Document KRZaZOE8Ezn6Eg8mov2ro1wYx

3M Environmental Laboratory 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 f*o cz r ~ T H {fi. __ UD m 33 . 2 ZE O C $ kO *M ro U3 Prepared by: Susan A. Beach Senior Environmental Biologist 3M Environmental Laboratory Building 2 -3E -09 935 Bush Avenue St Paul, MN 55144 000077 USEPA 8950 ASH010474 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 > in Xo o-t* Ji 4 M S' USEPA 8951 d?<?O 70 3 M Environm ental Laboratory Summary of Results . DuPont Washington Works Samples Sample Dates 5/8/97 (groundwater), 5/30/97 (soil) DuPont 3M LR No. Smpl. No. Matrix R2008-1 1 ground water R2008-2 2 ground water R2008-3 3 ground water R2008-4 4 ground water R2008-5 5 Dl blank R2008-6 none soil POAA'1, ppb 52 49 52 53 n.dm 364 Voi. & Semi Vol. F, Cl. Br by AED, ppm < M QLm < MQL < MQL < MOL < MQL . < MQL (1) POAA - Perfluorooctanoic acid anion (2) limit of detection/limit of quantitation 650 ppt. (3) Minimum quantitation limits: Br - 1.176 ppm in water, 1.18 7,1.2 2 0 ppm in soil C l 1.408 ppm in water, 1.253,1.461 ppm in soil F 0.280 ppm in water, 0.282 ppm in soil ASHO10476 O Q Q 07f USEPA 8952 i> .+ u / J _ I i-Ok w' u t. ) 1 1 , ' ,A il <HjO W uA 3 M Environm ental Laboratory Summary of Results DuPont Washington Works Groundwater Samples ASH010477 DuPont 3M LR No, Smpl. No. R2148-1 MW-1-1 R2148-2 MW-1-2 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 R2148-9 MW-4-2 MW-5-1 R2148-10 MW-5-2 R2148-11 MW-6-1 R2148-12 MW-6-2 POAA"> mg/L 5.64 5.32 0.234 0.234 0.487 0.477 0.0842 0.0590 < PL" < P0Lm < MDLP> < MDLP> Total Fluorine mg/L 8.0 16 3.3 3.5 4.2 3.3 4.0 4.2 3.0 2.8 2.3 4.2 Adsorb. Vol. & Semi- Trichlorotri- Fluoride Ion Organic Organic F, Vol. F by fluoroethane mg/L F, mg/L'41 mg/L AED, ppm |ig/L 0.20 7.8 4.5 0.20 < [F]< 2.5 820 0.20 16 4.2 0.20 < [F]< 2.5 730 0.16 3.1 0.28 0.20 < [F]< 2.5 1600 0.16 3.3 0.46 0.20 < [F]< 2.5 1500 0.14 4.1 1.1 0.20 <(FJ<2.5 2300 0.14 3.2 0.76 0.20 < {F]< 2.5 2400 0.11 3.9 0.19 0.20 < [F]< 2.5 760 0.11 4.1 0.14 0.20 < [F]< 2.5 670 <0.10 2.9 0.11 |F] < 0.05 130 <0.10 2.7 0.14 0.05 <[F]< 0.20 140 0.10 2.2 <0.05 |F] < 0.05 - ___ 0.10 4.1 <0.05 [F] < 0.05 -- Acetone m /l -- 10 -- -- -- -- 10 -- -- -- - Vo r< Yo QD OcinnN 00 O<h iWn 3 tert-Butyl DuPont Alcohol 3M LR No. Smpl. No. pg/L R2148-1 MW-1-1 59 R2148-2 MW-1-2 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 _ cis-1,2Dichloroethene pg/L 5.8 5.9 Chloroform pg/L 1,1.1trichloroethane pg/L 5.5 14 5.9 14 37 6.3 39 6.2 13 16 5.8 _ Trichloroethene pg/L _ 140 150 520 570 81 66 _ _ Tetrachloro- Trichlorofluoro ethene methane pg/L pg/L __ _ __ _ 16 _ 18 5 26 5.2 26 _ 5.9 _ __ __ _ _ __ (1) POAA - Perftuorooctanolc acid anion (2) Practical quant, limit - 0.0510 mg/L (3) Limit of detect. - 0 02 55 mg/L (4) Total Fluorine - FluorkJe Ion - Organic Fluorine a m tn viron m em ai Laooraiury Summary of Results DuPont Washington Works Soil Samples Sample Date 6/23/97 ASH0I0478 Total DuPont Fluoride, POAA", Sulfate, Sulfite, 3M LR No. Sample No. mg/kg mg/kg mg/kg mg/kg R2382-1 SS-1 0*2' 21,300 0.119 98 <2 R2382-2 SS-1 4-6' 20,100 0.17 99 <2 R2382-3 SS-1 8-10* 61,200 614 73 <2 R2382-4 SS-1 12-14' 78,300 207 54 <2 R2382-5 SS-1 16-18' 106,300 219 43 <2 R2382-6 SS-1 20-22' 82,700 39.8 70 <2 R2382-7 SS-1 24-26' 59,100 24.6 220 <2 R2382-8 SS-1 28-30' 37,600 29.3 150 <2 R2382-9 SS-1 32-34' 33,500 13.1 100 <2 R2382-10 SS-106-68' 41,200 6.78 63 <2 R2382-11 SS-1 38-40' 30,300 2.11 46 <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 * pH in water 7.7 7.7 7.3 6.7 5.7 6.0 5.8 6.8 5.8 6.1 6.8 pH in CaCI, 7.2 7.3 7.0 6.3 5.3 5.5 5.3 6.3 5.2 5.4 6.2 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, % 12.3 12.7 15.5 18.9 18.3 19.2 20.0 18.1 13.6 17.9 22.2 (1) POAA * Perfluorooctanoic acid anion o0 0 o Oc sr On 00 < Oh W0D0 * t; 3M Environmental Laboratory Project Description Three coolers were received from E.l. 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 analyses of: POAA, Total, free, organic and adsorbable fluoride, volatiles and semi-volatiles, nitrate, sulfate, and sulfide, and soil pH, percent moisture and cation exchange capacity. ASHO10479 *> 4 >2$ USEPA 8955 -0 * 3M Environmental Laboratory POAA Analyses in Groundwater and Soil (5/97 Samples) 7*4 USEPA8956 C 0 0 0 S 3 ASHO10480 3M Environmental Laboratory Data Transmittal Summary Final Lab Request #: R2008 Date Received: 3M Study#: Contract Laboratory # Sponsor or Client: Representative Name Company Name DuPont Company Address Phone Project Lead: Kris Hansen (8-6018) Group Leader Tun Johnson (8-5294) I^ A ._; . ' Analyte(s) or Test Method #: POAA Sample Matrix: water and soil Analysis Dates: 9/97-11/97 Author: kjh reject Lead (or designee): James D. Johnson (or designee): Analyses): GML, JJ, kjh Data Reviewed by: Internal JDJ: Sent by: / Date kjh on 10/21/97 QAU (Archives): LIRN System: Project Manager: Sue Beach____________ ___________________________________________ Others (List R ecipients/A ddress/P hone/F A X ) Sent by: / Date T. DiPasquale, 22-1 IE-03; 3-1891; 736-3257 kjh on 11/10/97 ASHO10481 A copy of the rep o rt including this form and the client cover page is to be given to QAU LIR N an d to th e G roup Leader. 3 1*5 USEPA 8 9 ^ r Q O S 4 \ 3M Environmental Laboratory- Advanced Method Development Team Kris Hanses Sr. Analytical Chemist Advanced Method Development Team Building 2-3E-09 612-778-6018 kjhansen@ nunm .com Report - Analytical Study Determination of POAA in Soil and Water 1.0 Summary One soil sample and five water samples were submitted by DuPont for quantitative analysis of perfluorooctanoic add anion (POAA). The soil sample was assigned number R2008-6; the water samples were given numbers R2008-1 through R2008-5. Analysis of the samples by negative ion electrospray mass spectrometry (ES/MS) determined that perfluorooctanoate add anion is present in all samples except R2008-5. Specific results are listed in Table 1. T able 1. Concentration of POAA in R2008 m nlx. ' Sample # R2008-6 D ilution M atrix Factor Extractability soil n a. n.a. C o rrected concentration (PPb) 0.364 mg/kg A verage (PPb) Std. Dev. n.a. n.a. R2008-1-1 water 2 1.3 R2008-1-2 water 2 1.3 R2008-2-1 water 2 1.3 R2008-2-2 water 2 1.3 R2008-3-1 water 2 1.3 R2008-3-2 water 2 1.3 R2008-4-1 water 2 1.3 R2008-4-2 water 2 1.3 R2008-5-1 water 2 1.3 R2008-5-2 water 2 1.3 lim it of detection/limit of quantitation is 650 ppt. 52 52 49 49 52 52 57 49 n.<L* n.d.* 52 0 49 0 52 0 53 6 rna. rna. 2.0 TEST MATERIALS One soil and five water samples were received from DuPont on 06/10/97. The samples were stored at 4C until extraction; extracts were stored at 4C until analysis. ASH010482 3.0 EXPERIMENTAL-OVERVIEW AND M ETHODS.... 3.1.1 Sample, soil TVicattse no uncontaminated m il was available for blank analysis, the method o f standard aHHiHnn tn fWyrming the concentration irfPOAA in the sofl received from DuPont. A n eight point standard curve was prepared by spiking 2 gram samples o fthe soil w ith some amount o fPOAA solution between 500 ppt and 1.0 ppm. The soil was mixed with approximately 1 gram o f diatomaceous earth and into a 10 mL sled extraction cartridge; The spiked samples w o e extracted using high pressure solvent extraction (HPSE) with methanol; the extracts were dried w ith nitrogen and reconstituted with ACN/water (1:1). After analysis by negative ion ES/MS, the data was subjected to linw r regression afut the resulting prediction equation was used to determine the concentration o f analyte Word Version 6.0 Lab Request #R2008 R200SJDOC 4 IX 5 USEPA 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 standard addition assumes there are no interferences in the analysis and that the extraction efficiency of the analyte from the matrix is not dependent upon analyte concentration. The first assumption is addressed by the selectivity of the both the extraction and the analysis; the lattw has been verified in another study that focuses on a similar m atrix . 3.1.2 Sam ple, w ater For method development, two series of samples were prepared for analysis by ES/MS. In series A, the target analyte was extracted from 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 ofPOAA resulting from Series A and Series B analysis were in close agreement All five water samples were prepared, in duplicate, for analysis using the Series B protocol. The samples were analyzed by ES/MS between two unextracted curves of POAA in ACN/H20. The reproducibility of the curves was within 15%. 3.2 C alibration and controls, w ater A set of controls, including a milli-Q water blank, milli-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 from water and subsequently determine; an accurate extractability factor for final concentration calculations. A POAA standard curve from 50 ppt to 1.0 ppm in ACN/H2Q (1:1) was prepared; all extracts and prepared samples were analyzed by negative ion ES/MS and quantitated relative to a standard curve. The unextracted standard curve was plotted according to linear regression with a coefficient of determination (r2) equal to 0.999. Two-1 mL aliquots of sample R2008-1 were spiked with POAA. These samples were designated the m atrix spike (MS) and the m atrix 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 was expected to be 52 ppb. The concentration of POAA recovered from the samples was evaluated relative to the standard curve. 3.3 E xtraction specifics, soil . The soil samples were extracted with the ISCO 3560 Accelerated Extraction System, 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 volume-1: Static extraction time-2: Dynamic extraction tune-2: Restrictor flow rate: methanol, HPLC grade 2500 p 70 C 70 C 40 m inutes. 15 mL 2 minutes 2 minutes 2.5 "T-/min Samples were reconstituted in glass autovials with HFLC-grade ACN and milli-Q water. ASH010483 Word Version 6.0 Lab Request #R2008 R2008.DOC USEPA 8959 2 ID 4 A S 3.4 ES/MS Analysis specifics, soil and w ater ................ Negative ion ES/MS analysis was performed on a Micromass Platform n atmospheric pressure ionization mass spectrometer running M ass Lynx 2.1. A Hewlett Packard 1100 was used for the autosampler and HPLC system. Mobile phase: ACN/H20 (1:1) Flow rate: 60 yL/min Injection volume: 15pL Cone Voltage * >20 Capillary voltage 3 >2.36 Source Temperature 3 80C Analyzer Vacuum Pressure 3 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 solution and increases system sensitivity to the target analyte. . 4.0 DATA ANALYSIS 4.1 Sam ple, soil By the method o f standard addition, die soil was determined to contain 0.364 mg POAA/kg. This value was calculated using the prediction equation resulting from linear regression analysis of the eight point extracted curve. The coefficient of determination for the curve is 0.990. Calculations used to determine the concentration of POAA in the soil are shown in Appendix A. 4.2 Sam ples, w ater The concentration of POAA in each water sample was determined by comparison of detected peak areas resulting from analysis o f the samples to the average ofthe two unextracted calibration curves using the following formula: C .3 (P -I)/S (4) W here, C ,3 Concentration of POAA in sample (jig/mL) P = Peak area of sample (response) 1 3 Intercept of the calibration curve (response). S 3 Slope of the calibration curve (response / concentration) The concentration determined to be in the extract was converted to the concentration in the water samples according to the following equation: Cp * (C, * D)*E (5) W here, Cp 3 Concentration of POAA in actual sample Oxg/rnL) C, 3 Concentration of POAA in prepared sample (jrg/mL) D 3 Dilution Factor E 3 Extractability ASHO10484 Word Version 6.0 Lab Request #R2008 R2008.DOC 3 ^ 12 S ' C000S7 USEPA 8960 4.3 D eterm ination of percent recovery and extractability, w ater Matrix spike samples were analyzed to determine the recovery of POAA from the water. POAA recovery and the related extractability value are calculated as follows: %R = [(Q - C J / C,]*100% (6) where, %R = Percent recovery of POAA Q = Concentration of POAA found in MS/MSD (ng/mL) C , - Native concentration of POAA in sample before dilution adjustment (ng/mL) C, = Concentration of POAA spiked in MS sample (>ig/mL). As an example, the percent recovery for the R2008-1-1, MS sample is calculated as follows: therefore, C f- 0.057 ngfinL; C , * 0.020 ng/mL; C, * 0.052 ng/mL; ' %R * (0.057-0.020V0.052 x 100% =74% The extractability is equal to 100% divided by %R. The percent recoveries of POAA in the MS and MSD samples and the corresponding extractability fectors are presented in Table 2. Table 2 % recovery and extractability determ ined from analysis of MS and M SP. Recovered Spiked N ative Concentration C oncentration Concentration % Sam ple (ue/m L) (ue/m L) (ws/mL) Recovery MS 0.057 0.052 0.02 74 MSD 0.059 0.052 0.02 75 A verage 75 E x tra c ta b ility 1.3 1.3 1.3 5.0 CONCLUSION High pressure solvent extraction, ES/MS analysis and linear regression analysis were used to determine that 0.364 mg/kg of POAA is present in the soil sample received from D uPont W ater samples ' R2008-1 through R2008-4 also contain about 50 ppb POAA No POAA was detected in R2008-5. 6.0 MAINTENANCE OF RAW DATA AND RECORDS Hard copies of these data are filed in the AMDT archive. Soap) pupwrtic a : GML/JJ Aiutysic GMIAjk Report pnpanliao: kjh ASH010485 Word Version 6.0 Lab Request R2008 R2008.DOC USEPA 8961 4 /* 4 la s ' 000088 DATA TABLE 1.0 Spiked Standard Cone, of POAA in E xtract (ng/mL) Blank 0.0005 0.005 0.050 0.100 0.250 0.500 0.750 1.000 Cone, of POAA in Soil (pg/kg) 0.00 0.50 5.00 49.22 99.63 248.97 493.88 748.39 995.17 FIGURE 1.0 R-2008 DuPont Soil Data .POX'il^niisw^'CuIf nd Data Table Volume of E x trac t (mL) 2.0 2.0 2.0 2.0 2.0 2.0 2.0 2.0 2.0 Peak Area of . Extract-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 E x trac t-b 141494 396700 475027 623624 . 225468 395568 666830 786883 842187 Mass of Soil (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 Soil (pg/kg) 0.00 0.50 5.00 49.22 99.63 248.97 493.88 748.39 995.17 Extracted POAA S tandard Curve 9000000 E T T ^ -iirk 8000000 7000000 ,r; - ^ fc- j r -<.- 6000000 l- M ll S If e 5000000 4000000 3000000 2000000 1000000 w.-:- A Series1 " " Lineu (Series!) 0.00 200.00 400.00 60000 800.00 1000.00 1200.00 Coaceatradoa of POAA i t Soil (jif/V*) ASH010486 3 4 CC00S9 USEPA 8962 R-2008 DuPont Soil Data POAA Standard Curve and 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, from spiked standards, in the extract Volume X of Extract Mass of Soil X Convert g to kg * Cone, of POAA in Soil Pg X tnL 1 X 1000 g m Pg tnL 18 kg kg To calculate total Peak Area, the area integrated for peak "a" for the initial extraction o f the soil and the area integrated for peak "b" for the second extraction of the same soil are summed. ' Using the Method o f Standard Addition determine indigent analyte concentration by solving for for the x-intercept: where y = 0, and equation of the slope o f the line of Peak Area vs. Cone, o f POAA in Soil is: y - 6248 x + 2275109 x - -2275109 / 6248 x *-364 concentration o f indigent analyte POAA in soil determined to be 364 pg/kg ASHO10487 / y ^ s' USEPA 8 9 6 3 C 0 O O 9 O 3M Environmental Laboratory POAA Analyses in Groundwater (6/97 Samples) IS i US' C0G091 USEP 8964 ASHO10488 3M Environmental Laboratory Data Transmittal Summary Lab Request #: R2148_____________ Date Received: T #a^ 5 f S B ^ Contract Laboratory # Sponsor or Client: Representative Name Company Name DuPont Company Address Phone Project Lead: Kris Hansen (8-6018) Group Leader: rim Johnson (8-5294) Analyte(s) or Test Method #: POAA Sample Matrix: water Analysis Dates: 9/97-11/97 Analyses): LAC Author: LAC, kjh Data Reviewed by: PAR Project Lead (or designee):kjh James D. Johnson (or designee): Tntwnal Sent by: / Date JDJ: QAU (Archives): LIRN System: Project M anager Sue Beach_________________________ ______________________________ Others (List Recipients / Address / Phone / FAX) Sent by: / Date T. DiPasquale, 22-1 IE-03; 3-1891; 736-3257 kjh on 11/10/97 ASHO10489 A copy of the rep o rt including this form aad the client cover page is to be given to QAU, U R N an d to th e G roup Leader. U M S ' USEPA 8965C00032 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 W ater Samples Prepared 8/26/97 1.0 SUMMARY Twelve samples from DuPont were submitted to the 3M Environmental Laboratory for the analysis o f Surfactants. These samples were numbered R 2148-1 through R2148-12 (MW-1 through MW-6) and analyzed with an Electrospray Mass Spectrometer. This analysis determined that perfluorooctanoic acid anion is present in samples 1 through 10. Results are listed in table 1. . Table 1 Sample Results Sample # loo Count Dilution Concentration Average Std. Dev. Area Factor pg/m L (ppm ) R2148-1-1 (MW-1) 160473 20 5.71 R 2148-1-2 (MW-1) 157432 20 5.58 5.64 0.0872 R2148-2-1 (M W -l) 148341 20 5.21 R2148-2-2 (MW-1) 153530 20 5.42 5.32 0.149 R2148-3-1 (MW-2) R 2148-3-2 (MW-2) 79430 75610 2 2 0.242 0.226 0.234 0.0110 R2148-4-1 (MW-2) 80126 2 0.245 R2148-4-2 (MW-2) 74915 2 0.224 0.234 0.0149 R 2148-5-1 (MW-3) 1 R 2148-5-2 (MW-3) 135558 143990 2 2 0.469 0.504 0.487 0.0242 R2148-6-1 (MW-3) R2148-6-2 (MW-3) 135283 139707 2 2 0.468 0.486 0.477 0.0127 R2148-7-1 (MW-4) R2148-7-2 (MW-4) 43324 37814 2 2 0.0954 0.0731 0.0842 0.0158 R2148-8-1 (MW-4) R2148-8-2 (MW-4) 35756 32916 2 2 0.0647 0.0532 0.0590 0.00814 R2148-9-1 (MW-5) R2148-9-2 (MW-5) 24116 23264 2 2 <PQL <PQL <PQL <PQL R2148-10-1 (MW-5) R2148-10-2 (MW-5) 21873 26025 2 2 <PQL <PQL <PQL <PQL R 2148-11-1 (MW-6) R 2148-11-2 (MW-6) 11696 11932 2 2 <MDL <MDL <MDL <MDL R2148-12-1 (MW-6) R2148-12-2 (MW-6) 9132 10595 2 2 <MDL <MDL <MDL <MDL ASHO10490 Word Version 6.0 R2148.DOC Page i o f S J7 ^ I S ' CC0093 USEPA 8966 2.0 TEST MATERIALS Twelve water samples were received from DuPont on 07/02/97 (MW-1-1, 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 surfactants. The samples were stored at 4C until preparation and analysis. 3.0 EXPERIMENTAL-OVERVIEW AND METHODS 3.1 Investigative Samples One half mL was removed from each sample and diluted with 0.5 mL o f acetonitrile (ACN, TN-A-1504) for a final sample solvent composition o f 1:1 ACN:Water. 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 from sample R2148-12-1 with 0.5 mL o f ACN. The MS and MSD samples were each spiked with 0.005 mL o f a 101.1 pg/mL (ppm) ammonium perfluorooctanoate standard solution (W397-741) for final concentrations o f 0.503pg/mL. 3.3 Calibration Ammonium Perfluorooctanoate calibration standards, ranging in concentration from 0.0500-1.01 pg/mL, were analyzed bracketing the samples. The calibration curve was developed by plotting the mean of two standard peak areas o f ammonium perfluorooctanoate versus the concentration o f ammonium perfluorooctanoate standards 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 pL Flow Rate: 0.080 mL/min 3.5 Continuing Calibration Standards Continuing calibration standards at 0.253 ppm ammonium perfluoroctanoate were analyzed bracketing every ten samples during sample analysis. ASH010491 Word Version 6.0 R214S.DOC Page 2 of 5 8 4 USEPA 8967000094 3.6 Detection Limits The method detection limit (MDL) is equal to approximately 3 times the baseline noise and half the practical quantitation limit (PQL). The PQL corresponds to the lowest point on the calibration curve. The PQL is 0.0510 pg/mL; the method detection limit is 0.0255 pg/mL. 4.0 DATA ANALYSIS 4.1 C alibration Curve Average peak areas from the initial curve were plotted against the concentration o f ammonium perfluorooctanoate in the calibration standards. The standard curve was linear (R2> 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 the following equation: Equation 1 %D = Rj x 100% where, %D = relative percent difference R, - area 0.253 ppm calibration standard from the initial calibration R, * area 0.253 ppm calibration standard from the continuing calibration 4.3 Investigative Samples 4.3.1 Calculations Concentrations o f ammonium perfluorooctanoate were determined by comparison o f detected peak areas to the calibration curve using the following formula: Equation 2 ASH010492 Where, # C, = Concentration o f ammonium perfluorooctanoate in extract (pg/mL) P = Peak area of sample I = Intercept o f the calibration curve Word Version 6.0 R2148.DOC Page 3 o f 5 n 4 ms C0999S USEPA 8968 S = Slope of the calibration curve (mL/pg) 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 - C ex D Where, Cp= Concentration o f ammonium perfluorooctanoate in water sample (pg/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 pg/mL and D = 20; thus Cf = 0.285 pg/mL x 20 = 5.71 pg/mL (ppm). 4.4 M atrix Spike Samples Matrix spike samples were analyzed to determine the recovery o f ammonium perfluorooctanoate. Recovery was calculated using the following equation: Equation 4 %R = -- x 100% Cm* where, %R = Percent recovery o f ammonium perfluorooctanoate CB= Detected concentration o f ammonium perfluorooctanoate in MS sample (pg/mL) Q, = Average background concentration o f ammonium perfluorooctanoate in sample (pg/mL) CM - Expected concentration of ammonium perfluorooctanoate in MS sample (pg/mL). As an example, the percent recovery for the R2148-12-1, MS sample is calculated as follows: C,, = 0.404 pg/mL; Ch = 0.00 pg/mL; CM = 0.503 pg/mL; therefore, %R = (0.404-0.00)/0.503 x 100% - 80%. A S H 0 10493 Word Version 6.0 R2148.DOC Page 4 of 5 4 ' S ' USEPA 8969 C 0 0 0 9 6 The percent recoveries o f ammonium perfluorooctanoate in the MS and MSD samples are presented in Table 2. Table 2 M atrix Spike Results Sample Type Sam ple ED Recovered Expected Concentration Concentration1 (jig/mL) (Hg/mL) % Recovery DuPont Water R2148-12-1, MS R2148-12-1, MSD 0.404 0.401 0.503 0.503 Average 80 80 80 Notes: 1 Recovered concentration is equal to the concentration detected in the spiked sample minus the average concentration detected in associated unspiked samples. 5.0 CONCLUSION The results of ES/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 O F RAW DATA AND RECORDS Hard copies o f these data are filed in the AMDT archive. 7.0 APPENDICES The appendices are not included with these data. They are filed in the AMDT archive. 7.1 Extraction Logbook 7.2 Instrument Runlog 7 3 Curve and Chromatograms 7.4 Results ASH010494 LAC 8/29/97 Word Version 6.0 R2148.DOC Page 5 of 5 USEPA 8970 3M Environmental Laboratory POAA Analyses in Soil (6/97 Samples) > a o s!VO1 32. 4 1 2 S ' USEPA 8971 C0 0 0 3 8 ASHO10496 A copy of the report including this fora aad the client cover page b to be given to QAU, LIRN and to the G roup Leader. 4P>0 9 9 9 - ^ , USEPA 8972 3M Environmental Laboratory- Advanced Method Development Team Kris Hansen Sr. Analytical Chemist Advanced Method Development Team Building 2-3E-09 612-778-6018 kjhansen@ nm un.com Report - Analytical Study Determination of POAA in SoO and Water Lab request - R2382 1.0 Summary anion (POAA). The soil samples were assigned number R2382-1 through -11. Extraction o f the soils using high pressure solvent extraction (HPSE) followed by analysis of the extracts by negative ion electrospray ma. spectrometry (ES/MS) determined that POAA is present in all samples. The concentration of POAA in R2382-1 was determined using the method of standard additions. All other soils were evaluated relative to the curve generated in the standard additions analysis. Specific results are . listed in Table 1. T able 1. C oncentration of POAA in R2382 samples. lim it of detection/limit of quantitation is 0.100 mg (100 ppb). 2.0 TEST MATERIALS Eleven soil samples were received from DuPont on 06/10/97. The samples were stored at 4C until extraction; extracts were stored at 4C until analysis. ASH010497 3.0 EXPERIM ENTAL-OVERVIEW AND METHODS 3.1.1 Sam ple, soil ' W ify<?n*amiwanl nil M availahlg fhr blank analysis, the method o f standard addition was used to the w v e ntu tHMi of POAA in die soil received fiom DuPont. _Afive point standard curve was prepared by spiking 2 gram "pi* of the soil (B23S2-i) with some amount o f POAA solution between 500 ppt and 1.0 ppm. Two-gram samples ofdie ten remaining soils, and the spiked soils were each with [ynwriim itiy i gram o f diatomaceous earth and loaded into a 10 mL stainless steel extraction cartridge. The samples were extracted using high pressure solvent extraction (HPSE) w ith methanoL Each sample was extracted into an `a* (primary extract) and `b ' (secondary extract) viaL The Word Version 6.0 Lab Request #R2382 R2382DOC 2H 4 U S USEPA 8973 COiOO: lO O 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 the concentration o f analyte in the unspiked sample R2382-1 (see Figure I, attached). The remaining soils were evaluated relative to this curve. Soil from samples R2382-2 through *11 was prepared in the same way. For most samples, dilutions of the 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 the same method, using a standard curve generated that day (see Figure 2, attached). The method of standard addition assumes there are no interferences in the analysis and that the extraction efficiency of die analyte from the matrix is not dependent upon analyte concentration. The first assumption is addressed by the selectivity o f both the extraction and the analysis; the latter has been verified in another study that focuses on a similar matrix. 3.1 Extraction specifics The soil samples were extracted with the 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 volume-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 Negative ion ES/MS analysis was performed on a Micromass Platform II atmospheric pressure ionization mass spectrometer running Mass Lynx 2.1 operating system. A Hewlett Packard 1100 was used for the autosampler and HPLC system. Mobile phase: ACN/H20 (1:1) Flow rate: 60 pL/min Injection volume: 15pL Cone Voltage * -20 Capillary voltage * -2.56 Source Temperature = 80#C Analyzer Vacuum Pressure - 0.000079 noBar Quantitative results were based on the instrumental response generated by monitoring a single ion characteristic of the analyte. This type o f monitoring minimizes interference by other ions in the extract and increases system sensitivity to the target analyte. ASH010498 4.0 DATA ANALYSIS By the method o f standard addition, sample R2382-1 was determined to contain 0,119mg/kg o f POAA. This value was calculated using the prediction equation resulting from linear regression analysis of the five-point extracted curve. The coefficient o f determination for die curve is 0.999. Calculations used to determine the concentration o f POAA in the soil are shown m Appendix A. The concentration of POAA in samples R2382-2 through R2382-11 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 #R2382 R2382.DOC 2 JF 4 U S' C C O lO l USEPA 8974 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 of POAA is present in the eleven soil samples received from DuPont 6.0 MAINTENANCE OF RAW DATA AND RECORDS Hard copies of these data are filed in the AMDT archive. Sample preparation: GMLftJ Analysis: GMLflJ/kjh Report preparation: kjh/JJ W ord Version 6.0 Lab Request #R2382 R2382.DOC 3 ,, __ C0Q3L02 USEPA 8975 R-2382- DuPont Soil Data Appendix A R-2382 POAA Determination Calculations For Determination of "indigent" amount in Standard Additions Curve for R2382-1 Step 1: From Plot of Peak Area vs Spiked POAA Standard Concentration determine equation o f the linear regression by least squares analysis, for y * mx + b Example: y = 126000 x + 15000 . Step 2: Solve linear equation for x, where y m 0, for the x-intercept of die line. Example: 0 - 126000 x + 15000 x - -15000/126000 X --.119 Step 3: . Indigent amount will equal absolute value of x. Eot-Soil R-2382 Soils 2-11 Step 1: (Peak Area - Y intercept)/ Response =* Diluted Cone, of POAA (ug/ml) Peak Area, intercept, and response from std.additions carve calculated in ug/ml Example: (31000 - 15000yi26000 - 0.127 ug/ml Step 2: (Diluted Cone, of POAA ug/ml Dilution Factor) + Indigent Cone. ug/mL= Adjusted Cone, o f POAA ug/ml Example: (0.127 ug/ml 50) + .119 ug/ml * 6.47 ug/ml Step 3: , Adjusted Cone, (ug/ml) * 2ml extract/mass (g) * 1000 g/kg * 1 mg/1000 ug Total Cone, o f POAA (mg/kg) . Example: 6.47 ug/ml 2ml extract/1.9999 g 1000 g/kg Im g /1000 ug - 6.47 mg/kg POAA Step 4: Add Total Cone, o f POAA determined for Peaks "a" and "b* " Total determined POAA (mg/kg) Example: 6.47 mg/kg + 0.43 mg/kg * 6.90 mg/kg A S H 0 10500 Calculations R 2382J03097 8:59 PM 11/4/97 47 4 CO0 1 0 3 USEPA 8976 R-2382- DuPont Soil Data Picure 1 R-2382-.1. Soil-Standard Addition Curve Cue/ml extract Cone, o f POAA Spiked into Soil (ug/m l) 0.05 0.10 0.25 0.50 0.75 File D102897B Peak Area o f Extracts-a 20000 25000 40000 71000 96000 File D102897B File D102897B File D102S97D Peak Area of Total Peak Area Total Peak Area Extracts-b (a+b) (a+b) 1000 21000 3000 28000 4000 44000 9000 80000 14000 110000 Average of Initial &. Final Curve 21000 29000 46000 80000 109000 File D102897D File D102897D Peak-a Peak-b 0.05 20000 1000 0.10 27000 3000 0.25 44000 4000 0.50 71000 9000 0.75 94000 14000 21000 30000 48000 80000 108000 Y-intercept Curve Equation: 15000 Slope (m)___________________ X-intercept 126000 -0.119 Indigent POAA analyte (Absolute value of X-intercept): 0.119 ug/ml ASH010501 Soil 1 Curve ugml R2382_103097 9:00 PM 11/4/97 C 0004 USEPA 8977 R-2382- DuPont Soil Data Figure 2 R-2382-1 Soil- Standard Addition Curve Analyzed bv ESMS on I l/fU/07 Cone, o f POAA Spiked into Soil (ug/ml) 0.05 0.10 0.25 0.50 0.75 File Dt 10497B Peak Area of Extracts-a 21000 26000 41000 67000 94000 File D110497B File D110497B Peak Area of Total Peak Area Extracts-b (a+b) 1700 22700 3200 29200 4400 45400 8200 75200 13700 107700 Extracted POAA Standard Curve POAA Cone, (of/nl) Y-intereept____________________ Slope (m) Curve Equation: 16000 120000 Indigent POAA analyte (Absolute value o f X-intercept): X-intercept -0.133 0.133 ASHO10502 11.04 Curve ugml R2382J03097 8:58 PM 11/4/97 C0 0 1 0 5 USEPA 8978 3M Environmental Laboratory Volatiles and Semi-volatiles in Groundwater by Purge and Trap Concentration with GC/MS Analyses (6/97 Samples) 30 4 USEPA 8979 G 0 Q 1 0 6 ASH0I0503 ANALYTICAL SUMMARY Department: 3048 Lab Request: R2148 Project Description: DuPont Water Summary Prepared by: Dennis Seeger, Pace-I Contract Lab: Pace*I Project Lead: Dennis R. Seeger Sample Matrix: Water Date: 10/7/97 Analytical Tests Requested Twelve water samples were submitted for identification and quantitation o f volatile organic sample components by purge and trap sample concentration with gas chromatography/mass spectrometry (GC/MS) analysis. Analytical Results The results o f the 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 the practical quantitation limit (J footnote), the reported values should be considered as estimates. Analytical Summary Gas Chromatography Methods Summary The samples were analyzed using the GC/MS instrument and sample concentrator conditions listed below. Procedure G C/M S Parameters (Instrum ent ID "A lphie") Sam ple C o n cen trato r Tekmar model 2000 sample concentrator and model 2050 vial autosampler. Trap: Purge time: Purge gas flow: Desorb time: Desorb temp.: Desorb flow: Carbopack B/Carboxen 1000 St 1001 (Vocarb 3000) 11 min. 40 mL/min. 0.5 min. 270 C 30 mL/min GC column: Restek RTx-624,60 m x 0.32 mm I.D., 1.8 pm film thickness. > Vi XO U 4*. 1 3\ 4 US' C0 0 1 0 7 USEPA 8980 C C conditions and oven tem perature program: Initial temp.: Oven temp, ramp: Injection port temp.: Interface temp.: Purge B: Head pressure: Split flow: 40*C; 2.0 min. hold 12C/min. to 220C; 1.0 min. hold 250C 250C Initial value ON 19.6 psig 30 mL/min. Mass spectrom eter: Solvent delay: Electron m ultiplier Scan range: Scans per second: Scan threshold: 2.2 min. 2053 volts 35 to 260 amu 2.17 100. Instrum ent Calibration Prior to sample analyses, the analysis of 50 ng of bromofluorobenzene (BFB) demonstrated vm *vufey?and resolution o f the mass spectrometer. A calibration check standard containing e; of fm vaspA analytes at the midpoint concentration of the 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 the criteria specified for analyzing samples by EPA method 8260. Closing This analytical summary and associated analytical results have been reviewed and are approved for release. 1 ,,. . (612)778-6093 * w ~ ASH010505 2 3* ^ US' USEPA 8981 G O Q 3.Q 8 Appendix A: Report of Laboratory Analysis ASH010506 C 'C '0 1 .0 9 USEPA 8982 33 i M S ' Method 8260 Results for R2148 Com pound Dichlorodifluoromethane Chloromethane Vinyl Chloride Bromomethane Chloroethane T richlorofiuoromethane Ethyl Ether T richlorotrifluoroethane Acrolein 1,1-Dichloroethene Acetone Isopropyl Alcohol Carbon Disulfide Allyl Chloride Methylene Chloride tert-Butyl Alcohol tert-Methyl Butyl Ether trans-1,2-Dichloroethene Acrylonitrile Isopropyl Ether 1,1 -Dichloroethane 2,2-Dichloropropane Ethyl Acetate cis-1,2-Dichloroethene 2-Butanone 2-Butanol Bromochloromethane Tetrahydrofuran Chloroform 1,1,1 -T richloroethane Carbon Tetrachloride 1,1-Dichloropropene Isobutanol Benzene 1 ,2-D ichloroethane n-Butanol Trichloroethene 1,2-Dichloropropane Dibromomethane Bromod chloromethane 2-Chloroethyl Vinyl Ether 2-Nitropropane cis-1,3-Dichloropropene 4 -M ethyl-2-pentanone Toluene 4-Methyl-2-Pentanol PRL ! (ug/L)! R2148-1 10 i 10 I 10 ' 10 1 io ! 10 J 5' 5i 40 ! 5' 10 i 60 ! 5' 5i 5! 20 J 5; 5! 40 J 5' 5t 5! 10 ' 5 10 I 60 \ 5J 10 i 5! 5! 5i 52 100 ' 5 S2 ioo 2 5; 5i s2 52 10 io 2 52 10 ! 51 60 2 - 820 -' - 2.7 J 59 - 1.8 J - S a m p le C o n c e n tra tio n s (u g /L ) R2148-2 R2148-3 R2148-4 R2148-5 -. -- -. - - _ -- - 16 18 26 ---- 730 1600 1500 2300 --- - - - 3.7 J - 10 - - 7.8 J ---- ---- --- 2.9 J 49 - - 2.3 J -- --- - - - - 2.9 J --- - --- - ---- -- -- - - 3.3 J ------ - --- - 5.5 - - 14 -- - --- --- --- - -. - - - --- - 1.5 J 140 150 520 -, - - - --- - --- - - - - - --- - --- - --- - --- - --- - R2148-6 . . 26 - 2400 - 8.0 J - 2.7 J -` 3.0 J - 3.5 J - 5.9 14 570 - `- ASH010507 PRL - Practical Quantitation Limit J T h e concentration is below the practical quantitation limit C 00110 Page 4 USEPA 8983 3H 4 U S Method 8260 Results for R2148 PRL Compound (ug/L) trans-1,3-Dichloropropene 1,1,2-T richloroethane Tetrachloroethene 1,3-Dichloropropane 2-Hexanone 5 5 5 5 10 Dibromochloromethane 1,2-Dibromoethane Chlorobenzene Ethylbenzene 5 5 5 5 1,1,1,2-Tetrachloroethane m & p-Xylene 5 5 o-Xylene 5 Styrene 5 Bromoform Isopropyl benzene 5 5 Cyclohexanone 60 1,1,2,2-Tetrachloroethane 5 Bromobenzene 5 n-Propyl benzene 1,2,3-T richloropropane 5 5 2-Chlorotoluene 5 1,3,5-Trimethylbenzene 5 4-Chlorotoluene 5 tert-Butyl benzene 5 1 ,2,4-T rim eth ylb e n zen e 5 sec-Butylbenzene 5 p-lsopropyltoluene 5 1,3-Dichlorobenzene 5 1,4-Dichlorobenzene 5 n-Butyl benzene 5 1,2-Dichlorobenzene 5 1,2-X)ibromo-3-Chloropropane 5 1,2 ,4 -T richlorobenzene Hexachlorobutadiene' Naphthalene 1,2,3-Trichlorobenzene 5 5 5 5 R2148-1 .3.6 J - - - -. - Sam ple Concentrations (ug/L) R2148-2 R2148-3 R2148-4 R2148-5 R2148-6 - . 1.1 J 5 5.2 . . _ . . . - - - - -- - -- - 1.7 J - 1.8 J - - - - - - - - ---- - - - -' - - --- - -- - - - -- - - - --- - - ---- --- - - -- -- -- -- - --- - - --- - - -- - - --- - ---- ---- --- - ---- --- - - - - - --- - - - - -. - - --- - ASHO10508 PRL - Practical Quantitation Limit J - The concentration is below the practical quantitation lim it I C0 0 1 1 1 Page 5 3 5 * ^ T USEPA 8984 Method 8260 Results for R2148 Com pound Dichlorodifluoromethane Chloromethane Vinyl Chloride Bromomethane Chloroethane Trichlorofluoromethane Ethyl Ether Trichlorotrifluoroethane Acrolein 1,1-Dichloroethene Acetone Isopropyl Alcohol Carbon Disulfide Allyl Chloride Methylene Chloride tert-Butyl Alcohol tert-Methyl Butyl Ether trans-1,2-Dichloroethene Acrylonitrile Isopropyl Ether 1,1-Dichloroethane 2,2-Dichloropropane Ethyl Acetate cis-1,2-Dichloroethene 2-Butanone 2-Butanol Bromochloromethane Tetrahydrofuran Chloroform 1,1,1-Trichloroethane Carbon Tetrachloride 1,1 -Dichloropropene isobutanol Benzene 1,2-Dichloroethane n-Butanol Trichloroethene 1,2-Dichloropropane Dibromomethane Bromodichloromethane 2-Chloroethyl Vinyl Ether 2-Nitropropane cis-1,3-Dichloropropene 4 -M ethyl-2-pentanone Toluene 4-Methyi-2-Pentanol PRL ! (ug/L)! R2148-7 10 i 10 ! 10 ' 10 10 ! 10 ; 5 5.9 - 5! 40 ! 5! 10 t 60 ! 5I 5i 5! 20 ' 5' 5! 760 - 6.7 J 40 | - 5' 5i - 5! - 10 ' - 5i 10 ! 60 ! 5! 10 i 5.8 - 5 ! 37 5! 5i 6.3 - 5! 100 ' 5 - 5 !. * 100 \ - 5 J 81 5i - 5! - 5J - 10 - 10 I - 5! 10 ; 5S 60 i - - S a m p le C o n c e n tra tio n s (u g /L) R2148-8 _ . - R2148-9 . . . R2148-10 R2148-11 . . . . R2148-12 . - 670 130 140 3.2 J 1.8 J .. - . . 10 - - . 5.6 J --- - --- - - - - . * - - '- - - - - _- - -- - - --. - - -- - --- - --- -- - - - - -- ,- 5.9 2.7 J 2.6 J - '- - - - - - - .- _- ---- - 39 13 16 - - 6.2 5.8 - - * - - - `- ---- - --- - . ;- - - - - -- - 66 - - - --- - - - - - - - - _- - - - - - -- - - - - - - - - -- - - - - - - o --- - - PRL - Practical Quantitation Limit J - The concentration is below the practical quantitation limit 1 Page 6 ASHO10509 " " 3 i 4 145" USEPA 8985 C0 0112 Method 8260 Results for R2148 PRL i Com pound (ug/L)! R2148- trans-1,3-Dichloropropene 1,1,2-T richloroethane Tetrachloroethene 1,3-Dichloropropane 2-Hexanone 5i 5! 5! 5! 10 ! - 4.8 J - Dibromochloromethane 1,2-Dibromoethane Chlorobenzene Ethylbenzene 5! 5i 5! 5; - 1,1,1,2-Tetrachloroethane m & p-Xyiene o-Xytene 5\ 5i 5! - Styrene Bromoform 5 5i - Isopropyl benzene Cyclohexanone 5! 60 ; - 1 ,1 ,2,2 -T e tra ch lo ro e th a n e 5 - Bromobenzene 5i - n-Propyl benzene 1,2,3-T richloropropane 2-Chlorotoluene 1,3,5-T rimethylbenzene 5! 5\ 5i 5! - 4-Chlorotoluene tert-Butyl benzene 5! 5J - 1,2,4-Trimethylbenzene sec-Butylbenzene p-lsopropyltoluene 1,3-Dichlorobenzene 1,4-Dichlorobenzene 5i 5J 5j 5i 5! - n-Butyl benzene 1,2-Dichlorobenzene 5! 5i * - 1,2-Oibromo-3-Chloropropane 5 i - 1,2,4-Trichlorobenzene 5\ - Hexachlorobutadiene Naphthalene 1,2,3-T richlorobenzene 5 5i 5 - Sample Concentrations (ug/L) R2148-8 R2148-9 R2148-10 R2148-11 R2148-12 5.8 ASH010510 PRL - Practical Quantitation Limit J - The concentration is below the practical quantitation limit Page 7 USEPA 8986 3M Environmental Laboratory Volatiles by AED (5/97 Samples) ASH010511 USEPA 8987 38 4 \XS C C 0 I.1 4 3M Environmental Laboratory Data Transm 1Summary Preliminary (Tini (circle one) Lab Request # Date Received: 3M Study #: 3 ^ 4 9 /3<^S~9 Contract Laboratory # Sponsor or Client: Representative Name Company Name Q uPort't' Company Address Phone Project Lead: Name / Phone Kblcvi / %(5$| $ Group Leader: Name / Phone JDJohnson/85294 Analyte(s) or Test Method #: 'P'0 A'A Sample Matrix: So 1 1 Analysis Dates: 0 b ( ^ rici'? '- 0 ^ 2 ^ Analyst(s): $ M l! Author: S F M 1 1U Data Reviewed by: Project Lead (or designee): Internal ....................... ..... Sent by: / Date JDJ: . QAU (Archives): LIRN System: Project Manager: `Stig. %C<c {a ____________________________________ Others (List Recipients / Address / Phone / FAX) .... Sent by : / Date ASH010512 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. USEPA 8988 3M Environmental Laboratory - Advanced Method Development Team Contact: Kris Hansen Building 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 eight soil samples from DuPont were analyzed for the presence of fluorine, chlorine, bromine, carbon, and hydrogen using headspace sampling 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. 2.0 INTRODUCTION Five water samples and eight soil samples were received from DuPont under request #2008. The samples were to be analyzed for the presence o f perfluorooctanoic 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 the samples into the GC/AED. The samples were monitored for fluorine (F690), bromine (Br478), chlorine (0 4 7 9 ), hydrogen (H486), and carbon (C496). 3.0 TEST MATERIALS The five water samples were labeled on large amber glass bottles as follows: Lab Request R2008-1 R2008-2 R2008-3 R2008-4 R2008-5 # of Bottles_________________________ Sample Description_____________________ 1 DuPont Wash. W orks Ranney Well FC143 1:48 pm 1 DuPont Wash. Works Ranney Well FC143 1:48 pm 1 DuPont Wash. W orks Ranney Well FC 143 1:50 pm 1.. ,, DuPont Wash. Works Ranney Well FC143 1:50 pm 1 D I Water ..... ............ ...................... ASH010513 3M Environmental Laboratory, Lab Request R2008 Page 1 o f 5 USEPA 8989 VO C00116 The eight soil samples were labeled on 1L plastic containers as follows: Lab Request it # of Containers___________ Sample Description R2008-6 8 DuPont Washington Dirt 5/30/97 11:00 All samples were refrigerated at approximately 4C until sample preparation and analysis. 4.0 EXPERIM ENTAL - OVERVIEW Sample Preparation The water samples were prepared by pipetting lOmL o f each sample into 20mL glass headspace vials. Each sample was "salted" by adding approximately 2 to 3 grams o f sodium chloride (this was done to increase the ionic strength o f the solution). The soil samples were prepared by transferring 10 0.5 grams o f soil (weight recorded) into headspace vials. The soil samples were not salted. The standard curves were prepared using two different standards, para- bromofluorobenzene (p-BFB) and ortho-dichlorobenzene (o-DCB). The p-BFB was prepared in acetone and the o-DCB was prepared in methanol. The standards were spiked into lOmL Milli-Q water at levels o f 25pi, 50pl, and 100pi. Acetone and methanol spikes (lOOpl each) in lOmL Milli-Q as well as a lOmL Milli-Q blank were also analyzed. Since all eight containers o f soil were the same, three of the eight samples were used to make a standard curve. These were spiked exactly as the waters were. One soil sample was spiked with acetone and methanol, leaving four containers of soil to be treated as "samples." . 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. 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 ASH010514 3M Environmental Laboratory, Lab Request R2008 Page 2 of 5 <// tjj USEPA 8990 C 0 ! 7 Gas Chromatograph: Hewlett Packard 5890 Series II Column: DB-5 (J&W Scientific) 30 x .25 x .25, serial # 2633586 Oven Program: 1 min @ 60, 10/min 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, 10/min to 200 for 5 min Injection Port: 225C, split Atomic Emission Detector: Hewlett Packard 5921A "Fio" GC Block/Transfer Line Temp 275 Cavity Block Temp 275 . 5.0 DATA ANALYSIS SAMPLE RESULTS: Lab Request #_____ Column________ Element_______________________ Results* R2008-1 DB-5 F no peaks detected R2008-2 DB-5 F no peaks detected R2008-3 DB-5 F no peaks detected R2008-4 DB-5 F no peaks detected R2008-5 DB-5 F no peaks detected R2008-6 DB-5 F no peaks detected *minimum quantitation limit: 0.280 ppm F in water, 0282 ppm F in soil Lab Request # Column Elements Results* R2008-1 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, 1220 ppm Br in soil 1.408 ppm Cl in water, 1.461 ppm Cl in soil Lab Request # Column Element Results* R2008-1 DB-624 F no peaks detected 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 R2008-6 DB-624 F no peaks detected 'm inimum quantitation limit: 0.280 ppm F in water, 0.282 ppm F in soil ASH010515 3M Environmental Laboratory, Lab Request R2008 Page 3 of 5 USEPA 8991 va 4 U S ' Lab Request it R2008-1 R2008-2 R2008-3 R2008-4 Column DB-624 DB-624 DB-624 DB-624 Elements H, C, Br, Cl H, C, Br, Cl H, C, Br, Cl H, C, Br, Cl Results* 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 peaks detected on Cl channel (below mql), no peaks on other channels R2008-5 DB-624 H, C, Br, Cl no peaks detected R2008-6 DB-624 H, C, Br, Cl no peaks detected minimum quantitation limits: 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 o f standard curves taken from the analyses: F Curve for DuPont Soil (DB-5) Cl Curve for DuPont W ater (DB-624) ASH010516 3M Environmental Laboratory, Lab Request R2008 " k **..V.' ; - ' i Page 4 of 5 USEPA 8992 C0 0 1 1 9 HI 4 6.0 CONCLUSION Qualitative analysis o f DuPont water and soil revealed very little was present in any o f the samples. Cl-containing compounds were found using the DB-624 column in water samples R2008-1 through R2008-4. The levels o f these compounds were not quantitated because they were present in levels below the lowest standard. 7.0 MAINTENANCE OF RAW DATA Hard copies of the data are filed in the AMDT archive. SE Miller 110797 ASH010517 3M Environmental Laboratory, Lab Request R2008 Page 5 o f 5 <500120 H 'i i USEPA 8993 tX S 3M E nvironm ental Laboratory Volatiles by AED (6/97 Samples) H S ef, U S ' USEPA 899<} 0 0 1 2 1 - ASH010518 3M Environmental Laboratory Data Trans 1Summary Preliminary xnalj)(circle one) Lab Request #: Pam s Date Received: 3M Study #: Contract Laboratory # Sponsor or Client: Representative Name Company Name i X c P o w t Company Address Phone Project Lead: Nam e/ Phone K-\Aouy\<*oy\ j 1*41% Group Leader: Name / Phone JDJohnson/85294 Analyte(s) or Test Method #: Sample Matrix: W a H v Analysis Dates: Author: SS M il^v* Project Lead (or designee): James D. Johnson (or designee): 7 Analyst(s): S f M jlliv Data Reviewed by: PA fW vr^ru M A hkS u/11 16 7 JDJ: QAU (Archives): * LIRN System: Project Manager: __________________ i___________________________________ Others (List Recipients /Address / Phone / FAX) Sent by: / Date ASH010519 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. USEPA 8995 4 3 S C00122 3M Environmental Laboratory-Advanced Method Development Team Contact: Kris Hansen Building 02-3E-09 612-778-6018 kjhansen@ m m m .com Final Report - Lab Request R2148 DuPont W ater Samples 07 November 1997 1.0 SUMMARY Twelve water samples were received from DuPont on July 2, 1997. The samples were analyzed for the presence o f fluorine, chlorine, bromine, carbon, and hydrogen using headspace sampling 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 o f no less than R2=0.99 were generated during each analysis. Column Samples DB-5 l-8 Results Description halogenated organics DB-5 9-10 low levels o f halogenated organics DB-5 11-12 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 Levels* 0.23-1.3 ppm F, 0.29-0.86 ppm C, 0.39-2.5 ppm Cl 0.32-0.35 ppm C, F and Cl areas less than low standard response C area less than low standard response 0.23-1.1 ppm F, 0.24-0.50 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 the DB-5 and in one sample on the DB-624. ASH010520 3M Environmental Laboratory, Lab Request R2148 Page 1 o f 8 H7 4 U S ' USEPA 8996 nLi-'rj o iJL* 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 o f organofluorines. A headspace sampler was used to introduce any volatile or semi-volatile components o f 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 # R2148-1 R 2 148-2 R 2 148-3 R2148-4 R2148-5 R2148-6 R2148-7 R2148-8 R2148-9 R2148-10 R2148-11 R2148-12 Sample Description MW-1 1 of 2 MW-1 2 o f 2 MW-2 l of 2 MW-2 2 of 2 MW-3 1 of 2 MW-3 2 of 2 MW-4 1 o f 2 MW-4 2 o f 2 MW-5 1 of2 MW-5 2 o f 2 MW-6 1 o f2 MW-6 2 of 2 All samples were refrigerated at approximately 4C until sample preparation and analysis. 4.0 EXPERIMENTAL - OVERVIEW Sample Preparation The water samples were prepared by transferring approximately lOmL o f each sample into tared headspace vials containing approximately 4 0.1 grams o f sodium chloride. The vials were rewieghed to get the weight o f the water. This was done instead o f pipetting an exact volume so that exposure to air was kept to a minimum, and the possibility o f losing volatile components reduced. Standard curves were prepared using two different standards, para- bromofluorobenzene (p-BFB) and ortho-dichlorobenzene (o-DCB). Two standard curves were necessary so calibration curves could be generated for all elements o f interest: fluorine, carbon, hydrogen, and bromine from p-BFB; carbon, hydrogen, and chlorine from o-DCB. The p-BFB was prepared in acetone and the o-DCB was prepared in methanol. The standards were spiked into lOmL Milli-Q water (salted) at levels o f 5|iL, 3M Environmental Laboratory, Lab Request R2148 Page 2 o f 8 A S H 0 10521 H8 ^ J25 " USEPA 8997 C0 0 1 2 4 25pL, 50pL, 75pL, and lOOpL. Acetone and methanol spikes (lOOpL each) in lOmL Milli-Q as well as a lOmL Milli-Q blank were also analyzed. The combination o f 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, the 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 II Column: DB-5 (J&W Scientific) 30m x .25mm x .25pm, serial # 2633586 Oven Program: 1 min @ 40, 10/min to 300 for 3 min Column: DB-624 (J&W Scientific) 30m x .32mmx 1.8pm, serial# 5812142 Oven Program: 1 min @ 40, 10/min to 240 for 5 min Injection Port: 225C, split Atomic Emission D etector Hewlett Packard 5921A "Flo" A S H 0 10522 3M Environmental Laboratory, Lab Request R2148 Page 3 of 8 USEPA 8998 5.0 DATA ANALYSIS SAMPLE ANAL YSIS: Column: DB-5 Lab Request # R2148-1 R2148-2 R2148-3 R2148-4 R2148-5 R2148-6 R2148-7 R2148-8 R2148-9 R2148-10 R2148-11 R2148-12 low standard concentration: 0.056 ppm F F690* 0.23 ppm, 1peak<lowstd. response 0.23 ppm, 1peak<lowstd. response 0.079 ppm, 0.55 ppm 0.34 ppm, 1peak<lowstd. response 0.26 ppm, 0.57 ppm 0.39 ppm, 0.90 ppm 0.066 ppm, 021 ppm 0.075 ppm, 0 2 2 ppm 2 peaks < lowstd. response 2 peaks < lowstd. response none detected none detected C o lu m n : DB-624 L ab R equest # R2148-1 R2148-2 R2148-3 R2148-4 R2148-5 R2148-6 R2148-7 R2148-8 R2148-9 R2148-10 R2148-11 R2148-12 F690* 0.26 ppmF, 3 peaks < lowstd. response 0.23 ppmF, 3 peaks < lowstd. response 0.075 ppm, 0.44 ppmF, 2 peaks<lowstd. response 0.074 ppm, 0.42 ppmF, 2 peaks<lowstd. response 0.086 ppm, 0.27 ppm, 0.70 ppmF, 3 peaks< low std. response 0.080 ppm, 0.23 ppm, 0.59 ppmF, 3 peaks <low std. response 0.087 ppm, 0.20 ppmF, 2 peaks< lowstdresponse 0.083 ppm, 0.16 ppmF, 2 peaks<lowstd. response 5 peaks < lowstd. response 0.082 ppmF, 4 peaks <lowstdresponse 1 peak<lowstd. response none detected same low standard concentration as above ' ASHO10523 3M Environmental Laboratory, Lab Request R2148 Page 4 of 8 USEPA 8999 S o 4 S' C0 0 1 2 6 Column: DB-5 Lab Request # R2148-1 R2148-2 R2148-3 C496* l peak < low std. response l 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 < low std. response 1 peak < low std. response 0.13 ppm, 2 peaks < low std. response C1479* 0.39 ppm 0.46 ppm 12 ppm, 2 peaks < low std. response 1.0 ppm, 2 peaks < low std. response 0.43 ppm, 1.2 ppm, 0.31 ppm R2148-6 0.36 ppm, 0.30 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 R2148-8 0.29 ppm, 2 peaks < low std. response 2 peaks < low std. response l peak < tow std. response none detected 0.46 ppm, 2 peaks < low std. response 0.46 ppm, 2 peaks < low std response R2148-9 0.32 ppm, 2 peaks < low none detected std. response 2 peaks < low std. response R2148-10 0.35 ppm, 2 peaks < low none detected std. response 2 peaks < low std. response R2148-11 l peak < low std. response none detected none detected R2148-12 1 peak < low std. none detected none detected response low standard concentrations: 0,21 ppm C, 0.060 ppm H, 0.28 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 none detected none detected ASH010524 3M Environmental Laboratory, Lab Request R2148 Page 5 o f 8 S 4 US' USEPA 9000 Column: OB-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 1 peak < low std. response R2148-5 0.34 ppm, 3 peaks < low std. response R2148-6 O.SO ppm, 3 peaks < 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 < low std. response *same low standard concentrations as above H486* none detected none detected none detected none detected none detected 1 peak < low std. response none detected none detected none detected none detected none detected none detected 0479* 0.57 ppm Br478* none detected 0.45 ppm none detected 1.2 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 < low 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 o f water = 1g/mL. ASH010525 3M Environmental Laboratory, Lab Request R 2148 Page 6 o f 8 USEPA 9001 SX 4 M S 00128 STANDARD CURVES: Example of a standard curve from the analysis (all standard curves had R2 of 0.99 or greater): P Curve for R2148 (D&624) s ppm F 1.2 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 the samples evidence o f at least one of the elements targeted. Many peaks were detected but not quantitated because the peak area was less than die low standard response for that elem ent 7.0 MAINTENANCE OF RAW DATA Copies o f all data will be filed in the AMDT archive. 8.0 APPENDICES Appendix A: Chromatogram o f sample 6 (MW-3 2 o f 2) F690 DB-624 SEMiller 110797 ASH010526 3M Environmental Laboratory, Lab Request R2148 Page 7 o f 8 USEPA 9002 A ppendix A: Chromatogram o f sample 6 (MW-3 2 of 2) F690 DB-624 F S90 o f 1300T: F021R13R.D F 690 of 1300T:F02lfl13R. D Ti me- ( m i n . ) 3M Environmental Laboratory, Lab Request R2148 Page 8 o f 8 > 00 o to ^ SH 4 U S' USEPA 9003 C 0 0 1 3 0 3M Environmental Laboratory total Fluoride in Soil (6/97 Samples) 31 USEPA 9004 ASHO10528 3M Environmental Laboratory Data Transmittal Summary Preliminary / Final (circle one) Sponsor or Client: Roger Zipfel Dupont Washington Works Plant Project Lead: Name / Phone Kris Hansen / (612) 778-6018 Analyte(s) or Test Method #: Total Fluoride Sample Matrix: Soil Analysis Dates: 9/29/97 through 10/01/97 Analyses): Daniel Howman Author: Daniel Howman Data Reviewed by: Kris Hansen Internal Reviewer: James D. Johnson QAU (Archives): Rich Youngblom LIRN System: Denise Appleton Project Manager: Sue Beach Others (List Recipients /Address / Phone / FAX) Project Lead: Kris Hansen Sent by: / Date D R H /11-07-97 Sent by: / Date D R H /11-07-97 ASHO10529 A copy of the report including this form and the client cover page is to be given to QAU, LOIN and to the Group Leader. S U 12. USEPA 9005 CO0 1 3 2 3_MEnvironmental Laboratory - Advanced Method Development Team Kris Hansen - Sr. Analytical Chemist Advanced Method Development Team Building 2-3E-09 612-778-6018 kjhansen@mmm.com Final Report D eterm ination 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 through 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. The following table contains a summary o f the results. The Total Fluoride values are the average o f three replicates o f the same sample, and are given in the table along with the standard deviation o f the three replicates. Total fluoride is defined as the concentration of F- measured following complete combustion of the sample. A S H 0 10530 2.0 TEST MATERIALS * The soil samples were sent from Dupont, Washington Works Plant, and received at the Environmental Laboratory in St. Paul on 6/6/97. The samples were logged in under Lab Request R2382, samples l through 11. Samples were refrigerated at 4C until analysis. Analyst / Date Daniel Howman /10-1-97 Page l of 7 S7 4 nb C00133 USEPA 9006 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 Vaporization/Drying time = 240 seconds Bake time = 300 seconds Collection fluid = 3.0 mL o f 1:1 TISAB/Milli-Q H20 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 o f 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 o f the standards were collected in 3 mL o f 1:1 TTSAB II/HjO. The collection vial was placed so that the tip o f the combustion tube was in the collection fluid. Gases released during pyrolysis bubble through the collection fluid; the F- partitions into the collection fluid. The concentration of fluoride in the collection vial was determined by direct measurement with the Orion EA940 Expandable Ion Analyzer with Orion 9609BN Combination Fluoride Electrode. The Orion EA940 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 F*. Standards were prepared using Coming Sodium Fluoride (TN-A-0572) and diluted in 1:1 TISAB n/H 20 . A S H 0 10531 4.2 Blanks Prior to analysis of the samples and standards, O.lmL o f Milli-Q was extracted on the Dohrmann DX2000 Halide Analyzer in the same way as the standards to insure the system was free o f any fluoride contamination. Total fluoride was then measured on the Orion EA940. Analyst / Date Daniel Howman /10-1 -97 Page 2 of 7 USEPA 9007 ss j U S' 000134 4.3 Samples For sample analysis, 0.02 gram samples of soil were extracted in triplicate on the Dohrmann DX-2000 in the same way as the standards. The EOXSolids computer program was used for sample extraction. The concentration o f fluoride extracted was determined by direct measurement with the 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 o f POAA is 66.10%, thus, the concentration o f fluoride in the standards was determined by multiplying the concentration o f POAA by 66.10%. Concentration o f F- = (Standard concentration) * (0.661) Concentration of F- = (25ppm POAA) * (0.661) Concentration o f F- in 25ppm POAA = 16.5ppm These calculated values were plotted and a standard curve calculated using linear regression. The equation o f the regression is y = 0.0067x - 0.1061. A linear correlation coefficient o f 0.9962 was obtained for the standard range of 25 - 1000 ppm APO. 5.2 Blanks No further analysis was done on the blanks. 5.3 Samples The Total Fluoride in the samples is reported as the average o f 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 of R2382-1-1 + 0.1061) / (0.0067) Calculated F- (mg/L) - (0.8047 + 0.1061) / (0.0067) Calculated F- o f R2382-1-1 - 136mg/L Calculated F- (mg/Kg) = (Calculated F- (mg/L)) (Collection Volume) / (Sample Weight) Calculated F- (mg/Kg) = (136mg/L) (3m l)/ (0.0203grams) Calculated F- (mg/Kg) 20100mg/Kg . Analysis blanks and calibration check standards were analyzed periodically to verify that the system continued to operate properly. Analyst / Date D a n ie l H o w m a n / 1 0 -1-9 7 Page 3 of 7 A SH010532 s i 4 /A ? CQ0135 USEPA 9008 6.0 CONCLUSIONS Triplicate analysis o f the pyrolysis products o f R2382-1 to R2382-11 determined that fluorine is present in all samples. Total fluoride concentration varies from 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 R2382-6 and the lowest levels in samples R2382-1 and R2382-2. A S H 0 10533 Analyst / Date Daniel Howman / 10-1-97 Page 4 of 7 USEPA9009 UO ^ C0 0 1 3 6 Standard Curve POAA ASHO10534 lr> C5 T'i O Meter Reading USEPA 9010 Analyst / Date Daniel Howman /10-1-97 Page 5 of 7 Project: R2382 ____________________________________ Dupont Washington Soil Samples Calculations fo r Standard Curve Calculated F- (mg/L) * Meter Rearing * Cotecbon Volume / Sam ple Volume Sam ple Oilubon Sam ple 10 VokJtMtmU Analysis 0RH 9-29-97 QC 4 33PPM ERA CHECK 2 BLANK-1 1 0.01 BLANK-2 1 0.01 BLANK-3 1 0.01 25PPM W 397-919 1 0.01 25PPM W 397-919 1 0.01 25PPM W 397-919 1 0.01 25PPM W 397-919 1 0.01 QC 1 OPPM CHECK 1 0.01 50PPM W 397-920 1 0.01 SOPPM W 397-920 1 0.01 50PPM W 397-920 1 0.01 2S0PPM W397-921 1 0.01 250PPM W397-921 1 0.01 QC 1 OPPM CHECK 1 BLANK-1 1 0.02 BLANK-2 1 0.02 BLANK-3 1 0.02 25PPM W 397-919 1 0.02 25PPM W 397-919 1 0.02 25PPM W 397-919 1 0.02 50PPM W 397-920 1 0.02 50PPM W 397-920 1 0.02 50PPM W 397-920 1 002 QC 1 OPPM CHECK 1 250PPM W 397-921 1 0.02 250PPM W397-921 1 0.02 250PPM W397-921 1 0.02 500PPM W 397-922 1 0.02 500PPM W 397-922 1 002 500PPM WO97-922 1 0.02 1000PPM W 397-923 1 0.02 1000PPM W 397-920 1 0.02 1000PPM W 397-923 1 0.02 QC 1 OPPM CHECK 1 Noteoook Reterenca: Cartton-SA-2. 0 20-21 C otecb o n Volume (mU 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 30 Calculated F- (mgA.) 18.3 16.5 12.8 13.9 30.5 28.2 21.7 111.7 128.4 13.7 17.2 16.0 26.5 28.6 26.5 130.6 146.5 144.1 301.6 300.6 3 1 4 .4 ' 645.2 672.1 658.5 StandaM FConcentration (mq/L) 16.5 16.5 16.5 165 33.1 33.1 33.1 165.3 165.3 . 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 6610 Meter, Reading % Rec. C om m ents 2.062 0.05853 0.03891 0.02618 0.06097 0.05506 0.04256 0.04638 0.9685 0.1016 0.08735 0.07239 0.3724 0.4279 0.9845 0.07984 0.02783 0.02694 0.09136 0.1149 0.1067 0.1764 0.1906 0.1764 0.9725 0.8710 0.9765 0.9607 2.012 2.004 2.096 4.301 4.461 4.390 0.9646 95 25 110.69 99.96 77.26 84.20 96.85 9222 79.29 65.71 87.61 77.68 98.45 Oue to low m eter roarings and low recovery; decided to rerun using 20uL as sam ple voiumeslll 8293 104.25 96.86 80.04 86.50 30.04 97 25 79.06 88.64 87.20 91.32 90 95 95.13 97.61 101.68 99.63 96.46 Analyst / Oat* Daniel Howman /10-1-97 > C K otLL-Onn __ C0 0 1 3 8 USEPA 9011 Project: R2382 Soil Samples from Dupont Washington Calculations for Total Fluoride in Soil C alculated F- (mg/L) (Meter Reading * Intercept) / Slope C alculated F- (mg/Kg) C alculated F- (mg/L) *Collection Volume / Sam pie W eight Sam ple Dilution 10 Analysis: 0RH 9-30-97 QC 4.33PPM ERA CHECK 2 BLANK-1 1 BLANK-2 1 BLANK-3 1 R2382-1-1 R 23 8 2 -1 -2 R 23 8 2 -1 -3 R23S2-2-1 R 238 2 -2 -2 R 2 382-2-3 QC 1.OPPM CHECK 1 R2382-3-1 R 2382-3-2 R 2382-3-3 R2382-4-1 R 2 3 8 2 -4 -2 R2382-4-3 R 2382-4-4 v410uL spike ol 10.000oom POAA R2382-5-1 R 2 3 82-S -2 R 2382-5-3 QC. 1.OPPM CHECK 1 R 2 382-8-1 R 2382-8-2 R 2 382-6-3 R2382-7-1 R 2 3 8 2 -7 -2 R 2382-7-3 R 2 382-8-1 R2382-8-2 R 2 3 8 2 -8 -3 QC 1.OPPM CHECK 1 R2382-9-1 R 2 382-9-2 R 2382-9-3 QC 1.OPPM CHECK 1 A nalysis: ORH 10-1-97 OC 4.33PPM ERA CHECK 2 BLANK-1 1 BLANK-2 1 BLANK-3 1 R 23 8 2 -1 0 -1 R 2 382-10-2 R 2 362-10-3 R 2 3 8 2 -1 1 -1 R 2 3 8 2 -1 1 -2 R 23 2-11-3 QC 1 OPPM CHECK 1 Sam ple Collection Weight (g) Volume (mL) 0.0203 0.0231 0.023 0.0236 0.0215 0.0219 0.0204 0.0225 0.0202 0.0235 0.0227 0.0225 0.023 0.0228 0.023 0.0226 0.021 0.021 0.0214 0.0218 0.0201 0.021 0.022 0.0216 0.0215 0.0209 0.021 0.0203 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 0.0203 0.0201 0.0208 0.0218 0.0223 0.022 3.0 3.0 3.0 3.0 3.0 3.0 3 .0 3.0 3.0 M eter Calculated Reading F- (mg/L) 2.079 0.07719 0.05811 0.06166 0.8047 0.8870 1.155 0.8080 0.9163 0.9542 0.9698 2.485 2.983 2.841 3.668 3.898 4.109 6.189 136 148 188 136 153 158 387 461 440 563 598 629 940 5.349 5.436 5.136 0.9856 3.835 3.789 3.774 2.983 2.588 2.415 1.811 1.841 1.503 0.9777 1.485 1.509 1.342 0.9737 814 827 782 588 561 579 461 402 376 286 291 240 237 241 216 2.019 0.1319 0.06430 0.05910 1.665 1.741 1909 1288 1.471 1.402 0.9420 264 276 301 208 235 225 N otebook R eference: Cailtan-SA -2. B-21-23 Calculated Statistics % F- (mg/Kg) (mg/Kg) ^M ovtfy 96.0 20.100 19200 24.500 17,300 21.300 21.700 AVE 21300 STO 2800 CV 13 AVE 20100 STO 2400 CV 12 56200 61.500 65.300 71200 79.000 83.900 122,600 AVE STO CV AVE STO CV 61200 4200 7 78300 6000 8 107.100 107,900 103.900 AVE 106300 STO 2100 CV 2 84.000 83.000 81200 63,400 60.000 53.800 39,000 40,400 33200 AVE STO CV AVE STO CV AVE STO CV 82700 1400 2 59100 4900 8 37600 3600 10 34,100 34,400 31.900 AVE 33500 STO 1400 CV 4 97.0 51.4 98.6 97.8 97.4 932 39,100 41,100 43.400 28.600 31,700 30.700 AVE STO CV AVE STO CV 41200 2200 5 30300 1600 5 942 Com m ents > on X oLuo>ns Analyst / Data Daniel Howman /10-1-97 Page 7 o l7 Li 4 US' C C 0139 USEPA 9012 3M Environmental Laboratory Total, Organic and Adsorbable Fluoride in Groundwater (6/97 Samples) ASHO10537 USEPA 9013 4 U S' 00140 3M Environmental Laboratory Data Transmittal Summary Preliminary / Final (circle one) 'f Lab Request #: 3M Study #: R-2148 Bigenenvir Date Received: Contract Laboratory # Sponsor or Client: Representative Name Dale Bacon / Robert Howell Company Name 3M Company Address 935 Bush A ve., S t Paul, MN Phone 778-4736/778-7540 Project Lead: Name / Phone Kris Hansen Group Leader N am e/ 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 Schtz, Nancy Bergman Author: Jan Schtz Data Reviewed by: Project Lead (or designee): PatRethwill 10/03/97 James D. Johnson (or designee): Internal JDJ: Kris Hansen QAU (Archives): Rich Youngblom LIRN System: Denise Appleton Project M anager Sue Beach Others (List Recipients / Address / Phone / FAX) Sent by: / Date JGS /1 1/07/97 JGS /1 1/07/97 JGS /1 1/07/97 JG S /1 1/07/97 Sent by: / Date ASH010538 A copy of the report Deluding this form and the client cover page is to be given to QAU, LIRN and to the Group Leader. is i US USEPA 9014 C 0 0 1 4 3M Environmental Laboratory - Advanced Method Development Team Contact: Kris Hansen - Sr. Analytical Chemist B uilding O2-3E-09................................................... 778-6018 kjhansen @ mmm.com Final Report - Lab Request R2148 Total Fluoride Analysis - DuPont 30 Septem ber 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 o f DIN method 38 402 H29 was used to measure the AOF. The following table contains a summary o f the results. Sample ID Sample Request MW-I-1 M W -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-6-1 MW-6-2 R2148-1 R2148-2 R 2 148-3 R2148-4 R2148-5 R2148-6 R2148-7 R2148-8 R2148-9 R2148-10 R2148-11 R2148-12 Fluoride Ion (pg/mL F-) 020 0.20 0.16 0.16 0.14 0.14 0.11 0.11 <0.10 <0.10 0.10 0.10 Total Fluorine (pg/mL F-) 8.0 16 3.3 3.5 42 3.3 4.0 42 3.0 2.8 22 42 Total Fluorine Fluoride Ion Gig/mL) 7.8 16 3.1 3.3 4.1 3.2 3.9 4.1 2.9 2.7 22 4.1 Adsorbable Organic Fluorine (pg/mL F-) 4.5 4.2 0.28 0.46 1.1 0.76 0.19 0.14 0.11 0.14 <0.05 <0.05 2.0 INTRODUCTION ASH010539 A request was made o f the 3M Environmental Laboratory to determine the amount o f 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. 3.0 TEST MATERIALS . 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 USEPA 9015 tote 4 M 500142 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 H/50% Milli-Q water 4.0 EXPERIM ENTAL - OVERVIEW 4.1 Fluoride Ion Analysis This analysis measured the amount o f fluoride ion in the sample without combusting the sample. For measurement of fluoride ion, an Orion EA940 meter was calibrated daily, using Coming standards over the range o f 0.05 - 1.5 ppm fluoride. One milliliter o f 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 o f 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 mL o f standard or sample (or an aliquot o f sample diluted 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 o f 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. 4 3 T otal Fluorine Analysis This analysis measured the amount o f total fluorine by combusting an aliquot o f unfiltered sample, collecting the off-gasses, and analyzing the 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 the off-gasses in 3.0 mL 1:1 TISAB D/Milli-Q water for analysis on the Orion EA940 meter. The water samples were analyzed following the same method as the standards. ASH010540 IN ST R U M E N TA T IO N Dohrmann DX2000 Organic Halide Analyzer modified for fluoride analysis Dohrmann Adsorption Module AD2000 3M Environmental Laboratory, Lab Request R2148 ' J USEPA 9016 u7 4 n s C 0014 IN ST R U M EN T A TIO N 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 1:1TISAB II/Milli-Qwater . REAGENTS Fluoride Standard 100 ppm, purchased from Corning (part #478170, lot #1113022) Total Ionic Strength Adjustment Buffer (TISAB II)Orion (part#940909, lot ARI) 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 o f calibration standards made from Coming fluoride stock standard. An acceptable correlation coefficient is = 0.9950. date 18-21 August 1997 18 August 1997 15-25 August 1997 analysis done Total Fluorine Analysis / POAA standard curve Fluoride ion analysis AOF Analysis / POAA standardcurve correlation coefficient (R2) >0.9993 >0.9998 >0.9999 A standard curve for total fluorine was generated by combusting 0.1 mL aliquots o f 2.0, 5.0, 20, 50, and 100 pg/mL POAA standard (POAA is 66.1% fluoride) in the Dohrmann DX2000 Modified Organic Halide Analyzer. The off-gasses were collected in 3 mL o f 1:1TISAB II/ Milli-Q water and analyzed with the Orion meter. Using least squares linear regression, plotting the fluoride concentration o f the standard on the x-axis, and the Orion meter response on the y-axis, the following curve was generated: Y - 0.034 lx 0.0157 and R2= 0.9988. A standard curve for adsorbable organic fluorine (AOF) was generated by pushing 100 mLs each o f 5 standards containing 4.9, 14.4,23.6,33.5, and 43.1 pg/mL fluorine as POAA through two carbon columns. The carbon columns were combusted in the Modified Dohrmann DX2000 Organic Halide Analyzer. The effluent was collected in 3 mL o f 1:1 TISAB II / Milli-Q water and analyzed with the Orion meter. Using least squares linear regression, plotting the fluoride concentration o f the standard on the x axis, and the Orion meter response on the y axis, the following curve was generated: Y =0.2894x + 0.0196 and R2= 0.9949. A S H 0 10541 3M Environmental Laboratory, Lab Request R2148 USEPA 9017 0 0 1 4 US' SAMPLE ANALYSIS Fluoride loo Analysis Sample tt Meter Reading Dilution Factor Quantity of Sample (mL) Fluoride Ion in Sample (pgftnL) R2148-1 0.1005 2 1.0 0.20 R 2 148-2 0.1017 2 1.0 0.20 R2148-3 0.0813 2 1.0 0.16 R 2 148-4 0.0801 2 1.0 0.16 R 2 148-5 0.0701 2 1.0 0.14 R 2 148-6 0.0696 2 1.0 0.14 R2148-7 0.0567 2 1.0 0.11 R 2 148-8 0.0556 2 1.0 0.11 R 2 148-9 0.0465 2 1.0 <0.10* R2148-10 0.0463 2 1.0 <0.10* R 2 148-11 0.0491 2 1.0 <0.10* R2148-12 0.0497 2 1.0 <0.10 `Method detection limit (MDL) = 0.100 ppm (lowest calibration standardx dilution factor) AOF Standard Curve Total Ammonium Perfluorooctanoate Standard in Columns (top + bottom) Sample ED * POAA Standard 1 0.072 ppm POAA Standard 2 0.217 ppm POAA Standard 3 0.362 ppm POAA Standard 4 0.507 ppm POAA Standard 5 0.652 ppm A Standard is 66.1% Fluoride Quantity Combined Spiked Sample Orion Meter pg/mL F- (mL) Reading in Sample (jig/mL F-) 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 R2- 0.9949 AOF Sample Analysis Sample ID Combined Quantity of Sample Adsorbable Organic Fluorine Meter Reading (mL) in Sample (jig/mL) R2148-1 (top + bottom) R 2148-2 (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) R 2148-11 (top + bosom) R2148-12 (top + bottom) *MDL * 0.05 pg/mL. 6.544 6.063 6.776 11.30 3235 2229 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 ASHO10542 4.5 4.2 0.28 0.46 1.1 0.76 0.19 0.14 0.11 0.13 <0.05* <0.05* ` USEPA 9018 i MS' CC0145 Total Fluorine Standard Curve Ammonium Perfluorooctanoate in Milli-Q w ater Sample ID POAA standard 1 - 2.00 ppm POAA standard 2 - 5.00 ppm POAA standard 3 - 20.0 ppm POAA standard 4 - 50.0 ppm POAA standard 5 - 100 ppm Q u a ntity Sample OnL) 0.100 0.100 0.100 0.100 0.100 Orion Meter Reading (pg/mL F-)1 0.048 0.100 0.421 1.089 2.248 Spiked pg/mL F- in Sample * 1.32 3.31 13.2 33.1 66.1 'Based on the average of three replicates. Y - 0.034lx - 0.0157 R2- 0.9988 ammonium perfluorooctanoate standard is 66.1 % Fluoride Total Fluorine Sample Analysis Sample ID Meter Reading MW-1-1 M W -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-6-1 MW-6-2 R 2 148-1 R 2 148-2 R 2 148-3 R2148-4 R 2 148-5 R2148-6 R2148-7 R2148-8 R2148-9 R2148-10 R2148-11 R 2 143-12 0.2568 0.5217 0.0964 0.1051 0.1279 0.0963 0.1199 0.1260 0.0960 0.0802 0.0636 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 pg/mL F- in Sample 8.0 16 3.3 3.5 4.2 3.3 4.0 4.2 3.0 2.8 23 42 6.0 CONCLUSION Fluoride ion concentrations range from <0.10 to 0.20 pg/mL, <0.05 to 4.5 pg/mL F- for adsorbable organic fluorine analysis, and 2.3 to 16 pg/mL F- for total fluorine analysis. The large difference in concentration o f total fluorine for samples, R 2148-1 and R 2148-2 (duplicate samples) may have been caused by differences in the amount o f solid particulate matter in the sample aliquots. The results for the adsorbable organic fluorine analysis may be lower than expected, due to the fact that the solid particulate matter was filtered from the AOF samples, and some polymers may not adsorb on to the charcoal columns. 7.0 M AINTENANCE OF RAW DATA Hard copies o f the data are filed in the AMDT archive. JG Schtz 09-30-97 AS'HO 10543 3M Environmental Laboratory, Lab Request R 2 148 70 eg U S ' USEPA 9019 CO01/16 Curve ASHO10544 \</X 'Tr*l, "o USEPA 9020 Orion Data ASH010545 DATA FOR AlMMONIUM PERFUJORO CTANOA1 E AOF ST/INDARD CURVI C alc. ------------------ [------------------ F- Cone, Sam ple ID A ctual M eter reading (ppm F-) C ollect D ilution Voi (mL) Factor Sam ple Volum e C alc AO F of column Total o f Orion read top&bottom TOTAL AOF in % (T o p i. Standard Recovery ^ B o t t o n O ^ (pgfmL) Std # 1 bottom 0 1522 0.4538 0.3701 3 .0 3 .0 3. 1 1 1 1 100 1 0 .4 5 6 5 0.01361 0 .0 1 1 1 0 -- -------- ------------- -- -- -- ------------------ CM 41 hntfnm 0.3643 3;o - 1 100 0 .0 1 0 9 2 9 6 cih # 4 bottom CM M* hnlfnm 0.1815 0.1232 3 .0 3 .0 1 1 100 100 0 .0 0 5 4 4 0 .0 0 3 7 0 CM M 1 Inn CM M0 Inn RM 4 1 Inn CM MA Inn Std # 5 tOD QC check 5.0 0.0544 1.1620 3.8126 6.3834 9.1307 12.764 5.098 1 3 .0 3 .0 3.0 3 .0 3 .0 3 .0 1 .0 1 1 1 1 1 1 1 100 100 100 100 100 100 1 0 .0 0 1 6 3 0 .0 3 4 8 6 0.1144" 0 .1 9 1 5 0 .2 7 3 9 0 .3 8 2 9 5 .0 9 8 1.616 4 .1 8 3 6 .7 4 8 9 .3 1 2 12.887 0 .0 4 8 0 .1 2 5 0.2 02 0 .2 7 9 0 .3 8 7 0 .0 4 9 0 .1 4 4 0 .2 3 9 0 .3 3 5 0.431 100% 87% ----------------- 85% 83% 90% FLUORIDE l<)N ANALY SIS Total Fluoride S a m n lA ID Mater Read TISABVol Dilution Sample Voi HP. rhork f M n 0.5018 1 .0 1 1.0 foig/mL) 0 .5 0 ? 100% R2148-1 R2148-2 R2148-3 R2148-4 R2148-5 R2148-6 R2148-7 0.1005 0.1017 0.0813 0.0801 0.0701 0.0696 0.0567 1 .0 1 .0 1 .0 1 .0 1 .0 1 .0 1 .0 2 1.0 2 1.0 2 1.0 2 1.0 2 1.0 2 1.0 2 1.0 0 .2 0 ? 0 .2 0 3 0 .1 6 3 0 .1 6 0 0 .1 4 0 0 .1 3 9 0.113" R2148-8 0.0556 1 .0 2 1.0 0 .1 1 1 R2148-9 0.0465 1 .0 2 1.0 0 .0 9 3 R2148-10 0.0463 1 .0 2 1.0 0 .0 9 3 R2148-11 0.0491 1 .0 2 1.0 0 .0 9 8 R2148-12 QC check 0.50 pp 0.0497 0.5039 1 .0 1 .0 2 1.0 1 1.0 0 .0 9 9 0"504 101% USEPA 9021 S co V T*j o e o Page 1 R2148.xls Orion Data ASM010546 kOF ANALYSIS Intercept)/ slope) / sample volume OF Calc. (fig/mL) = ((total meter reading^ Calc. Adsorbable M eter Reading Organic Fluorine Total ftop&bottom) (ng/mL)_ y=0.2894+0.0196 Comments % Recovery Ci r*' '>0 O C O IN. USEPA 9022 Page 2 R 21 4 8 .x ls USEPA 9023 Orion Data ASH010547 A O F Calc, (pg /m l) = ((total meter reading - intercept)/ slope) / sample volume AOF ANALYSIS Calc. Adsorbable y = 0 .2 8 9 4 + 0 .0 1 9 6 Sam ple M eter Collect Dilution Sample M eter Reading Organic Fluorine Comments % ________ !2 ________ Reading Vol (mL) Factor Vol (m L) Total (top&bottom) (to p & b o tto m )_____________ Recovery________ R2148-9bottom R2148-10 bottom R2148-11 bottom R2148-12 bottom R2148-9top 2148-10 top R2148-11 top R2148-12 top R2148-7MS Bottom R2148-7 MS Top QCcal chocIt4.33 ppm R 2148-11 bottom R 2148-12 bottom R 2146-11 Top R 2148-12 Top QC chock 0.050 ppm 0.2705 0.2784 0.1188 0.0713 1.2856 1.6588 0 .3 5 2 0 0 .2 6 8 3 0.1134 3 .0 2 9 7 2 .2 2 8 0 .0 7 6 0 0 .0 8 3 9 0.4608 0 .4 5 1 8 0 .4 9 8 8 3 .0 3 .0 3.0 3 .0 3 .0 3 .0 3 .0 3 .0 3 .0 3 .0 1 .0 3 .0 3 .0 3 .0 3 .0 1 .0 1 1 1 1 1 1 1 1 1 1 2 1 1 1 1 1 50 50 50 50 50 50 50 50 100 100 1 100 100 100 100 1 1.5561 1.9372 0 .4 7 0 7 0 .3 3 9 6 3 .1 4 3 0 .5 3 6 8 0 .5 3 5 7 0 .1 0 6 2 0 .1 3 2 5 0 .0 3 1 2 0 .0 2 2 1 0 .1 0 7 9 4 .4 5 6 readbatowlowit<1. m-run madbelowlowltd. m-run 103% 0 .0 1 7 6 0 .0 1 7 5 98% '3 kC o Page3 R2148.xls measured electrode responce (ppm F-) POAA CURVE ASH010548 Thermally Extracted Perfluorooctanoate Curve 2 .5 0 0 0 0 y = 0.0341x - (1.0157 2.00000 ---------- F2= 0.99{ oO---------- Va 1/3 f t <?*j O vc Va TCtN- o Os <PWi 05 1.50000 1.00000 0 .5 0 0 0 0 0.00000 ____ __ 10 20 30 40 50 STANDARD CONCENTRATION (PPM F-) 60 Page 1 70 DUP0NT1.xls 11/7/97 3:30 PM Perfluorooctanoate Standard Curve 3fl kii..ifok..O ERA 4.33PPM STD Q C 1.0P P M STD CHECK BLK-1 BLK-2 BLK-3 PO AA1.0 PPM W 397-795 PO AA 1.0 PPM W 397-795 POAA 1.0 PPM W 397-795 ERA4.33PPM STD QC1.0PPM STD CHECK BLK-1 BLK-2 BLK-3 POAA 2.0PPM W 397-801 POAA 2.0PPM W 397-801 POAA 2.0PPM W 397-801 POAA 5.0 PPM W 397-796 POAA 5.0 PPM W 397-796 POAA 5.0 PPM W 397-796 QC 1.0 PPM CHECK POAA 20PPM W 397-797 POAA 20PPM W 397-797 POAA 20PPM W 397-797 POAA 50PPM W 397-798 POAA 50PPM W 397-798 POAA 50PPM W 397-798 POAA 100PPM W 397-799 POAA 100PPM W 397-799 POAA 100PPM W 397-799 QC 1.0 PPM CHECK uLAUaMd lAill 2 1 0.1 1 0.1 1 0.1 1 0.1 1 0.1 1 0.1 3. 3 3 3 3 3 1 0.1 1 0.1 1 0.1 1 0.1 1 0.1 1 0.1 1 0.1 1 0.1 1 0.1 1 0.1 1 0.1 1 0.1 1 0.1 1 0.1 1 0.1 1 0.1 1 0.1 1 0.1 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 1.47 1 .0 2 0 .4 8 1.16 0 .9 7 1.40 1.473 1.473 1.397 2 .8 2 3.22 2 .9 9 1 2 .1 0 12.80 12.96 3 1 .9 2 33.12 3 2 .9 7 6 6 .5 4 6 9 .6 0 6 6 .2 7 ASHO10549 0.661 0.661 0.661 1.322 1.322 1.322 3.31 3.31 3.31 13.22 13.22 13.22 33.05 33.05 33.05 66.10 66.10 66.10 2.2 00 0 .9 6 5 2 0.0491 0 .0 3 4 0 0.0161 0 .0 3 8 8 0 .0 3 2 3 0 .0 4 6 7 2.162 0.6864 0.01599 0.01455 0.01491 0.04911 0.04911 0.04655 0.0939 0.1074 0.0998 0.9691 0.4033 0.4268 0.4321 1.064 1.104 1.099 2.218 2.320 2.209 0 .9 9 3 0 1 0 1 .6 96.52 176 BELOW DETECTIO N LEVEL 147 USE 2.0PPM STD DATA 2 1 2 NO T INCLUDED IN CURVE 9 9 .8 6 9 8 .6 4 111 111 106 85.2 9 7 .5 9 0 .6 9 6 .9 9 1 .5 9 6 .9 98.1 9 6 .6 100 9 9 .8 101 105 100 99.3 111 111 106 CM T*1 V Oc u i<OnN Os < Pwcnh Page 1 0U PO N T1.xls I calculated (ppmH = reading intercept) i alope) ^ O 01 - s s r r s s . - ' - " "-""" CALC. K 4 .3 3 P P M S T D l o c t.Q P P M S I P B j g --------- o T [ b l k -T - o1 J b LK-2 o! IBLK-3 ------- ----te fT iO P P M CHECK---------------g y R 2 1 4 8 -1 1 -1 01 IR 2148-11-2 Q1 IR 7148-11-3 ----- -------------- --- < jT JR 2148-12-1 Q1 1R 2148-12-2 Q1 IR 2 1 4 8 -1 2 -3 ------------ ,,------- IR 2148-10*1 1R 2148-10-2 01 01 | p 2148-10-3 --------- IQ C 1 .0 P P M CHbC/K -------------- g y |R 2 1 4 8 -9 -i IR 2148-9-2 |R 2 148-9-3 IR 2148-8-1 IR 2148-8-2 R 2 1 4 8 -8 -3 ____ R5c T o p p m s t d c ^ c k _ 2 .1 6 2 0 .9 8 6 4 '001599^ 0 .0 1 4 5 5 0 .0 1 4 9 1 0 .9 7 4 3 ~ 0 .0 5 5 5 5 0 .0 6 0 3 1 007499 "0 1 6 9 9 " 0 .1233 0 .09247 0 .0 8 3 7 9 0 .0 6 2 8 4 0 .09400 0.9 6 6 3 0 .1 0 4 2 " 0 .0 7 9 1 0 0 ,0 7 2 8 6 "0 1 3 6 ? " 0 .1 2 7 9 0 .1 1 3 1 0 .9 6 2 4 CV ASH010550 9 9 .8 6 1 9 8 .6 4 1 9 7 .4 3 1 90241 77 4 U S ' USEPA 9026 G O Q 5 .S 3 DUP0NT1 .xls 11/7/97 3:17 PM TABLE contiued : R2148 F- DETERMINATION: SAMPLES DUPONT INC. SAMPLE COLLET A ctual CALC. m m m m if M STATS n il ERA 4.33PPM STD IQ C 1.0 PPM STD CHECK Ib lk -1 IB L K -2 1BLK-3 |R 2 148-7-1 m 2148-7-2 J R 2 1 4 8 -7 -3 JR2148-4-1 |R 2148-4-2 |R 2148-4-3 IQ C 1.0PPM STD CHECK IQ C 1.0PPM STD CHECK [R 2 1 4 8 -3 -1 R 248-3-2 R 2148-3-3 R 21 4 8 -6 -1 R 2148-6-2 R 2 1 4 8 -6 -3 JR2148-5-1 R 2148-5-2 R 21 48 -5-3 QC 1.0PPM STD CHECK R 2 1 48 -1-1 R 2 1 4 8 -1 -2 R 2148-1-3 R 2148-2-1 R 2148-2-2 R 21 48 -2-3 IQ C 1.0PPM STD CHECK 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 0.1 0 .1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 2 .1 7 9 0.9781 3 0.05542 2 .0 9 3 0 .0 4 1 6 9 1 .6 8 3 0.03074 1.36 3 0 .1 0 8 8 3 .6 5 3 0 .1 0 7 5 3.61 3 0 .1 4 3 5 4 .6 7 3 0 .1 3 2 3 4 .3 4 3 0 .1 0 2 8 3 .4 8 3 0 .0 8 0 2 4 2.81 0 .9 5 0 7 0.9941 3 0 .1 0 0 3 3 .4 0 3 0 .0 9 0 6 5 3.12 3 0 .0 9 8 3 3 3 .3 4 3 0 .1 0 2 4 3 .4 6 3 0 .0 9 5 5 7 3 .2 6 3 0 .0 9 1 0 2 3 .1 3 3 0 .1 2 2 5 4 .0 5 3 0 .1 5 3 8 4 .9 7 3 0 .1 0 7 5 3.61 0 .9 6 2 3 2 8 .6 8 3 0 .1 8 0 9 5.77 3 0.2924 9.04 3 0 .2 9 7 2 9 .1 8 3 0 .4 6 4 8 14.09 3 0.4517 13.71 3 0 .6 4 8 7 19.48 0 .9 6 2 3 AVE STD CV AVE STD CV AVE STD CV 1.71 0 .3 6 2 1.2 3.98 0 .6 0 15.1 3 .5 4 0 .7 7 21 .6 AVE STD CV AVE STD CV AVE STD CV 3 .2 9 0 .1 5 4 .5 3 .2 9 0 .1 7 5.11 4.21 0 .6 9 16.4 AVE STD CV AVE STD CV 7 .9 9 1.9 24.1 15.76 3.2 2 0 .5 % REC 100. 97.81 9 5 .0 7 99.41 9 6 .2 3 96.23 m T 'i to a ASH01055I t-" 0O4 Os <Ph wcn P 3M Environmental Laboratory Soil Properties and Nutrient Concentration Analyses (6/97 Samples) USEPA 9028 ASHO10552 3M Ecotoxicology and Environmental Fate Laboratory Soil Properties and Nutrient Concentration Analyses of Samples Received From the E. I. DuPont de Nemours and Company Facility in Parkersburg, West Virginia ASH010553 STUDY COMPLETED: August 27,1997 FINAL REPORT COMPLETED: October 31,1997 Lab Request No. R2382 Prepared by: Susan A. Beach Senior Environm ental Biologist 3M Environmental Laboratory Building 2-3 E -09 935 Bush Avenue St Paul, MN 55144 USEPA 9029 SO $ i * c C0 0 1 5 6 3M Ecotoxicology and Environmental Fate Laboratory 1.0 Introduction Eleven soil samples were received from E.l. 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..LR. Nq. 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' S S -1 4-6* SS-1 8-10' S S -1 12-14' S S -1 16-18' SS-1 20-22' S S -1 24-26' S S -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 Sulfate, Sulfite, Sampi No. mg/kg mg/L R2382-1 SS-1 0 -2 R2382-2 SS-1 4-6' R2382-3 SS-1 8- ia 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* R2382-1C SS-1 36-38* R2382-11 SS-1 38-40* 98 99 73 54 43 70 220 150 100 63 46 <2 <2 <2 <2 <2 <2 <2 <2 <2 <2 <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 pH in CaCI2 7.2 7.3 7.0 6.3 5 .3 5.5 5.3 6.3 5 .2 5 .4 6.2 pH in 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 ASH010554 2 Si \2S~ C H 0 5 7 USEPA 9030 3M Ecotoxicology and Environmental Fate Laboratory 3.0 Initial Observations 3.1 Sam ple 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/silt/sand, more silt/sand. 3.5 Sample R2382-9 Appears to be sand/silt. 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. Soil was crushed, as necessary with a mortar and pestle, and passed through a 2.00 mm stainless steel sieve. Soil prepared this way was used for pH analyses. ASH010555 3 USEPA 9031 CC01S8 3M Ecotoxicology 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 W ater 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 * 6.2 Soil pH 6.2.1 pH in Water Ten grams of 2.00 mm-sieved soil and 10 mL Miili-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. ASH010556 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.ON pH 8.2 NaOAC were placed into 250 mL conical polypropylene centrifuge tubes. The , 000159 4 3 4 I* ? USEPA 9032 3M Ecotoxicology 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 NH4 OAC 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. mq/U/23 oven-dried weight of soil, g* x 100 = meq / 1 0 0 g soil 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. ASH0I0557 Zi 4 U S 5 USEPA 9033 C C O IG O 3M Ecotoxicology and Environmental Fate Laboratory Copies of Raw Data and Contract Laboratory Reports S S cf IZS~ c o o le r USEPA 9034 ASH010558 ENVIRONMENTAL LABORATORY WORKSHEET LR ^ . 3 8 2 page / OF / DATE 8 1 5 / f1/ ANA^YSi^ . 3 J jj/'ita L _____________________________________________ __________________ _ ,p a j y i f e s l - f / t r u y / $ / / J ifir f a ^d if ..H P . * -------------------- / f a f f < jf J L ' o /u n (ri J u f t k A s r . f t / y J ' b e Ls & M //3 //t d fp f.A * ^ f r f - j s & id fii tt' ilil& i ..... - ...- - ................. . u jb ftr /ijM /M ja -iln .-< 2 A f.J b (rt n a rf S u a d . 'flfifts d J fS f .* * {* ; * M ,i* 0 flr /C , ^ L j * ^ f c t : . 7 X 4 L .,e a & t & ^ '4 r jtte $ fu 7 Y r d f r r f n a z a m c , M /j- f l r j M l F a i L a t y s f c . ______ _____ ______ __ _________________ L------------------- 0>0 X _ USEPA 9035 e y c( / o r C001G2 ENVIRONMENTAL LABORATORY S O IL W A TE R C O N T E N T PERCENTAGE OF WATER IN THE SAMPLE ON A DRY-MASS BASIS G ardner, W alter. 1986. W ater Content, p. 493 -5 44 . In Arnold Klute (E d .). M ethods of Soil Analysis, Part 1. Physical and M ineralogical M ethods. Agronomy M onograph No. 9 (2nd Edition). % W ater Content - W eight of W et Soil - W eight o f Drv Soil x Weight of Dry Soil 100 SAMPLE DESCRIPTION 2.-1 2/ -4 A Ip 1 5? 4 fO n Wet Soil gMcdiWB) .33.* 1* 2 3 , \iZ. 2J\ SR 1 21/.&4 Z Z sIpIO 2.*1.(#4S 31. Sot# 2.2-SO*1 244^0 3L,. 1 2 $ DrySoil g (oven-dried) .=*">, 122 20.580 2-2.1SR 2S.3S3.23.041, NETLOSSg 3.1#35 2.1/12, * ,.4 3 2 , -4,1*3 3 . Sta -.442, lA.ftll# 21.11/8........................ 23.U54 2 . U ei{ f..srfn % 1L.* 17,4 /.< * r /,<? 19. Zj TA .b tt.f /3 . /# /%<? Z 2 t?j ANAl y s -DATE: OD ...... o3= Uot o 87 ^ I2S~ E N V IR O N M E N TA L LA B O R A TO R Y S O IL pH and LIM E R EQ U IR E M E N T(LR ) M cLean, E . 0 . 1982. Soil pH and Lim e Requirem ent, p. 199-224. In A. L. Page, R. H. M iller & D . R. Keeney (Eds.) M ethods of Soil Analysis, Part 2 . C hem ical and Microbiological Properties, Agronomy Monograph No. 9 (2nd Edition). 2 .0 0 mm air-dried soil used. Soil - to - M illipore M illi-Q TM W ater Ratio 1 :1 ,1 0 g plus 10 mL. For LR, S M P single-buffer method used. Soil - to - SM P Buffer Ratio 1: 2 ,10 g plus 20 mL. SAMPLE DESCRIPTION z. 5 it < 9 10 ll pHw (pH In water) *1.1 7 . u .i A /f) 5 ,$ is . * s .n L it /f.A pHs (pH in 0.01 M CaCI2) %2t /* ,* > 7 > ,2 > Soil-Buffer pH LR (T/A) ANAL<^S ^ D A T E :Z 5 ^ ^ 4 .> ------------- C/2 ac *3 4 U USEPA 9037 C0 0 1 6 4 USEPA 9038 EN V IR O N M E N TA L LA BO RA TO R Y S O IL W ATER CO N TEN T PERCENTAGE OF WATER IN THE SAMPLE ON A DRY-MASS BASIS G ardner, W alter. 1986. W ater Content, p. 493-544. In Arnold Klute (Ed.). Methods of Soil Analysis, Part 1. Physical and M ineralogical Methods. Agronomy Monograph No. 9 (2nd Edition). % W a ter C ontent = W eight of W et Soil - W eight of Drv Soil x 100 W eight of Dry Soil USEPA 9039 10 4 U S C001G6 * ENVIRONMENTAL LABORATORY C A TIO N EXC HA N G E C A PA C ITY (C E C ) BY S O D IU M SA TU R A TIO N R hoades, J. D. 1982. Cation Exchange C apacity, p. 149-157. In A. L. Page, R. H . M iller & D. R. Keeney (E ds.) M ethods of Soil Analysis, Part 2. Chem ical and Microbiological Properties, Agronomy Monograph N o. 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 equilibrium method (over-night) with 1.0N NH40AC pH 7.0 as extraction solution. C E C E Q U A T IO N ; ( 0 . 1 N a ppm / 23 / oven-dried wt. of soil g ) x 100 m e q /100 g soil SAMPLE DESCRIPTION ......-.. . 1 2A TCl la 'I 4 in it AIR-DRIEDWT. g 5 .0 0 0 A.OOO <, <500 A. non C. .T.oon OVEN-DRIEDWT. g 4. <15*1 4.^SPI 4.5 S 4,Rt*fe 4-.RL.1 .... .4. O 4 ^ *0 .^. 4.4B mgNa/ L IM mo ICO l 110 zm ICO ISO ISO no 72- meq/100 gsoil /S A /R .4 I.S n .s /6 .4 /frS _ /7 ___ ll _______ ______________ A N A L jg g j^rS DATE y ij-M r C0 cf j }%~ C001G7 USEPA 9040 LABORATORIES, 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 W E A R E A N E Q U A L O P P O R T U N IT Y E M P LO Y E R Me Mb e R AC11 Report To: Rochelle Robidean 3M Environmental Lab 935 Bush Ave., Bldg. 20 S t Paul, MN 55106 Date: W ork Orden D ate Received: 27 August 1997 10-0447 25 August 1997 Page 1 o f4 Inorganics Lab N .................... S4352 S4353 S4354 S4355 S4355 S43J7 Soil Lab No................................ W -547 W -548 W-549 W-550 W-551 W-552 Sample LD.................................. R2382-1 R2382-2 R2382-3 R2382-4 R2382-5 R2382-6 A n alyte Nitrite Nitrogen (mg/Kg N ) . . 0.41 0.41 0.36 0.14 < 0 .1 < 0.1 Sulfate (m g/K g)..................... 98.4 98.6 73.3 53.9 43.4 70.4 Sulfite (m g/L).......................... <2 <2 <2 <2 <2 <2 Report approved by: Anthony R. Koebele ^ By and for Minnesota Valley Testing Laboratories, Inc. > C/3 o L/1 ON MVTL c u arta tM the m arner * the analysa t a e m the p i a wbmittad fer M k . Il ta aol p w b le t e l i m . te fnaraMn te * a est n m h obuned a perticate sample will bs the m m b any other empie ii s l m all nraiftlrrns `V - f p h i m b u n e n . f i n m utual pntarTliieir if"**" p -" *** -* -- 1 r ` " " f 1 ----- VaiiUr f t r >w^ ** 11 *1 "llirt* e fd io e ie , end m h u ia rin ii h r pubttaatiaa rfs te n m --n , am daeisee a r Q ueta fram e r ragnrdU goar r a p ta is raearvad pandto w w ritten e p p w ia t ' . ' i .. C 001G 8 USEPA 9041 LABORATORIES, Inc. P.O. BOX 249, 1126 N. FRONT STREET NEW ULM, MN 56073-0249 PHONE (507) 354-6517 WATS (800) 782-3557 FAX (507) 359-2890 WE A R E A N EQUAL O PP O R TU N ITY EM PLO YER M EM B g R AOL Report To: Rochelle Robideaa 3M Environmental Lab 93S Bush Ave., Bldg. 20 S t Paul, MN 55106 Date: W ork Orden D ate Received: 27 August 1997 10-0447 25 August 1997 Page 2 o f4 Inorganics Lab N o .................... Soil Lab N o................................. Sample LD.................................. S4358 W -553 R2382-7 S4359 W -554 R2382-8 S4360 S4361 S4362 W-555 W-556 W-557 R2382-9 R2382-10 R2382-11 A aalyte Nitrite Nitrogen (mg/Kg N ) . . <0.1 0.11 <0.1 < 0 .1 < 0 .1 Sulfate (m g/K g)...................... 217 153 102 63.3 46.2 Sulfite (m g/L ).......................... <2 <2 <2 <2 <2 Report approved by: Arilhoay R. Koebele a t jS , B y and for M innesotaValley Testing Laboratories, Inc. M V T L fttarm ateas the accu racy o f the aaebma dene ea the tempi e a ip la n a le a s a lts a e d iiie e ia flb c tia g th e -- p U a ra th a a a tc U e su , aad aw theriaattoe far puhttratma r f d a iw t i, a r tem ple w ffl be the m m m, a ? a th * a subm itted as the run ftd se rta l p i party USEPA 9042 ASH010566 LABORATORIES, 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 W E A B E A N E Q U A L O P P O R T U N IT Y E M P LO Y E R MEMBg n A ailyte Nitrite Nitrogen Analysis of 3M Samples Page 1 o f 1 Detection Level 0.1 mg/KgN Method Reference Methods o f Soil Analysis, 2nd Edition, 33-8 Sulfate 40 mg/Kg on a 5 g sample SW-846, Method 9038 . Sulfite 2.00 mg/L EPA Method 377.1 >tz> oUl ON ttV T L |U H M th . m n >7 oftfe* w f e * te > m tk> a p l i 1 > M fer UMU* &I* aat p nrfhb t r MVTL p n M th * IM t n n k M a ri a t prttelr w i f e ffl b> tka m m t m m , ** i -- T'T rnf-rr- -- i, iadadlM-- Iprtfriniw rtl--H. thrw irtitoiitUljwng**" of M W in rtn t r p nhHnorta i US' USEPA 9043 c 00170 DATE: 08 1/1997 3M ENVIRONMENTAL LABORATORY CONTRACT LA&GPATGRY U.ORK ORDER BY PARAMETER LAB REQUEST NO. R2332 CONTRACT LAB PROJECT NUMBER SHIP CATE nVTL SIGENENVIR Conp-tsr C-de T e s t Nane FROJECT LEAD: RD HOUiELL TELEPHONE FAX : : 612-778-6176 Sample Numbers Sample Available Date Result Due .Date N 02-N 03 /*,*> NITRITE NITROGEN - as H` 1, 2 i 3 , A , 5 , ^ i 7, 3 , 9 , 10, 11 SULFITE 1 2 , 3 , A , 5 , 6 , 7 , S, 9 , 10, 11 SUu-PATE - as SOA It 2, 3 , A, 5 , * 7 , 9 , 9 , 10, 1.1 03/13/1??? 03/27/1997 08/13/1997 08/27/1997 08/13/1997 03/27/1997 ASHO10568 <\5 4 G00171 USEPA 9044 3M Ecotoxicology and Environmental Fate Laboratory Copies of Soil Methods ASHO10569 USEPA 9045 4 >25" C 0 0 1 /7 2 3M ENVIRONMENTAL LABORATORY PRELIMINARY PREPARATION OF SOIL SAMPLES FOR LABORATORY ANALYSIS 2.00 mm A ir-D ry Soil Air-dry (ambient room temperature) soil samples on flat trays for 24 to 48 hours or und thoroughly dry (constant weight). If desired, samples cart be oven-dried at 35C overnight (18 4 hours).* Pass air-dried soil (crushed and mixed via mortar and pestle) throu^t a 2.00 mm (10 mesh) stainless steel sieve. This removes large pieces of foreign material such as stones, gravel and twigs. Partition the sample by the 'quarter' system or by passing through a riffle sampler (sample spfetter). If desired, quarters can be further divided into smaller portions. The soil sample is now ready for laboratory analysis. Use the 2.00 mm air-dry sofl far sol reaction tests and for soluble salts analysis or store in a cool, dark room. This soil is also used for physical characteristic analysis. s o il rea ctio n TESTS pH Lime Requirement Gypsun Requirement SOLUBLE SALTS ANALYSIS Etecsical Conductivity C l'.S O A ftaW y PHSaCALCaABACIEBlSnCS Sol textereanddassiflcaiten 0.500 mm A ir-D ry Soil Obtain about 20 to 40 g of a representative portion of the 2.00 mm soil and grind in an agate mortar and pestle unt3 the entire sample passes through a 0.500 mm (35 mesh) sieve. Use this soil for exchange activity tests (Cation Exchange Capacity, Base Saturation. SAP. ESP) and (or nutrient analysis (N. P. S). 0.063 mm O ven-Dry Soil Obtain about 10 to 20 g of a representative portion of the 2.00 mm sol and finely grind in an agate ball mil unto the entire sample passes through a 0.063 mm (250 mesh) sieve. Oven-dry (105-110C) the above sample (placed in a tared aluminum weighing dteh) overnight and report the loss in weight Use this finely ground (bafl miled) oven-dry soil for total elemental analysis (1CP, AA). total fluoride and TOC analysis. S P E C IA L NOTE All dried soi samples are placed in impermeable, polypropylene bottles. They are stored in the soil cabinet (dark and at ambient room temperature) far one year after testing. Oisposal for a l sols and their extracts Sf by incineration. ASH010570 REFERENCES * Page. A. U Mller R. H. A Keeney D. a (Eds.) 1982. Methods ol Sol Analysis. Part 2. Chemical and Mforobiological Properties. Agronomy Monograph No. 9 (2nd Edition). Elk. K. and R. H. Gelderman.1988. Sol Sample Preparation, p. 2-4. In: Recommended Chemical Sol Test Procedures for the North Central Region. North Central Regional PubHeadon No. 221 (Revised). 'N O T E . if nitrate analyses are to be determined, the sol should be dried within twelve hours of samplng to prevent changes in the nitrate content. (Revised 12/94 RRR) . 17 4 U S 000173 USEPA 9046 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 tillage are dependent on the water content, however, the amount of plant available water in the soil is dependent 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 been expressed as the ratio of the mass of water present in the sample to the mass of the sample after it has been dried at 105 *C to a constant mass. Thus, the water content as usually used in soil studies is a dimensionless ratio of two masses or is expressed as a percentage resulting from multiplying the dimensionless rat by 100. a The laboratory procedure employed here is water content measurements by the gravimetric method. It involves weighing the wet sample, removing the water, and reweighing the sample to determine the amount of water removed. Water content is determined by dividing the 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 dy soil, then multiplied by 100. This is now the percentage of the water in the sample on a dry-mass or dry-weight basis. RANGE AND SENSITIVITY The range and sensitivity will depend on the time necessary to reach constant weight and the analytical balance used. IN T E R F E R E N C E S Factors that may influence the results include: Failure of temperature control The drying oven used must maintain a temperature in the range of 105 to 1 1 0 *C. 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 basis, can be grossly misleading. PRECISION ANO ACCURACY Accuracy and reproducibility of water content measurements, assuming that the weighing precision is consistent with the desired precision of the water content measurements, depend upon the drying technique and how used (whether 24 hours is adequate in obtaining a constant weight). ASH010571 1 18 4 U S ' .j USEPA 9047 CO 0174 EQUIPMENT AND REAGENTS 1). Analytical balance accurate to 0.001 g. 2). Oven-dried aluminum weighing dishes. ' 3). Drying oven with temperature control device that will maintain a temperature between 105-110 *C. Forced -air circulating ovens will dry samples more rapidly, but convection ovens are sufficient 4). Desiccators containing active desiccant 5) No reagents are required. WATER CONTENT PROCEDURE 1). Obtain at a minimum 10 to 40 g representative portion of either a ban milled (air-dried) sample or as received (wet) sample. 2). Place in oven-dried aluminum weighing dish. 3). Weigh the sample to the nearest 0.001 g as soon as possible. 4). Place the sample in the drying oven and dry it to a constant weight (at a minimum 24 hours). 5). Remove the sample from the oven and place it in a desiccator until cooled to ambient room temperature. 6). Reweigh the sample to the nearest 0.001 g. 7). Calculate the water content as percentage of water in the sample on a dry-mass basis: V. Water Content. IWeioht of Wet Soil Pan - Weight of Otv SoiUPanl X 100 Weight of Dry Soil .......v REFERENCES Gardner, W. 1986. Water Content p. 493-544. In: Arnold Wute (Ed.). Methods of Soil Analysis, Part 1. Physical and Mineraiogicai Methods. Agronomy Monograph No. 9 (2nd Edition). ASH010572 2 USEPA 9048 3M ENVIRONMENTAL LABORATORY SOIL pH METHOD PRINCIPLE OF THE SOIL pH METHOD Soil pH is ona of the most indicative measurements of the chemical properties of a soil. Whether a soil is acidic, neutral, or basic has much to do with the solubility of various compounds, the relative bonding of ions to exchange sites, and the activity of various microorganisms. Three soil pH ranges are particularly informative: a pH <4 indicates the presence of free acids generally from oxidation of sulfides; a pH <5.5 suggests the likely occurrence of exchangeable Al; and a pH from 7.8 to 8.2 indicates the presence of CaCOg. Soil pH is a measure of the activity of H+ in the soil solution. Ionized H is in equilibrium with the adsorbed nonionized H but usually is a small fraction of 1 Much of the nonionized acidity is exchangeable only at higher pH. Although other criteria are sometimes used as indices of Sms needs of acid soils, the 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. 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. IN T E R F E R E N C E S Factors that may influence the measured pH include: The nature and type of inorganic and organic constituents that contrtoute to soil acktity. ( Hydrogen ions may dissociate from the exchange sites or may be displaced by hydrolysis.) The soii/soiution ratio (1:1 is the most commonly used). 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 COg content (COg from the atmosphere or soil air) dissolves in water forming carbonic acid (HgCOg) which can lower the pH. In the actual measurement of soil pH, the soil and water are shaken so they come to equilibrium with the COg 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 free CaCOg . does the COg concentration of the air has any appreciable measurement effect on pH. Errors' associated with equipment standardization and liquid junction potential. The use of 0.01 M CaCtg 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 the H+ or Al3*. In addition, errors due to the liquid junction potential are decreased. PRECISION AND ACCURACY 9 Random variation of 0.1 to 0.2 pH units is allowable in replicate determinations and can be expected from one laboratory to another. Dehydrated and scratched electrodes wffl give erratic values. ASH0I0573 "I. l o o U S ' USEPA 9049 C O O IN G EQUIPMENT AND REAGENTS 1). pH meter equipped with a combination electrode ( or soil pH electrode, Cole-Parmer Model #5992-60) and automatic temperature compensation (ATC) probe. 2). Standard buffers, pH 7.0 and pH 4.0. 3) . 50 mL conical, polypropylene centrifuge tubes. 4) . Automatic pipets. 5) . Gyratory shaker. 6) . MilBpore M3li-QTM water. 7). Calcium chloride (CaClg) solution, 1 M or 0.01 M. pH w AND pHs PROCEDURES 1). Calibrate pH meter with commercially prepared buffer solutions of 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 tube. 3). With automatic pipet, add 10 mL of MilO-QTM water to each tube. 4). Mix thoroughly for 5 minutes, preferably on a gyratory shaker. (Option: mix for one hour.) . 5). Let stand for 10 minutes. (Option: let stand for one hour.) 6). Insert the electrodes into the container. Note; the test mature after settling will have an upper, relatively dear layer (supernatant layer) and a lower layer of opaque soil suspension. Immerse the electrode into this mature until the pH sensitive bulb is covered by the opaque soil suspension while leaving the reference contact in the supernatant layer. 7). Allow time for the electrode to reach equifibrium (-1 to 3 min.) and record as soil pH in water, pHw. 8). To determine the sol pH in 0.01 M CaC(2, add 0.10 mL of 1M C ad 2 solution to the soil water . suspension. 9). Mix intermittently for 30 minutes. (Option: mix 30 minutes, let stand 30 minutes.) 10). Insert electrodes, and record as soi pH in 0.01 M CaClg. pH*. Alternatively, the soil pH in 0.01 M CaClg may be determined directly by substituting 0.01 M CaClg for the water in step 2. 11) If the lime requirement is to be determined on the samples (pH < 8.9), save them for this purpose after reading the pH * or pH*. ................................... REFERENCES McLean, E. 0 . 1982. S oi pH and Lime Requirement p. 199-224. In: A L Page. R .H . Miller & O. R. Keeney (Eds.) Methods of S o i Andysis. Part 2. Chemical and Microbiological Properties, Agronomy Monograph No. 9 (2 nd Edition). Eckeit, D. J. 1988. Recommended pH and Lime Requirement Testa, p. 6 -8 . In: Recommended Chemical Soi Test Procedures for th North Central Region. North Central Ragionai Publication No. 221 (Revtaed). ASH010574 2 loi 4 ias~ C00177 USEPA 9050 3M ENVIRONMENTAL LABORATORY CATION EXCHANGE CAPACITY (CEC) BY SODIUM SATURATION BATCH EQUILIBRIUM METHOD P R IN C IP L E O F TH E C EC M ETHO D Soils possess an electrostatic charge as a result of the atomic substitution in the lattices of the soil minerals and as a result of hydrolysis reactions on broken edges of the lattices and surfaces of the oxides, hydroxides, hydrous oxides and organic matter. These charges attract exchangeable ions and form the exchange complex. The cation exchange capacity (CEC) is the measure of the quantity of cations reversibly adsorbed per unit weight of soil. It is expressed in milliequivalents per 100 grams of oven-dried soil. (An equivalent weight is that quantity that is chemically equal to one gram of hydrogen.) The principle of the method described here measures CEC by saturating the cation exchange sites in the soil with a specific cation, sodium; removal of the excess saturating solution (washing); and finally replacing the adsorbed cation, sodium with the ammonium ion (desorption) which is measured by an appropriate method (e.g. ICP). R A N G E A ND S E N S IT IV IT Y The range and sensitivity of the method are dependent on the complicating interactions between saturating, washing, and extracting solutions and the soil constituents. IN T E R F E R E N C E S Potential errors exist in each step of the CEC method use. The three steps are saturation of the cation exchange sites with a specific cation; the removal of the excess saturating solution; and replacement of the saturating cation. Possible factors of error influencing these steps are: Saturation Step. Exchange sites may not be completely saturated with the saturating cation due to other cations in the saturating solution competing for adsorption sites or may be due to the saturating cation's replacing power is insufficient to replace the more strongly adsorbed cations, such as exchangeable aluminum and its hydroxy forms. (Exchangeable aluminum and its hydroxy forms are not readily exchanged with monovalent cation saturating solutions.) This effect causes an underestimate of the CEC. Another problem associated with this step could be the presence of other cations in the saturating solution (dissolution of calcium carbonate, gypsum and silicate minerals). Washing Step. This step has the most potential sources of errors. The adsorbed cation may be removed by hydrolysis and replaced by a hydrogen ion. It may also be replaced by cations brought into - solution in the washing solvent from the dissolution of calcium carbonate, gypsum and silicates. Fine clay particles and organic matter may be lost during the decanting (these exchangers have a tendency to disperse as the excess electrolyte is removed during washing). Some of the saturating solution may ' be retained in the soil and later extracted as an exchangeable cation if the washing is incomplete or if the salt is retained. The majority of these errors cause the CEC to be underestimated. Replacement Step. Adsorbed cation could be trapped between interlayers by contraction of expandable 2:1 layer silicates (this is especially true in vermiculites and weathered micas) thus, preventing its replacement during extraction. The end result is an underestimate of the CEC. The second factor causing potential error is that nonexchangeable cations may be extracted from zeolites, feldspathoid, feldspar, and mafic minerals by the extracting solution. The error gives high CEC values. P R E C IS IO N A N D A C C U R A C Y Errors can be reduced by using a method of CEC determination that employs reagents of similar concentration and pH to those of the soil to be analyzed. 1 /PA. e$ USEPA 9051 000178 ASHO10575 EQUIPMENT AND REAGENTS 250 mL cortical, polypropylene centrifuge tubes. Automatic pipets. Gyratory shaker. Programmable centrifuge. 1.0 N, pH 8.2 NaOAc (Sodium acetate), identified as Reagent #1: For each liter of solution, dissolve 82.03 g of NaC2H3C>2in Milfi-QTM 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 acid {CH3COOH) or sodium hydroxide (NaOH) to bring the reaction of the solution to pH 8.2. 1.0 N, pH 7.0 NH4OAC (Ammonium acetate), identified as Reagent #2: For each liter of solution, add 58 mL of glacial acetic add (CH3COOH) to approximately 600 mL of Milli-QTM water and then add 70 mL of concentrated ammonium hydroxide (NH4OH, specific gravity 0.90). It is best to add the NH4OH 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 CH3COOH or NH4OH. Dilute the soiution to volume, mix it and store until ready for use. Recheck the pH prior to using the solution. Reagent grade, 2-propanol (99% isopropyl alcohol). P R O C E D U R E F O R C EC BY S O D IU M S A T U R A T IO N Weigh 5.000 g of a 0.500 mm air-dried soil sample and transfer the sample to a 250 mL oonical, polypropylene centrifuge tube. Add 132 mL of 1.0 N. pH 8.2 NaOAC 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. Remove the sample from the shaker and place it in the centrifuge. Centrifuge 10 minutes at 3000 rpm. This recommended time and speed wilt be sufficient; a dear supernatant will be obtained. Decant the supernatant and discard the liquid. NOTE: Careful decanting is very important. Particles of soil tost during the decanting steps will effect the final CEC result; a lower CEC value is the end result of this which leads to a false interpretation: poor soil quality. 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 for 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) Add 100 mL of 1.0 N, pH 7.0 NH4OAC (Reagent #2) to the sample, stopper the 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. 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. Determine the sodium (Na) content by available methods, e.g. ICP. 2 USEPA 9052 ASHO10576 C A L C U L A T IO N CEC EQUATION: Q-1Nacom/g3_____ x 100 - meq/IOOg sol oven-dried weight of sol (g)* * % soil moisture was previously determined. REFERENCES Chapman, H. 0.1965. Cation Exchange Capacity, p. 891-900. In: C. A Black (Ed.) Methods of Sol Analysis, Part 2. Chemical and Microbiological Properties, Agronomy Monograph No. 9 (1st Edition). Rhoades, J. 0.1982. Cation Exchange Capacity, p. 149-'57. In: A L Page, R. H. Miller & D. R. Keeney (Eds.) Methods of Sol Analysis, Part 2. Chemical and Microbiological Properties. Agronomy Monograph No. 9 (2nd Edition). , Brown, J. R. and D. Wamcke. 1988. Recommended Cation Tests and Measures of Cation Exchange Capacity, p. 15-16. In: Recommended Chemical Soil Test Procedures for the North Central Region. North Central Regional Publication No. 221 (Revised). ASH010577 3 M 4 WF USEPA 9053 c o o is o 3M Environmental Laboratory Copies of Chain of Custody, Shipping Papers, Lab Requests ASH0I0578 /5 " M S- U SEPA 905O O Sl lmAm lmSHIPPING HEMORANDUMOm (FOR NO-CHARGE SHIPMENTS ONLY) S h i p Co 4tn 3M E n v i r o n m e n t a l T e c h n o l o g y & |D a te 4m S e r v i c e L a b o r a t o r y , B - 2 - 3 E - 0 9 |R o u tin g 4m 9 3 5 B u sh A v e n u e 4m S t . P a u l , M in n e s o ta 5 5 1 4 4 -1 0 0 0 |F .O .B . | D ate |S h ip p e d 4m A t t n : R o b e r t H o w e ll |B /L I 4m Q u a n t i t y P ro d u ct Code / D e sc rip tio n 4m I C o n ta in e r o f W ater Sam ples 4m I 4m I 4m I 4m I 4m I 4m I 4m 0 5 /0 8 /9 7 No. 38-972 W eight 48 lb s 4ra " | I 4m | S p e c i a l I n s t 4 m A b s o lu te ly m u s t a r r i v e F r id a y AM/Time r e s t r a i n t s . F r e i g h t C l a s s 4m 4m 4m 4 m 0 r i g i n a t o r VERA L WIGAL Phone 304-863-4895 4m Charge (C o st Code) 8309019511001280 I |MSDS S h e e t s R e q u i r e d ? 4m Purchase O rder No. I {H azardous M a te ria l? N 4m V alue f o r C ustom s I | MATERIAL CLASSIFICATION S h ip From A m S tores, B ld g . 4 4m 4m 4m | I |C o rro s iv e '_ . | Flam m able * * AUTHORIZATION * * T oxic O ther 0m | 0m I 4m | | 0m I 4m | | 0m I 4m | | 0m > oo X on -V4O l o b <6 U S ' C001S2 USEPA 9055 Purcltaaa Order # 1_11_1l_11--11--11--11--11--1 Project Name u f a f i S i LaJ6% H ia )& Tc' P LaJ O K & S fa / n- Pro)act Manager APhono Report Copy to: K .|i ( Z . -7 -1 r f C i - fL , F f r - Requeetad Completion Data: Sampling Requirement* A6Af#r~C n# sown Npocs nena m w _ k l_ Sampta Diepoeal: Olajjoy* Rahmt Sampling typ* Matita CLIENT SAMPLE (9 CHARACTERS) ffr/' lO U '0 * -' ASMO 10580 1 * .AflV%... / '! , A -. ;r,rr . v* ANALYSES REQUESTED USEPA 9056 SHADED AREA-FOR I U8C ONLY Quota# Pro)act # KHRoqueat # .( No#of Sowoflto - i . . COCRav" L. :.s.rJ*iJ REMARKS P A V L J t'C r e r u 3^ yG STjcsrx/S ot b<yi KX. UMBYta k - I .'WJw* -E i - A o' Ju/i *_> 55? J x b c Sampled ByATitle /? 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P a u l , M i n n e s o t a 5 5 1 4 4 -1 0 0 0 |F .O .B . | D ate |S h ip p e d I 4m A t t n : R o b e r t H o w e ll IB /L I 4m Q u a n t i t y | P ro d u ct Code / D e s c rip tio n 0 6 /2 6 /9 7 Om No. 38-9737950m Om Om Om . I W eight Om 0m 4m 7 | C o o lers c o n ta in in g w ater sa m p le s/v a te r & ic e I 40 each 0m 4m I I 4m I 4m I 4m I 4m I 4m *? Om 0m 0m 0m Om Om 4m I 4m 1 4m Om Om Om S p e c ia l I n s t 4mNeed 7 la b e ls , O v e rn ig h t A ir, D e liv e r 6 /2 7 b e f o re noon Om F r e i g h t C l a s s 4m Om 4m Om 4m 4 m 0 r i g i n a t o r VERA L WIGAL Phone 304-863-4895 4m Charge (C o st C ode) 8309066742001280 |HSDS S h e e t s R e q u i r e d ? 4m Purchase O rd er No. (H azardous M a te ria l? N 4m V alue f o r C ustom s S h ip From 4 m S to res, B ldg. 4 4m 4m 4m| I 4m | I 4m | I 4m | | MATERIAL CLASSIFICATION |C o rro siv e T oxic |F lam m able * * AUTHORIZATION * * O th er 0m ( 0m | 0m | 0m | 0m Om Om Om Om Om Om Om ASHO10584 111 jj C 'X I S V USEPA 9060 USEPA 9061 0 O O 1 S 8 Z906 vdasn CH2M HILL Anafytlcaf Servicas Montgomary, AL 36)16-1022 (334)271-1444 FAX (334) 271-3429 LRD 5000 Calarpflar Rond Raddfctg, CA 06003-1412 (916) 244-5227 FAX(918)244-4109 jP rojadf Purehaaa Ordar # e1mfju.,,p1,n,J i1n1m^ 4v tataftoo. nliio, Canada N2V 2CS (519)747-2575 FAX (519) 747-3606 CVO2300NWWWnutBoidavwd Cavalla, O aom 973303636 (541)752-4271 FAX (514) 752-0276 eoe _ Raquaatad Analytical Uathod # THISAREAFOfl LABUSE ONLY Lab* Paga oV CD CO or. T 'i c> e P o f d r f T lA J m iiV L T t* ' U j ^ S ICompany Nama _______ o P ^ r ___________ Raport Copy lo: 1 A ja Pp l J tm T T C n ) I ComptottoftOMi! 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Oj fb /* T { M frti/T S J Company Name fo fo J T drfbO^^S|M^^A^Mnl^^OeTas(eMSaCI IAn lw l2ft Report Copy to: to J n fo M H tir r & l- Requested ComptattonOsta; Stia ID Sampling Type Matto Date Urna m. x>< Ml Sample Otapoasl: B een IMum jr CLIENTSAMPLED ( CHARACTERS) LAB QC <S> e*' \ o zz USOLBAaWthuUrestm, UirontA1n2a,lyWticsaleltltoaon, nnM , Ontario, iik. Canada N2V 2CS (SIB) 747-2575 FAX (518) 747-3606 O CVO2300 NWWMnut Botdevaid Conrads, Oregon 87330-3536 (541) 752-4271 FAX (614) 752-0276 coca TP M -A cv Raquselad Analytical Method a TMSAREAFOR LABUSE ONLY Lab# Page of o c mvoo Ov < Lab PM Custody Review Ph w CO ft P Pieearvatlve (1 $ PH Custody Seale Y N loo QC Level 1 2 3 Other YN Cooler Temperature Alternate Deeertptlon I ID ASH010589 SpaetatlnalnMltom: !>a ten --a taaBtaOoneandAgreementr wvtalonsonWavareaSMa Rsttogalshad thk fu Z B - c ^ 4 netoIsMbuprMiahiMed BHiya flSIBStipifl#fMRM| Dilafflfm . t DsWTIme Shipped Via UPS Fad-Ea Other. 9in|i|ii-n--pMf 4A _ asmaunON: Origlimi-LAB, Yttom-UkB, PWtr-CflerV USEPA 9066 C H 2M H IU . Analytlcal Services U wm<a cu u r m m v uiivv Montgomery, AL36110-1622 (334)271-1444 FAX(334) 271-3428 LRO5000CaterpMar Roed fledA n, CA96003-1412 (916) 244-6227 FAX(916) 244-4109 Pm ftl* Purch#Order f I1rfwfVOKIW nf I O i / f p s ' Y k J ft< \ff^ r A ) f CofUfMfiyNmm ___D u f / s r _____ b a tte Deport Copy te: 1AMtev mcn&J 10k|umM CMRpMtonPiff; Stelo ItN.-mn iptLiwi p Type Manti Date Time -SampleOtapoeel: Mapese Mvm Q" CLIENTSAMPLE 10 (9 CHARACTERS) LAS OC OD I V JJSH a u i, n n li in u m in in H u u u r n i n , in c , 60 Beihuraf, UM 12. MUMertoo,Orearlo, Canada N2V2C5 (519) 747-2675 FAX (519) 747-3606 CVO 2300 NWMMnul BtxAevaid Corvatta, Oregon 97330-3636 (541)762-4271 FAX (614) 762-0276 C0C9_ Requaated Analytleal Mettod f IMS AREAFOR LABUSE0NLY Lab Page of V7 l V ** & 4 <c H I< t U. * "> K * 2^ LabPM Cuatody Review pH Cuatody Seele Y N lee OC Laval 1 2 3 Ortrer Cooler Temperature A lternate Description YN Labio ASHO10590 oe ByaTW ym et /3 to k = se I SpecialInetnMtMa: fW*f>epMnM MebwMbneand Adreormrrt P m k h m on Davor* SM <> IWIH^mnNBy SMppedVta UPS FedEx 0r\fM>i--mmIiSjpiMrfpWH--I Oilrar. Datafftaie . 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