as in the saturation step. 7). Remove the sample from the shaker and place it in the centrifuge. Centrifuge 10 minutes at 3000 rpm and decant the supernatant into a 125 mL polypropylene bottle. 8). Determine the sodium (Na) content by available methods, e.g. ICP. 2 /03 4 U^~ EID129675 CALCULATION CEC EQUATION: O/INajapmea 100 - magrtOOo soil oven-dried weight o( SOSfay * % soil moisture was previously determined. REFERENCES Chapman, H. 0.1965. Cation Exchange Capacity, p. 891-900. In: C. A. Blade (Ed.) Methods of Soil Agronomy Monograph No. 9 (1st Edition).;,;. ; Analysis, Part 2. Chemical and MicrobiologicalProperties. :,:1:;!: -.irfc'-,.- Rhoades. J. 0.1982. Cation Exchange Capacity, p. 149-'57. In: A. L Paga. R. H. Microbiological Properties, Miller & D, Agronomy R. Kaeney Monograph No. (Eds.) Methods of So3 Analysis, Part 2. Chamical and 9 (2nd Edition). Brown, J. R. and 0. Warncke. 1988. Recommended Cation Tests and Chemical Soil Test Procedures Measures ot for the North Cation Exchange Central Regiqnj|gr)^,^,^ Qw Capacity, p. 15-16. hi: Recommended Central Regional Publication No. 221 (Revised). N.C ? 'l" -- ^ a 0 l-^ 0 ^l/l 3 161 ^ l^S' EID129676 Environmental Laboratory Copies of Chain of Custody, Shipping Papers, Lab Requests EID129677 lm4m ImSHIPPIKG MEMORANDUMOm (FOR NO-CHARGE SHIPMENTS ONLY) Ship to 4u 3K Environmental Technology & jDate 05/08/97 4m Service Laboratory. B-2-3E-09 (Routing 4m 935 Bush Avenue 4m St. Paul, Minnesota 55144-1000 |F.O.B. | Date |Shipped I 4m Attn: Robert Howell I JB/L 4m Quantity | . Product Code / Description 4m 1 | Container of Water Samples 4m | No. 38-972' I | Weight | 48 Ibs | 4m | | I I 4m | | I I 4m | | 4m | | 1 I 4m j | 4m I I ' 4m | I ) I 4m | I Special Inst 4B&bsolutely must arrive Friday AM/Time restraints. ..-. Freight Class 4m 4m 4m 4ia0riginator VERA L WIGAL 4mCharge (Cost Code) 8309019511001280 4mPurchase Order Ho. 4mValue for Customs Ship From 4mStores, Bidg. 4 Phone 304-863-4895 |MSDS Sheets Required? |Hazardous Material? H | MATERIAL CLASSIFICATION [Corrosive Toxic 4m 4m 4m| 4ml |Flammable . ** AUTHORIZATION ** Other On |0m I Om 4m| I On 4n| I On oa t--* 8 ^ lOb ^ I^S' ^o EID129678 ASH010580 PurchiiiOrdrH ,>-jiiiji).iji-j.i-jiij Prolncl Him* p/^ ^cw^7 HpL^6^ i5upc/{^ u^^^A)&T^/^ U/O/^S # 6 0 F Project Mirifgar & Phons f RBportCopytD! 5?-i^! 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Ittstn/ctlons md Agreement Provisions on Reverse Side iSTRiBunoH:onieiH*i..LAB. w -------- -----. - ,,. - .,,,....,.,.. - -^sly'--------*--^--- la4a ImSHIPPING MEMOBAMDUMOm (FOR NO-CHARGE SHIPMENTS ONLY) Ship to 4ia 3M Environmental Technology & jDate 4n Service Laboratory, B-2-3E-09 (Routing 4ia 935 Bush Avenue 4m St Paul, Minesota 55144-1000 JF.O.B. 1 Date | Shipped 4m Attn: Robert Howell JB/L 4m Quantity | Product Code / Description 4m 1 | Container/Soil sample 4m | ' 06/02/9^r' 4m | Om Ho. 38-97320l0m OB Om Om Om | Weight Om | 30 Ibs Om 1 Om 1 Om 4m | 1 4m | 1 4m | 4m | I 4m | I 4m | 4m | Special Inst 4mShip Overnight 6/2--Must be delivered TUBS. AM Freight Glass 4m 4ra t i ' i " i 1 1 1 1 > * i ;->t).l.p ua'erT.3...gfsi- 4m 4m0riginator VERA L WIGAL Phone 304-863-4895 4mCharge (Cost Code) 8309019511001280 . |MSDS Sheets Required? ^v,^, 4mPurchase Order Ho. 1Hazardous Msiterial? N 4mValue for Customs 1 MATERIAL CLASSIFICATION Ship From 4mStores, Bidg. 4 1Corrosive Toxic 4n 4m 4n( |Flammable . ** AUTHORIZATION ** Other OB jOm 4m | |0m 1 1 4m| JOm Om On On Om Om Om Om Qn Om Om Om Om On ,. Om Om Om oa 4al I Om /OS ^ ^ a 0 * 0 u 00 1--t 1^ EID129680 -,*iw,.- \GINEERING <^JB^> COMPUTATION SHEET &-SS7?1C T,Ti.i^-^c. 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IHSTAIIATIONS ( EID129681 OM q----Environmental Request Form Laboratory ^ryy ,r;tr j7 f ^ 0 0 ^ i.ubnequwiNo -- omsu.a6M./6//-^^9- Address 3M Environmental Laboratory 935 Bush Ave. Building 2-3E-09 St Paul, MN 55106 Attn: Sample Custodian Phone (612) 778-6750 Fax (612) 778-6176 RequeBter N"ir -- i loailloii ^ t //?DT Pre|Kl PHaWlw (40 CMBaOT My.) .. ^ l^d^t $0r' (yromf^uieiw a/'< l<lhliiTSCAe(dlprojcl7(S*<bKlcfIclllnltn>cllon) [XjiL No. (Mln) PHijnNo. i Sub.Accl. MUST BE CHECKED Q Yes ^No pMlxmoinaing D RCRA D "rscA D CWA D CM D SDWA DBrN--Md Envlron AalMILwd n Routine 0 "3'03' PteniCoda Planning Status (^0 Clan/Johff'ro|tl No. QtA-Qi^) Clanffrlolily -SiE ^e. C^WerAs . D MSDS ^] (^fTQ/^er ^^>.er\/i SlelC<mcm/S|cllHniillnB ^^^h^ ^^& S-^ Cawmitt ^ j i i i < .Di^d^ STD^^ <^>eX3A- J- 11^ \m / Crf/H^u-jt H Tv0^ rC-.. - f f, -u 9 S <--?./-i,<-AZya-,SCfJyc (/ 6-0'.'=> 'to<-^^e-^ 3C>y8 ^ 30^% %T-<b^AA-^0\l"SL-R. Sampte No. (Range 0-999) -------^ / 2 'r/efa7 ^ftin ..:: . ;. :'. 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Unit 12, Vtetettoo.Onlario,Canada N2V2C5 (518)747-2575 FAX (619) 747-3006 a CVO 2300 NWWalmH Boulevard Cwallto, Owoon 973305638 (541) 752-4271 FAX (514) 762.0276 coc RtquMlMJ AnilytfMl MMhod THIS AREA FOR LAB isn-------- Pa {u \J <Sk. ? <s, ^ <j, S ^ (X ^ v> <A PlWWW ^ X \< S^ X' LabPM Cu ' pH Cuc lc QCLwl 1 a 3 Othw Coohr T*mpnhir Alternate DM>riptlon A SH SmpMBirTIU( ,, ^, <rf<MK<ilp.6lp&M^nw74 -^(^eyce^ vnyt{j^f9 ri-^inMvn '/ /Jy/L^s>^-^/^/r\ MdlWiBy / flMMH91l|MMM| SpMMlMlmlhM! (nrfnMikHM Mirf Aw--fflwit PwvWoru oil RWMW SM* Dt*rnm r ^ % 7 tuii/rim*/ ^^,^2^ R*UWM>1 B)! (WInquMKdBy A^houilplripMMMi ^(B.ti.ripiripMi--t ShlppdVl UPS F*d-& CMlMF ^;, ^; ^.: -;p i' 1""' "'' - "iw. ^ W DtrfTIlM ' Shipplnst /^^ nOtkOrtgtniS-UVB, Ytlow-L CH2MHILL Analytical Services 0 UKQ 2587 Ftlrtana Drive MoiHoonwy.AL36116.1K2 (334)271-1444 FAX (334) 271-3428 0 LKW Camiro AnalyticalIjtboretottoo, inc. 50 Bathunx, Un 12.Walatoo. 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AL 38110-1822 (334)271-1444 FAX (334) 271-3428 0 LRD 5090 CatMplfef Road Reddlno.CA 96003.1412 (816)2444227 FAX (916) 244-4108 D LKW CuwIroAmMlol Luborloriw, Inc. 50 Balhuref. UnX 12,Witorioo, Orterio, Caiud* N2V 2CS (619)747-2676 FAX (518)747-3806 0 CVO 2300 NW Walnut BcxJevairi Cotvalte. 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Environ 3M Environmental Laboratory 935 Bush Ave. Building 2-3E-09 Nuns F^CS^^l^hinciMWx.l Locailcm . PhorNo. ' .. . .. DdgNMCiKi n Routine n ptanlCixj* ProjaelLMi " RDH/^ Planning SHim ) St. Paul, MN 55106 Attn: Sample Custodian Phone (612) 778-6750 Fax (612) 778-6176 ^iW^i l>iPr^r \A/A^KIC]N<( islhlsTSCA8(d)pml<K<?(S*r^t3^ii<ii^on)^^ ^ f ^ SSSjtta. 1 ^ ' 1cla5/JoUPro)a;lND. MUSTBECHECKED 0 Yes ^No \^^^ IfilftPMOAARD D RCRA D tsCA D CWA D CAA D SDWA D MSDS D Y/) Olast/Pinill;' SslelyCwictiTH/SptcftI Handling ConumnM ; AS resllRnquiKKl Sampla No. (Range 0-B9B) ------ SamplaCode (12 Character Max)----1" " Sample Date & Time (MM/DD/YY. HHiMM) ------- Sample Description (12 Character Max)------ 3MI.D. 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