EPA/600/R-10/159 | December 2010 | www.epa.gov/ord United States Environmental Protection Agency Decontamination of Residual VX on Indoor Surfaces using Liquid Commercial Cleaners INVESTIGATION REPORT Office of Research and Development National Homeland Security Research Center ------- ------- Decontamination of Residual VX on Indoor Surfaces using Liquid Commercial Cleaners INVESTIGATION REPORT Office of Research and Development National Homeland Security Research Center ------- ------- Foreword Following the events of September 11, 2001, EPA's mission was expanded to address critical needs related to homeland security. Presidential Directives identify EPA as the primary federal agency responsible for the country's water supplies and for decontamination following a chemical, biological, and/or radiological (CBR) attack. As part of this expanded mission, the National Homeland Security Research Center (NHSRC) was established to conduct research and deliver products that improve the capability of the Agency to carry out its homeland security responsibilities. One specific focus area of our research is on decontamination methods and technologies that can be used in the recovery efforts resulting from a CBR contamination event. In recovering from an event and decontaminating the area, it is critical to identify and implement appropriate decontamination technologies. The selection and optimal operation of an appropriate technology depends on many factors including the type of contaminant and associated building materials, temperature, relative humidity, fumigant concentration, fumigation time, and others. This document provides information on how two commercially available technologies performed in treatment of VX deposited on interior industrial building materials at various operational conditions. These results, coupled with additional information in separate NHSRC publications (available at www.epa.gov/nhsrc), can be used to determine whether a particular decontamination technology can be effective in a given scenario. With these factors in consideration, the best technology or combination of technologies can be chosen that meets the clean up, cost and time goals for a particular decontamination scenario. NHSRC has made this publication available to assist the response community to prepare for and recover from disasters involving chemical contamination. This research is intended to move EPA one-step closer to achieving its homeland security goals and its overall mission of protecting human health and the environment while providing sustainable solutions to our environmental problems. Jonathan Herrmann, Director National Homeland Security Research Center ------- ------- Disclaimer The U.S. Environmental Protection Agency, through its Office of Research and Development, funded and managed this investigation through a blanket purchase agreement under U.S. General Services Administration contract number GS23F0011L-3 with Battelle. This document has been subjected to the Agency's review and has been approved for publication. Note that approval does not signify that the contents necessarily reflect the views of the Agency. Mention of trade names or commercial products in this document or in the methods referenced in this document does not constitute endorsement or recommendation for use. Questions concerning this document or its application should be addressed to: Sang Don Lee National Homeland Security Research Center Office of Research and Development (NG16) U.S. Environmental Protection Agency Mail Code E343-06 Research Triangle Park, NC 27711 (919)541-4531 lee. sangdon@epa.gov or Lukas Oudejans National Homeland Security Research Center Office of Research and Development (NG16) U.S. Environmental Protection Agency Mail Code E343-06 Research Triangle Park, NC 27711 (919) 541-2973 oudejans.lukas@epa.gov If you have difficulty accessing these PDF documents, please contact Nickel.Kathy@epa.gov or McCall.Amelia@epa.gov for assistance. ------- Acknowledgements The US EPA's National Homeland Security Research Center (NHSRC) would like to acknowledge the following organizations and individuals for their support in the development of this report, whether in contributing to the research or providing a peer review. U.S. Environmental Protection Agency Jeanelle Martinez Lawrence Kaelin Emily Gibb Snyder Battelle Memorial Institute ------- Contents Disclaimer. Acknowledgements vi List of Tables ix List of Figures xi Acronyms and Abbreviations xiii Executive Summary xv 1.0 Introduction 1 1.1 Objective 1 1.2 Approach 1 1.3 Experimental Design 1 1.3.1 Definition of Coupon Types 2 1.4 Final Test Matrix 2 2.0 Methods 5 2.1 VX Spiking 5 2.2 Decontamination 5 2.3 Coupon Extraction Method 5 2.3.1 Extraction Method Demonstration 5 2.3.2 Extraction Method Demonstration Results 7 2.4 Analytical Methods 8 2.5 VX and TBP Analysis 9 2.6 Calculation of VX Recovery and Percent Recovery 10 2.7 Calculation of Decontamination Efficacy 10 ------- 3.0 Quality Assurance / Quality Control 11 3.1 Performance Evaluation Audit 11 3.2 Technical Systems Audit 11 3.3 Data Quality Audit 11 3.4 Process Evaluation/TBP Extraction Results 11 3.5 Test Coupons 12 3.6 Blank Samples 13 3.7 Deviations 13 4.0 Results 15 4.1 Application of VX to Test Coupons 15 4.2 Environmental Conditions during Tests 15 4.3 Test Observations 15 4.4 Recovery of VX from Aged Test Coupons with and without Decontamination 16 4.4.1 One Day Aging and Decontamination 18 4.4.2 Seven Day Aging and Decontamination 18 4.4.3 Fourteen Day Aging and Decontamination 18 4.4.4 Twenty-One Day Aging and Decontamination 19 4.5 Decontamination Efficacy 19 5.0 Summary 21 6.0 Reference 23 Appendix A 25 ------- List of Tables Table E-1. Summary of decontamination efficacy for aged VX on building materials xv Table 1-1. Building materials used in decontamination investigation 2 Table 1-2. Summary of the test parameters for decontamination of aged VX on building materials 2 Table 1-3. Coupon treatments 2 Table 1-4. Test matrix for aged VX decontamination 3 Table 2-1. Liquid decontaminant volumes applied to test coupons 5 Table 2-2. Number of samples for sonication extraction method demonstration 6 Table 2-3. Day 7 serial extraction results 7 Table 2-4. Day 21 serial extraction results 8 Table 2-5. Analytical Measurement Parameters for Residual VX Decontamination 9 Table 2-6. GC/MS conditions for VX/TBP analysis 9 Table 3-1. PE Audit Results 11 Table 3-2. TBP recovery for aged VX decontamination trials 12 Table 3-3. Analysis results of procedural and laboratory blanks 14 Table 4-1. Results of VX spike control samples 15 Table 4-2. Average VXmass recovery (ug) from test coupons 17 Table 4-3. VX Recovery (%) from positive controls during aging period trials 17 Table 4-4. VX recovery on decontaminated test coupons after aging periods 17 Table 4-5. VX decontamination efficacy for bleach and ZEP® on aged test coupons 19 ------- Table 5-1. VX recovery efficiency for contaminated and decontaminated building materials after aging 21 Table 5-2. Decontamination efficacy of aged VX on building materials 22 ------- List of Figures Figure 2-1. Photographs of coupon spiking (left) and storage for aging studies (right) 6 Figure 2-2. Photographs of coupon transfer (left) and sonic bath extraction (right) after aging 7 Figure 3-1. Graph depicting the enhanced recovery of analytical check standards due to carpet extracts 12 Figure 3-2. Graph depicting the calibration check recovery after conditioning the instrument with carpet extracts 13 Figure 4-2. Representative photographs of VX droplets on metal coupons 16 Figure 4-3. Representative photographs of the KFS application to test coupons (left to right): metal, laminate, and carpet 16 Figure 4-4. Representative photographs of ZEP® application to test coupons (left to right): metal, laminate, and carpet 16 Figure 4-5. Average VX recovery (ug) from 1 day aging and decontamination of positive controls (POS) and test coupons of metal, laminate, and carpet 18 Figure 4-6. Average VX recovery (ug) from 7 day aging and decontamination of positive controls (POS) and test coupons of metal, laminate, and carpet 18 Figure 4-7. Average VX recovery (ug) from 14 day aging and decontamination of positive controls (POS) and test coupons of metal, laminate, and carpet 18 Figure 4-8. Average VX recovery (ug) from 21 day aging and decontamination of positive controls (POS) and test coupons of metal, laminate, and carpet 19 ------- ------- Abbreviations/Acronyms C Celsius CCV continuing calibration verification CWA chemical warfare agent cm centimeter DCMD Decontamination and Consequence Management Division EPA U.S. Environmental Protection Agency GC/MS gas chromatography/mass spectrometry HMRC Hazardous Materials Research Center IS internal standard ISO International Organization for Standardization KFS K-O-K® Bleach, Full Strength (5.25 % sodium hypochlorite in water) L length MDL method detection limit mg milligram mL milliliter MS mass spectrometry ND not determined NHSRC National Homeland Security Research Center NIST National Institute of Standards and Technology PE performance evaluation QA quality assurance QC quality control QMP quality management plan RDECOM U.S. Army Research, Development & Engineering Command SD standard deviation TBP tributyl phosphate TOPO Task Order Project Officer TSA technical systems audit ug microgram uL microliter W width ------- ------- Executive Summary In order to evaluate the potential decontamination of residual chemical agent-exposed building materials, samples of material coupons (galvanized metal, laminate, and industrial carpet) were treated with VX and allowed to age for periods ranging from 1 day to 21 days. After aging, coupon samples were treated for 30 minutes with either of two liquid decontaminants: full strength K-O-K® liquid bleach (5.25 % aqueous solution of NaOCl) or a 25 % aqueous solution of ZEP® Industrial Purple liquid cleaner (proprietary caustic cleaner containing surfactants). After decontamination the coupons were extracted using a serial sonication method, and the extracts analyzed by GC/MS to determine the residual VX remaining after decontamination. Decontamination efficacy was determined by measuring the amount of residual VX on test coupons and comparing with positive controls (spiked with chemical agent, not decontaminated and analyzed after aged for the same period as the decontamination coupons). Results of the testing are shown in Table E-l. Table E-l. Summary of Decontamination Efficacy for Residual VX on Building Materials Material Metal Laminate Carpet Aging Period (Day) 1 7 14 21 1 7 14 21 1 7 14 21 VX Recovery, Without Decontamination 66 ±16 0.7±0.1 0.8" <0.5 74 ±20 3±3 2 ±0.5 0.9 ±0.1 99 ± 12 20 ±3 8± 1 2± 1 Decontamination Efficacy, % ± SD (n=5) K-O-K8 Full Strength Liquid Bleach >99' >29' >38' NDC 97" >86' >72' >44' 84 ± 11 96" >93' >80' ZEP8 Industrial Purple (25% in water) % ± SD (n=5) 38 ± 15 0±24 29" NDC 40 ± 17 1±35 4±21 9±8 16 ± 13 18 ± 17 10 ±7 14 ±26 " Lower limit value; recovered VX amount in treated sample is below method quantification limit due to the combined effect of aging and decontamination procedure b Only one sample out of five yielded a measurable result (n = 1) 0 Non-determinant because both the positive control and the treated sample amounts were below detection limit. Using ZEP® Industrial Purple resulted in moderate decontamination of VX ranging from 16 % for carpet to approximately 40 % for metal and laminate coupons for 1 day aged samples. For subsequently aged materials, there was no improvement in decontamination efficacy, as shown in Table E-1. This lack of improvement was particularly evident in the carpet samples, where no difference in the decontamination efficacy was apparent for four sample aging periods. Decontamination efficacy for K-O-K® full strength liquid bleach is high on all samples. For decontamination efficacy listed as greater than (">") a value, no residual VX was detected on the coupons. The inability to measure the remaining VX amount after decontamination prevents the exact determination of the efficacy values. The test results suggest that K-O-K® full-strength liquid bleach is a better decontaminant for VX than ZEP® Industrial Purple, regardless of the aging period and substrate type. The effect of aging on decontamination efficacy is compounded by the significant loss of VX over time. The test materials showed different VX losses over time with a lower rate for carpet compared to metal and laminate. VX losses are presumed to occur through evaporation and/or degradation, such as hydrolysis or photo-degradation. A comprehensive analysis of degradation products was beyond the scope of this effort. Based on the test conditions and the physical properties of VX, photo-degradation was not expected to be a significant mechanism of VX loss. Recoveries from applied extraction procedures were found to be ------- dependent on the building material type. Repetition of the same extraction procedures were required to achieve complete extraction of VX from the carpet surface. Single extraction was required for metal and laminate surfaces. ------- 1.0 Introduction The EPA's National Homeland Security Research Center (NHSRC) is helping to protect human health and the environment from adverse impacts resulting from intentional acts of terror. With an emphasis on decontamination and consequence management, water infrastructure protection, and threat and consequence assessment, NHSRC is working to develop tools and information that will help detect the intentional introduction of chemical, biological, or radiological contaminants in buildings or water systems; contain these contaminants; decontaminate buildings and/or water systems; and facilitate the disposal of material resulting from cleanups. 1.1 Objective The imminent threat of a chemical agent release in a building or transportation hub is driving the EPA's NHSRC to develop a research program that systematically evaluates potential decontaminants of chemical agents. The EPA may be tasked to provide technical support for the clean up chemical agents after they are released and it is unclear how effective many currently available commercial technologies are against chemical agents. In addition, the optimal decontaminant concentrations and contact times may not be known or data may be inadequate, particularly for persistent agents such as VX or in situations where persistent agents have been present for extended periods of time. Under a Battelle task order contract, the EPA continued its systematic decontamination research program by evaluating decontamination strategies for environmentally persistent chemical agents. Previous technology investigations have been conducted using relatively short surface-aging times (minutes to hours) for chemical agents. The efficacy of decontaminants is unknown for the environmentally persistent and reactive chemical agent, VX, when it is aged for several days or weeks on surfaces. This testing was conducted to evaluate the effect of chemical agent (VX) surface aging on decontamination efficiency using two commercially available liquid decontamination technologies. Appropriate liquid decontamination technologies for VX on building materials were chosen based on short term exposure studies performed in other EPA chemical warfare agent research effort(1) and the two most efficacious decontaminants from that study were selected for this test. The efficacies of these decontaminants in the present effort were determined as a function of VX surface aging time. In addition, the effects of aging on decontaminant efficacy were determined for various interior building material surfaces (galvanized metal ductwork, surface laminate, and industrial-grade carpet). These three types of materials provided different surface porosity that could impact retention of VX and affect decontamination efficacy. 1.2 Approach The general approach developed and used for decontamination testing was to apply a known amount of VX to each of several test coupons of the same building material (replicate coupons, identical in size and shape) and allow these spiked test coupons to age for specified time periods under ambient laboratory conditions. After the desired aging periods (1,7, 14, and 21 days) samples were decontaminated with commercially available liquid decontaminants: either full-strength K-O-K® bleach (5.25% aqueous solution of NaOCl) (KFS) or 25 % solution of ZEP® Industrial Purple (proprietary caustic cleaner (pH~14) containing surfactants) (ZEP®) in water for 30 minutes. After this decontamination period, replicate test coupons were extracted using a sequential sonication method and the extracts were analyzed to determine the amount of VX remaining on the test coupon after aging and decontamination. The specific procedures for testing are described in Section 2.0. 1.3 Experimental Design This investigation focused on the effect of aging on VX decontamination of building materials. Table 1-1 specifies the building materials used in this investigation, which included galvanized metal ductwork, decorative laminate, and industrial grade carpet. Building materials were cut into test coupons of small, defined size (3.5 x 1.5 cm), consistent with other EPA testing efforts(3). Target challenge density was specified by EPA for indoor scenarios to be 1 g/m2. With a coupon area of approximately 5 cm2, VX was applied to the surface as a 1 uL drop, resulting in an actual challenge density of approximately 2 g/m2. ------- Table 1-1. Building Materials Used in Decontamination Investigation Material Description Manufacturer/ Supplier Name/Location Coupon Surface Material Size L x W (cm) Preparation Galvanized metal ductwork Decorative laminate Industrial-grade carpet Industry HVAC std; 24 gauge galvanized steel; thickness 0.7 mm Pionite* laminate/white matte finish; grade 10; nominal thickness 1.2 mm Shaw Industries, Inc. Style #M7832 color #00400; thickness -0.7 cm Adept Products, Inc./West „ _ T cc ™T 3'5 X I-5 Jefferson, OH A'Jack Inc./Columbus, OH 3.5 x 1.5 Carpet Corporation of America/Rome, GA Clean with acetone None None All decontamination testing was carried out at Battelle's certified chemical surety facility (Hazardous Materials Research Center [HMRC]) near West Jefferson, Ohio. In this investigation, the liquid decontamination tests were performed simultaneously for a given VX aging time. Liquid decontaminants were pipetted onto the coupon surfaces to simulate the volume applied from a spray application®. Table 1-2 presents a summary of the building materials, VX aging times, and liquid decontamination technologies used in this investigation. The liquid decontamination technologies were selected based upon screening test results in concurrent investigations of commercially available liquid decontamination products®. Table 1-2. Summary of the Test Parameters for Decontamination of Residual VX on Building Materials Material VX Aging Times (days) Liquid Decontamination Technologies KFS ZEP8 Galvanized Metal Ductwork Decorative Laminate Industrial Grade Carpet 1,7,14, and 21 Full strength K-O-K® liquid bleach 25 % ZEP* industrial cleaner in water 1.3.1 Definition of Coupon Types The types of test and control coupons used in this investigation are described in Table 1-3. Test coupons and positive control coupons were spiked with VX. Laboratory and procedural blanks were not spiked with VX. The test and procedural blank coupons were subjected to the decontamination treatment. Positive control coupons and laboratory blanks were not exposed to the decontamination treatment. Three spike controls, comprised of VX spiked on Teflon® coupons, were evaluated in conjunction with each aging duration test. Table 1-3. Coupon Treatments Coupon Test Positive Control Laboratory Blank Procedural Blank Spike Control Spiked yes yes no no yes Treatment Aged Decontaminated yes yes yes yes no yes no no yes no 1.4 Final Test Matrix Based on the experimental design discussed in Section 1.3 and the requirement to compare two liquid decontaminants, the test matrix was designed as shown in Table 1-4. Each exposure trial per coupon type consisted of two laboratory blanks, two procedural blanks, 10 test coupons, and 10 positive controls, for a total trial burden comprised of 72 test coupons per trial. Each aging period trial evaluated two liquid decontamination technologies. ------- Table 1-4. Test Matrix for Residual VX Decontamination Material Galvanized Metal Ductwork Decorative Laminate Industrial Grade Carpet Sample Type Laboratory blanks Procedural blanks Test coupons Positive controls Laboratory blanks Procedural blanks Test coupons Positive controls Laboratory blanks Procedural blanks Test coupons Positive controls Subtotal Total Number of Samples Coupon Aging Period (Days) 1 7 14 21 VX Decontaminant with Number of Samples N" KFS ZEP8 2 1 1 5 5 10 2 1 1 5 5 10 2 1 1 5 5 10 36 18 18 72 N KFS ZEP8 2 1 1 5 5 10 2 1 1 5 5 10 2 1 1 5 5 10 36 18 18 72 N KFS ZEP8 2 1 1 5 5 10 2 1 1 5 5 10 2 1 1 5 5 10 36 18 18 72 N KFS ZEP8 2 1 1 5 5 10 2 1 1 5 5 10 5 5 2 1 1 5 5 10 36 18 18 72 " Samples (N) that are not decontaminated. ------- ------- 2.0 Methods 2.1 VX Spiking Liquid VX (#900-80-1, 98.0% purity, (Edgewood Chemical Biological Center) was applied to coupons using a Hamilton repeating dispenser (50 uL total volume) (PB-600, Hamilton Co. USA, Reno, NV) equipped with a 21 gauge blunt-tipped needle. In this configuration(4), the syringe is capable of delivering a 1 uL drop. During each aging period spiking operation, three spike controls were generated to ensure reproducibility for the droplet delivery. Spike controls were comprised of three (3) one microliter drops of VX on each of three Teflon® coupons. The samples were not aged, but were immediately placed in 20 mL of chloroform containing IS and extracted via sonication for gas chromatography/mass spectrometry (GC/MS) analysis. 2.2 Decontamination Two liquid decontaminants were chosen for this investigation to evaluate two commercially available liquid decontaminants (see Section 1.3). After screening samples contaminated with VX to determine decontamination efficacy, application volumes were chosen based on the approximate liquid mass shown to cover the coupon surface using a pressure sprayer. The liquid decontaminant volumes are shown in Table 2-1. During testing, liquid decontaminants were applied to the surface using a Gilson Microman M250 (Gilson Inc., Middleton, WI) positive displacement pipette. Table 2-1. Liquid Decontaminant Volumes Applied to Test Coupons Liquid Decontaminant Amount QiL) The liquid decontaminants were allowed to sit on the surfaces of the coupons for 30 minutes prior to initiating the extraction procedure. 2.3 Coupon Sample Extraction Method After the aging and decontamination period, coupon samples were extracted using an Ultrasonik 57X sonic water bath (Ney Dental Inc., Yucaipa, CA). A serial extraction method was used to determine the potential for adsorbed VX to remain within porous materials after aging. The serial extraction method involved three repeated extraction cycles of the same coupon for a period of 10 minutes each, moving the coupon to a clean container with a fresh aliquot of solvent for each 10 minute cycle. A demonstration of this method is discussed below. 2.3.7 Extraction Method Demonstration An extraction method demonstration was conducted to establish sufficient extraction efficiencies (recoveries) for material and VX combinations at 7-day and 21-day aging periods. Test material coupons (galvanized metal ductwork, decorative laminate, and industrial-grade carpet) of a defined size (3.5 cm x 1.5 cm) were prepared for this demonstration. Table 2-2 shows the samples and numbers of sequence replicates for the extraction. The matrix is comprised of nine test samples for each aging period. In addition, three spike control samples were spiked with VX and extracted immediately as described in Section 2.1. Material Metal Laminate Carpet KFS/ZEP® 60 60 120 ------- Table 2-2. Number of Samples for Sonication Extraction Method Demonstration Material Sonication @ 50 kHz Metal Laminate Carpet 1" (10 min)" 3 -^b 3 -» 3 -» 7-Day Aging Period (10 min) 3 -» 3 -» 3 -» 3rd (10 min) 3 3 3 1" (10 min)" 3 -* 3 -» 3 -» 21-Day Aging Period (10 min) 3 -» 3 -» 3 -» 3rd (10 min) 3 3 3 " Recommended duration of Sonication was determined in a concurrent evaluation of commercial liquid decontaminants b The arrow signifies that the same three (3) samples were carried through the extraction procedure to the succeeding extraction. The coupons were spiked with a 1 uL drop of neat VX (# 900-78-1, purity = 94.8 %, (Edgewood Chemical Biological Center), to provide a surface concentration of approximately 2 g/m2. This surface concentration was chosen based on the EPA definition of an indoor contamination scenario and was consistent with other investigations of this type(1'2). The amount of spiked VX was confirmed where VX was spiked onto Teflon® coupons and immediately extracted with chloroform and analyzed. Battelle's HMRC routinely performs spike controls in this manner during agent operations to ensure that the spike application process is consistent and the agent recovery is within analytical targets (± 25%). For this particular spiking operation, a resulting VX mass concentration of 842 ug was measured, relative to a theoretical 948 ug applied (1 uL of 94.8% purity VX). Typical sample spikes were made and samples placed as shown in Figure 2-1 by spiking with a Hamilton repeating dispenser (PB-600, Hamilton Co. USA, Reno, NV) in the center of the coupon, then covering the samples with a clear plastic cover. The cover did not contact the sample, but enclosed the samples, protecting them from cross-contamination and significant air currents in the hood flow. The 7-day samples were placed on the right of the tray and 21-day samples were placed on the left of the tray. Figure 2-1. Photographs of coupon spiking (left) and storage for aging studies (right). At the conclusion of each aging period, the samples were extracted with 10 mL hexane containing the internal standard (IS, see section 2.4) as shown in Figure 2-2. The coupons were placed in 2 oz. glass jars (VWR/ OI, Perrysburg, OH). The samples were subjected to ultrasonic vibration (Ultrasonik 57X, Ney Dental Inc., Yucaipa, CA) at 50 kHz for 10 minutes. ------- Figure 2-2. Photographs of coupon transfer (left) and sonic bath extraction (right) after aging. After completion of the initial extraction, a 1 mL aliquot of extract was transferred to a 1.5 mL GC vial (Agilent/ Restek, Bellfonte, PA) and sealed. The coupons were individually rinsed with 5 mL of hexane and transferred to a new jar (VWR/OI, Perrysburg, OH) containing fresh hexane/IS and again subjected to ultrasonic vibration at 50 kHz for 10 minutes. At the conclusion of this period, a 1 mL aliquot was transferred to a GC vial and the coupon sample rinsed and transferred a third time, and the procedure repeated. The extracts were analyzed by GC/MS. Three replicates of each test material were prepared, aged, extracted, and analyzed. Liquid decontaminants were not used in this method demonstration. The extraction efficiency was determined as a percent of the agent recovered from the spiked coupon relative to the amount spiked. For the serial extractions, the total extracted VX equals Ml + M2 + M3, where Mn is the amount of VX extracted at the given step (n) in the sequence. Based on the results of the method demonstration, the criteria for following sequential extraction steps in the testing procedure were as follows: Table 2-3. Day-7 Serial Extraction Results • If the second extraction is >10% of first extraction, then perform a third extraction. • If during method demonstration, it is shown that the third extraction is <10% of second extraction (< 1% of first extraction), then only two extractions will be performed in testing. • Further, if the second sequence step extraction results are < 10% of the first extraction, only one extraction step will be performed during testing. 2.3.2 Extraction Method Demonstration Results The coupon extraction method demonstration results are given in Table 2-3 (Day 7) and Table 2-4 (Day 21). Since there are only three coupons in each sample set, variability is observed in the samples. As previously noted, the coupons were spiked with a 1 uL drop of neat VX, for an approximate surface concentration of 2 g/m2. The analysis of the spike control samples gave a resulting mass recovery of 842 ug VX per uL droplet. Material 1" Recovered VX (jig/coupon) after Extraction 2"11 3rd Total Total VX Recovery" (%) after Extraction Average Total VX Recovery (% ± SD) Metal Laminate Carpet 23.3 81.9 80.3 39.0 83.9 86.0 83.4 108.3 118.5 <5b <5 <5 <5 <5 <5 11.3 10.8 17.8 <5 <5 <5 <5 <5 <5 6.4 6.8 11.0 23.3 81.9 80.3 39.0 83.9 86.0 101.1 125.9 147.3 2.8 9.7 9.5 4.6 9.9 10.2 12.0 15.0 17.5 7.3 ± 4.0 8.3 ±3.2 14.8 ±2.7 " Calculated based on spike control mass recovery of 842 ug VX b Method quantification limit: 5 ug/coupon ------- For the 7-day aged samples, the serial extraction results indicated that the carpet retained VX after first and second extractions. The sum of these extractions yielded less VX than was originally spiked on the coupons. The lack of any appreciable second and third extraction recoveries for the metal and laminate samples after the low recoveries of the first extraction (approximately an order of magnitude loss) from the theoretical mass of agent (842 ug VX from spike control) suggested evaporation and/or decomposition of the agent. Table 2-4. Day-21 Serial Extraction Results VX may evaporate, even though it is generally considered to be "persistent." It has a measurable vapor pressure (0.0006 mm Hg at 20 °C) and may also degrade by various processes, including photo- and thermal degradation and acid/base assisted hydrolysis (4). All testing was performed under ambient laboratory conditions (see Appendix A), with no significant sources of extreme light or temperature. While samples were covered to limit exposure to air flow, evaporation was expected to contribute to losses over time. Some hydrolysis may also occur, given the ambient humidity in the air, but degradation by hydrolysis was not expected to be significant compared to evaporation. Material Metal Laminate Carpet 1" 5.5 5.4 5.9 6.1 7.5 6.8 11.4 27.8 20.5 Recovered VX (fig) after Extraction 2"11 3rd <5b <5 <5 <5 <5 <5 5.6 6.4 5.9 <5 <5 <5 <5 <5 <5 <5 <5 <5 Total VX Recovery" (%) after Extraction Total 5.5 5.4 5.9 6.1 7.5 6.8 17.0 34.2 26.4 0.65 0.64 0.70 0.72 0.89 0.81 2.02 4.06 3.13 Average Total VX Recovery, (% ± SD) 0.66 ± 0.03 0.81 ±0.08 3.1 ± 1.0 " Calculated based on spike control mass recovery of 842 ug VX 'Method quantification limit: 5 ug/coupon In coupons that were subjected to aging for 21 days, the samples lost roughly another order of magnitude of VX concentration over the 7-day aging samples. As with the 7-day aged samples, the carpet retained VX after the first extraction, but only in measurable amounts close to the detection limit in the second extraction. The metal and laminate samples showed a decrease in VX concentration relative to the 7-day aging for the first extraction with no measurable VX isolated in the second or third extractions. The results of this demonstration provided the following guidance for extraction in the aging period investigation: • Metal and laminate coupons were only extracted serially for the 1 day aging samples; otherwise, the multiple extractions were not necessary. • Three serial extractions were performed for carpet in all aging investigations. 2.4 Analytical Methods Table 2-5 shows the surrogate recovery compound (SRC) and the internal standard (IS) compound that were used in the quantitative chemical analysis (described in Section 2.0). The table also summarizes the preparation and analysis method for extracts of building materials. The number of sequential extractions for each sample was determined based on the initial demonstration of the sonication method extracting VX after it had aged for 7 days and 21 days on test coupons (see section 2.3.2). For relatively non-absorbing substrates (metal and laminate), a single extraction showed complete removal of the remaining VX, while for the more absorbing carpet substrate, three (3) extractions were still necessary for quantitative extraction of remaining VX. ------- Table 2-5. Analytical Measurement Parameters for Residual VX Decontamination Parameter Metal and Laminate Carpet SRC IS Extraction method No. of Sequential Extractions Analysis method TBP' Naphthalene -ds Sonication Ifor7, 14, and 21 day 3 for 1 day GC/MS TBP Naphthalene -ds Sonication 3 for all aging periods GC/MS "tributyl phosphate Extracts were analyzed on an Agilent Model 6890 GC equipped with a 5973 mass spectrometry detector (MSD) (Agilent, Santa Clara, CA) in full scan mode. Instrument conditions are noted in Table 2-6. A calibration curve ranging from 0.5 ug/mL to 50 ug/mL for VX and the SRC, tributyl phosphate (TBP), was analyzed prior to the analysis of the respective extractive samples. If the 50 ug/mL calibration sample did not show linearity (due to analyte saturation) this point was not included in the calibration curve. Continuing calibration verification (CCV) samples at concentrations of 0.5 ug/mL and 10 ug/mL were analyzed after the calibration curve and alternating concentrations after every fifth sample throughout the sequence. All CCVs were to have recoveries within 25% of the expected value for the samples to be considered valid. Table 2-6. GC/MS Conditions for VX/TBP Analysis Parameter Description GC Column: Carrier Gas: Injection Temperature: Injection Volume: Injection mode: Oven Profile: Run Time MS Transfer Line Temperature: Source Temperature: Quadrupole Temperature: Solvent Delay: Acquisition Mode: Agilent Model 6890 RTX-200MS, 30 m X 0.25 mm X 0.5 urn (Restek, Bellfonte, PA) Helium constant flow of 1.0 mL/min 250 °C Splitless (split 20 mL/min 1 min post injection) 50 °C hold for 2.0 minutes 20 °C /min to 250 °C hold for 0.0 minutes 35 °C /min to 300 °C hold for 0.5 minutes 13.93 minutes Agilent MSD 5973 280 °C 230 °C 150 °C 3.0 min Full scan (40 amu - 550 amu) The method detection limit for VX extracted from metal, laminate and carpet coupons was determined during a concurrent evaluation(2) of liquid decontamination technologies, and the results used to structure the analytical methodology for this investigation. Eight coupon samples of each type were spiked with a solution containing 10 ug VX. Sonic extraction in hexane and GC/MS analysis yielded the following results. For metal samples, the average recovery was 81% (MDL = 0.99 ug), laminate samples gave an average recovery of 72% (MDL = 1.28 ug), and carpet samples gave an average recovery of 86% (MDL = 1.57 ug). 2.5 VX and TBP Analysis To evaluate the extraction process of building material coupons, 1 uL of the TBP was first applied as neat material to the coupon just prior to extraction. The coupon was then loaded into a 40 mL extraction vial containing a 10 mL aliquot of hexane containing 5 ug/mL of the IS. The vial was shaken briefly and set aside while other samples were treated in the same fashion. Groups of up to 15 vials were transported to the analytical laboratory, where they were extracted using the Sonication method described in Section 2.3, and prepared for GC/MS analysis. The number of extractions for each coupon type was based on the sonication method demonstration summarized in Table 2-5. ------- 2.6 Calculation of VX Recovery and Percent Recovery Chemical agent concentration in an extract sample was determined by Equation 1: A W (l) JS where: Cs = Concentration of VX in the sample (ug/mL) CIS = Concentration of the internal standard (ug/mL) M = Slope of the GC calibration line As = Area of the VX peak in the sample AIS = Area of the internal standard peak W = Y intercept of the GC calibration line. GC/MS concentration results (|ag/mL) were converted to total mass by multiplying by extract volume, shown in Equation 2: Mm=CsxEv (2) where: Mm = measured mass of VX (|ag) Cs = GC concentration (|ag/mL), see Equation 1 Ey = volume of extract (mL). The total recovery of VX from the coupons via extraction was determined by summing the results from each of the serial extractions, as discussed in Section 2.3.1. The percent recovery of VX for a given test coupon was determined from the ratio of the total mass of VX (ug) recovered for a given coupon and aging period to the total mass of VX (ug) recovered from the spike control for that aging period, shown in Equation 3: % Recovery VX = Mm/Mspike x 100 (3) Where: Mm = measured mass of VX from test coupon extraction (ug) M , = measured mass of VX from spike control spike A extraction (ug) 2.7 Calculation of Decontamination Efficacy Decontamination efficacy was determined by measuring the amount of residual chemical agent on test coupons and comparing with positive controls (spiked with chemical agent, not decontaminated and analyzed after the same "aging period" as the test coupons). Aliquots of extracts from blanks, positive controls, and decontaminated coupons were analyzed for chemical agent according to the method described in Section 2.4. Decontamination efficacy was then defined in Equation 4 as: Mm of VXonTest Coupon _ Mm of VX on Positive Control Coupon where: Mm = measured mass of VX (|ag) E = decontamination efficacy or percent removal achieved during decontamination. Decontamination efficacy (mean ± standard deviation) was calculated for each type of test material spiked with VX. ------- 3.0 Quality Assurance / Quality Control QA/quality control (QC) procedures were performed in accordance with the test/QA plan and the applicable quality management plan (QMP)(5). QA/QC procedures are summarized below. 3.1 Performance Evaluation Audit A performance evaluation (PE) audit was performed on the GC/MS performance, specifically the TBP as it is a commercially available compound. Results are summarized in Table 3-1. To accomplish the PE audit a working source of TBP was purchased and used to create a set of calibration standards. The calibration range was from 0.5 ug/mL to 50 ug/mL in hexane/IS. Using these calibration standards a calibration curve for the TBP was generated. Due to instrument saturation (noted in Table 3-1) the 50 ug/mL calibration standard was excluded from the calibration curve leaving an acceptable calibration curve range of 0.5 ug/mL to 25 ug/mL. A second source of TBP (Aldrich Lot #06514EH, Milwaukee, WI) was purchased and using the second source TBP, a solution was created at a target concentration of 10 ug/mL in hexane/IS. The second source solution was analyzed with the working TBP calibration curve and a concentration generated from the calibration curve. The TBP second source PE audit acceptance criterion must agree within ±10% of expected concentration. The calculated concentration of the TBP second source solution was 9.83 ug/mL, or 98% of expected concentration. Table 3-1. Performance Evaluation Audit Results Sample Name hexane/IS 0.5 ug/mL std 11037 1.0 ug/mL std 11038 5.0 ug/mL std 11039 10 ug/mL std 11040 25 ug/mL std 11041 50 ug/mL std 11042 hexane/IS 0.5 ug/mL std 1 1043 CCV 10 ug/mL std 11044 CCV TBP 2nd source 52614-26-1 0.5 ug/mL std 11043 CCV TBP Final Result (Hg/mL) <0.5 0.50 0.98 5.19 10.23 23.80 39.08 <0.5 0.40 10.10 9.83 0.38 Standard Recovery, % ND 100 98 104 102 95 78' ND 80 101 98 76 " Excluded from calibration curve due to instrument saturation 3.2 Technical Systems Audit Battelle QA staff conducted a technical systems audit (TSA) during March 9, 2010 to ensure that the investigation was being conducted in accordance with the test/QA planand associated amendments and the quality management plan. As part of the TSA, a beginning-to-end inspection of the task order for the 7-day aging trial (EPAAGE D7), was performed to satisfy the TSA and PE audit requirements of the test/QA Plan and data acquisition and handling procedures were reviewed. This inspection included sample preparation, testing, data generation, instrumentation, training, documentation and ensuring the accuracy of reportable results. Staff involved in operations met facility and project-specific training requirements. Instruments used during operations were calibrated and calibration documentation was both evident and traceable to the instruments. Documentation was maintained and traceable for the source and purity of chemicals and standards, for materials used during testing and for laboratory activities to reflect compliance with the test/QA Plan, and applicable facility and project-specific SOPs. Observations and findings from the TSA were documented and submitted to the Battelle Task Order Leader for response. Minor QC issues were noted, but did not have any impact on the quality of results. TSA records were permanently stored with the Battelle QA Manager. 3.3 Data Quality Audit At least 10% of the data acquired during the investigation were audited. A Battelle QA auditor traced 100% of the data packet for the 7-day trial (EPAAGE D7) and performed a 10% check of all data results reported. Data results were also verified 100% to final reporting to ensure the integrity of the reported results. All calculations performed on the data undergoing the audit were checked. 3.4 Process Evaluation/Extraction Results A summary of the average TBP recoveries for each of the aging and decontamination samples is shown in Table 3-2. Analytical data for each sample are contained in Appendix A. Because this was an aging study, the TBP was not a surrogate recovery compound in the traditional sense. The TBP was applied to coupons after ------- the decontamination period (30 minutes), immediately prior to extraction to evaluate the efficiency of the extraction process. Table 3-2. TBP Recovery for Residual VX Decontamination Trials TBP Recovery, \ig ± SD (n=5) Material Aging Period (Day) 1 7 Metal 14 21 1 7 Laminate 14 21 1 7 Carpet 14 21 Positive Control 829 ± 29 928 ± 40 846 ± 138 885 ±119 865 ±119 914 ±77 907 ± 29 818 ±56 925 ± 47 948 ± 65 964 ± 86 918 ±62 KFS 882 ± 39 870 ±128 887 ± 14 821 ±40 903 ± 30 925 ± 45 898 ± 40 827 ± 25 930 ± 50 979 ± 54 981 ±67 847 ±135 ZEP8 831 ± 114 861 ± 124 881 ± 42 823 ± 24 903 ± 34 938 ±31 892 ± 50 833 ± 19 928 ± 85 934 ± 60 903 ± 48 872 ± 64 Based on the actual spiking of 1 uL of neat TBP (density = 0.9727 g/mL) and the extraction in 10 mL of hexane. the target mass recovery should be 972.7 ug. The % recovery based on this target mass ranged from 84% to 101% over all the samples. A listing of the % TBP recovery analytical data is provided in Appendix A. 3.5 Test Coupons During carpet sample analysis, abnormally high VX signals were observed from analytical check standards as added in the sequence of analysis of test coupons and positive controls. Based on the instrument response, the carpet extracts appeared to contain a matrix interference for VX, causing an increase in signal sensitivity after continued injection into the instrument. An example of this behavior is shown in Figure 2-3, where the red line denotes the upper limit of % recovery (125%) of the analytical standard VX. An initial set of carpet extracts was injected onto the GC/MS between the 1:43 and 3:39 sampling time. £ a -t 150% ^ 100% u 2 50% .a C3 U 0% . m m c 00 Gl r -s u D u H a H r T r T L 1 r H r 1 1 "I *t •= H rr) r sl rsl I n c t r H r I T L 0 r n u 1 T C 0 r T r 5 L 0 r C I D T- \l r "1 V 1 H P Sl T- H r ^ r H r 0 LJ -J 0 H C T r D r 3 C C 0 C D u 1 C T rn 3 ^H -J rsl Sampling Time Figure 3-1. Graph depicting the enhanced recovery of analytical check standards due to carpet extracts. The line depicts the upper acceptable limit for analyte recovery ------- This behavior was not observed in the metal or laminate extracts, nor was it observed during the method demonstration carpet analyses, presumably because of the small number of samples analyzed. This carpet extract signal enhancement caused enhanced recoveries for many of the CCVs for VX. account for this signal enhancement, carpet extracts were injected onto the instrument prior to running the calibration standards. After the conditioning and calibration samples, additional standards were run after every five analytical samples. Preconditioning To the instrument with carpet extracts allowed for the calibration to be generated accounting for the signal enhancement. Once conditioned, only carpet extracts were analyzed on the instrument, providing calibration check results such as shown in Figure 2-4, where the blank space at the beginning of the graph corresponds to the preconditioning samples, and subsequent points are calibration checks performed in between sets of five carpet extracts. Metal and laminate extracts were segregated and analyzed in a different sequence. 200% >. 1_ O) O 01 4-f "re c 2 100% - u f- c ~ 50% - re -Q re rw - Sampling Time Figure 3-2. Graph depicting the calibration check recovery after conditioning the instrument with carpet extracts. The line depicts the upper acceptable limit for analyte recovery 3.6 Blank Samples Control samples were analyzed with each aging trial, and consisted of a single procedural blank for each liquid decontaminant/coupon combination and two laboratory blanks of each coupon. Procedural blank coupons were not spiked with VX, but were decontaminated and extracted. Laboratory blanks were not spiked with VX or treated with decontaminant, but were allowed to sit in the hood for the appropriate time period, then extracted. All coupons were spiked with TBP prior to extraction. A summary of the analysis results for blank samples is given in Table 3 -3. All of the procedural and laboratory blank results were as expected, except for one procedural blank carpet sample (7-day aging, ZEP® decontaminant. shown in the shaded cell in Table 3-3) that showed a small amount of VX in the extraction. 3.7 Deviations Deviations from the test/QAplan(2) were documented. Staffs were notified of the deviations and corrective reports were filed: Section B3 of the test/QAplan states, "Hexane samples that are not analyzed immediately will be stored in a freezer at 4 ± 3 °C and analyzed the following day." Samples were stored for several days before running on the GC/MS because of high sample volume. Storage temperature for samples was at -20 °C. The deviation is minimal because of the insignificant evaporation of hexane at these temperatures. Throughout the test/QA plan, it states that sonication of samples will occur at 40 kHz for 10 minutes. However. the sonicator had a manufacturer's label affixed to it that included a range of 50-60 kHz. The impact of the deviation was minimal because all the samples including test, positive controls, procedural and laboratory blanks were extracted in identical manner. ------- Table 3-3. Analysis Results of Procedural and Laboratory Blanks Material Metal Laminate Carpet Aging Period (Day) 1 7 14 21 1 7 14 21 1 7 14 21 VX Mass, (ng) Procedural (n = 2) KFS <5 <5 <5 <5 <5 <5 <5 <5 <5 <5 <5 <5 ZEP8 <5 <5 <5 <5 <5 <5 <5 <5 <5 11 <5 <5 Laboratory (n = 2) <5 <5 <5 <5 <5 <5 <5 <5 <5 <5 <5 <5 TBP Mass, (fig) Procedural (n = 2) KFS 913 907 894 804 913 892 874 804 946 1058 961 928 ZEP8 891 865 872 784 913 954 938 853 1054 965 896 853 Laboratory (n = 2) 818 837 892 805 894 933 856 728 1002 959 948 925 This small recovery of VX on an unexposed procedural blank coupon suggested that this sample may have been compromised during the transfer or extraction process. No other instances of cross-contamination were observed during testing. The TBP recovery masses on the procedural and laboratory blank coupons were comparable to those obtained with the test coupons. The percent recovery ranged from 81% to 108% over all the procedural and blank samples. The analytical data summary for the TBP recovery of the procedural and laboratory blank samples is presented in Appendix A. ------- 4.0 Results Test results for spike controls, test coupons, procedural blanks and laboratory blanks are summarized in the following sections. 4.1 Application of VX to Test Coupons For each aging period, a set of three Teflon® coupons was each spiked with three 1 uL droplets of VX and extracted in 20 mL of chloroform containing IS to define the VX mass delivered to the coupons for each spiking activity. Based on the analysis of these samples, the mass of VX applied per drop was determined for each trial. The data are summarized in Table 4-1. Table 4-1. Results of VX Spike Control Samples Aging Period Recovered VX, Mass Average Recovered VX (fig) Mass (fig ± SD) Average Mass per Average VX Drop (fig ± SD) Recovery" (%) 1 Day 7 Day 14 Day 21 Day 3119 3191 3027 3364 3111 3018 2562 2856 2782 3066 3207 3325 3112 ±82 1037 ±27 109 3164 ±179 1055 ±60 111 2732 ±153 911 ±51 96 3199 ±129 1066 ±43 112 1 % recovery calculated based on a theoretical mass delivery per drop of 948 ug The amount of VX recovered from the spike controls was shown to be relatively consistent throughout the four different aging period trials. A somewhat lower VX recovery is noted for the 14-day trial spike control, but the amount is still within 25 % of the target mass delivery (948 ug), the acceptable criteria for analytical recovery. 4.2 Environmental Conditions during Tests The temperature and relative humidity were measured during spiking and decontamination activities for the trials and were approximately 22 °C and 40% RH. The investigation was not performed in a temperature- and humidity-controlled environment and there was no attempt made to control these parameters. Temperature and humidity measurements are given in Appendix A. During the aging portion of the test, test coupons were stored in a standard fume hood in groups of seven covered with a plastic jewelry case top to reduce rapid evaporative losses due to hood flow. Since the intent of this investigation was to determine the decontamination efficacy of VX after aging, as considered in a realistic building contamination scenario, the cover was not intended to be air tight and totally prevent losses. Rather it was to reduce any major losses that might occur due to the higher airflows necessitated by the hood environment. 4.3 Test Observations During testing, the surface behavior of the chemical agent and liquid decontaminants were observed and documented. The VX droplet soaked readily into the carpet, while it spread and pan-caked on the metal and laminate coupons. An example photograph of droplet behavior on metal coupons is shown in Figure 4-2. The VX looked oily on the metal surface. ------- Figure 4-2. Representative photograph of VX droplets on metal coupons. After the appropriate aging period, the coupons were treated with KFS and ZEP® as noted in Section 2.2. The liquid decontaminants behaved in a somewhat consistent manner on the surfaces of coupons. For 7, 14 and 21day aging samples, the KFS drop beaded on the surface of the carpet and spread on the metal and laminate samples as shown in representative photographs in Figure 4-3. During the 1-day decontamination procedure, the KFS soaked into the carpet. Figure 4-3. Representative photographs of KFS application to test coupons (left to right): metal, laminate, and carpet. Photographs from 14-day aging period. The ZEP® liquid drop consistently spread on the surface of metal and laminate coupons to a greater extent than the KFS and soaked into the carpet during all aging period tests. Representative photographs of this behavior are shown in Figure 4-4. Figure 4-4. Representative photographs of ZEP® application to test coupons (left to right): metal, laminate, and carpet. Photographs from 21-day aging period. 4.4 Recovery of VX from Aged Test Coupons With and Without Decontamination Summarized test results for the recovered mass of VX (ug) from positive controls, KFS-treated and ZEP®- treated samples are shown in Table 4-2. Analytical data for each aging trial are contained within Appendix A. The impact of aging was seen in the difference of VX recovery on the positive controls at the different age periods relative to the spike controls summarized in Table 4-1. The loss of VX may have been due most likely to evaporation and/or hydrolysis breakdown products. The analysis of breakdown products was not within the scope of this effort. ------- Table 4-2. Average VX Mass Recovery (jig) from Test Coupons Material Aging Period (Days) Metal Laminate Carpet 1 7 14 21 1 7 14 21 1 7 14 21 Positive Control (n=5) 679 ± 162 7± 1 8±3 <5 770 ± 205 37 ±33 18 ±4 9± 1 1031 ± 121 215 ±29 71 ± 13 25 ±7 Recovered VX (fig) KFS (n=5) <5 <5 <5 <5 211 <5 <5 <5 163 ± 109 8 a <5 <5 ZEP8 (n=5) 424 ± 100 9 ±2 5' <5 462 ± 132 36 ±13 17±4 8± 1 872 ± 137 177 ± 36 64 ±5 22 ±7 1 Only one sample out of five gave a measurable results (n-1) The percent VX recovery efficiency of the positive controls, samples exposed to VX but not decontaminated, is shown in Table 4-3. Evaluation of the results suggested that VX was more effectively held in the carpet, relative to the metal and laminate coupons. Loss of VX, presumably due to evaporation, was most pronounced from the metal substrate, showing a decrease in concentration of nearly two orders of magnitude with 7 days of aging. This could be due to the lack of absorption of VX by the metal coupon, making VX more susceptible to evaporation. Although known as a "persistent" chemical agent, VX will evaporate over time. Complete loss of VX (below the detection limit) was indicated from evaluation of the metal positive control coupons after 21 days. Table 4-3. VX Recovery (%) from Positive Controls after Aging Period Trials Material Metal Laminate Carpet Average VX Recovery from Positive Control Coupons at Day, % ± SD (n=5) 1 66 ± 16 74 ±20 99 ± 12 7 1±0.1 3±3 20 ±3 14 1±0.4 2 ±0.5 8±2 21 <0.5 1±0.1 2± 1 Test results for the VX recovery on test coupons treated with the two liquid decontaminants are shown in Table 4-4. Decontamination of test coupons with KFS showed a substantial decrease in recovered VX after 1 day of aging, compared to the use of ZEP® as a decontaminant. Efficient decontamination was indicated after both 1-day and 7-day aging. Further, loss of VX presumably due to evaporation at longer aging times (14 and 21 days) resulted in decontamination of VX with KFS to below detectable limits. Table 4-4. VX Recovery (%) from Decontaminated Test Coupons after Aging Periods Average VX Recovery from Test Coupon at Day, % ± SD (n=5) Material Metal Laminate Carpet KFS <0.5 2.0' 16 ± 11 1 ZEP8 41 ± 10 45 ± 13 84 ± 13 KFS <0.5 <0.5 0.771 7 ZEP8 1±0.2 4± 1 17±3 KFS <0.5 <0.5 <0.5 14 ZEP8 0.61 2 ±0.4 7± 1 KFS <0.5 <0.5 <0.5 21 ZEP8 <0.5 0.8 ±0.1 2±1 "Only one sample out of five gave a measurable result (n = 1) ------- The ZEP®-treated samples showed only a slight decrease in the amount of VX recovered after aging for 1 day. and the decontaminant showed little impact on samples aged for longer durations. 4.4.1 One Day Aging and Decontamination A graph depicting the average VX recovery results of the 1-day aging period positive control and test coupon samples is shown in Figure 4-5. Loss of VX was noted in all positive controls, presumably due to evaporation. In addition, the graph clearly showed the impact of using KFS over the ZEP® in decontaminating VX. Average VX Recovery -1 Day Average VX Recovery - 7 Day Metal Laminate Carpet Figure 4-5. Average VX recovery (fig) from 1-day aging and decontamination of positive controls (POS) and test coupons of metal, laminate, and carpet. 4.4.2 Seven Day Aging and Decontamination The average VX recovery results of the 7-day aging and subsequent decontamination are shown in Figure 4-6. Note the near complete loss of VX on metal coupons (positive controls) simply due to aging, by comparing the amount recovered to the amount recovered in the 1 day aging period trial (shown in Figure 4-4 above). The laminate coupons showed similar losses, but with a wider range of recovered VX than the metal coupons. In contrast, the carpet retained VX, losing it more slowly over time (comparing to the VX loss of positive controls in the 1-day aging). Decontamination of samples using KFS was significantly better than decontamination using ZEP® Industrial Purple. 300 250 — 200 - X~ £100- o: 50 - • POS QKFS • ZEP® Metal Laminate Carpet Figure 4-6. Average VX recovery (jig) from 7-day aging and decontamination of positive controls (POS) and test coupons of metal, laminate, and carpet. 4.4.3 Fourteen Day Aging and Decontamination The average VX recovery results from the 14 day aging and decontamination are shown in Figure 4-7. After 14 days of aging the amount of VX remaining on the metal and laminate coupons was near/below the detection limit. VX losses were apparent in the carpet as well. The ZEP® clearly did not provide effective decontamination, with resulting VX recovery on the test coupons nearly identical to the positive controls. Average VX Recovery -14 Day Metal Laminate Carpet Figure 4-7. Average VX recovery (jig) from 14-day aging and Decontamination of positive controls (POS) and test coupons of metal, laminate, and carpet. ------- 4.4.4 Twenty-One Day Aging and Decontamination The average VX recovery results from the 21 day aging and decontamination are shown in Figure 4-8. These results continued the trend observed in the 14 day aging and decontamination trials. There was no measurable VX remaining on the positive control metal coupons after 21 days. The amount of VX remaining on laminate coupons was small (near the detection limit); the amount of VX remaining in the carpet was also less than observed with the 14 day samples. KFS provided complete (below the detection limit) decontamination for all samples, whereas the ZEP® appeared to have little effect on the VX recovery. Average VX Recovery - 21 Day oo 30 - §25 - >20- "O 0) §15- o o a; -m cr iu 5 - n • POS QKFS • ZEP® n n ph n n Table 4-5. VX Decontamination Efficacy for Bleach and ZEP® on Aged Test Coupons Decontamination Efficacy, % ± SD, (n=5) Material Aging Period (Day) KFS ZEP8 Metal Laminate Carpet 1 7 14 21 1 7 14 21 1 7 14 21 >99' >29' >38' NDC 97" >86' >72' >44' 84±11 96" >93' >80' 38 ± 15 0±24 292b ND 40 ± 17 1±35 4±21 9±8 16 ± 13 18 ± 17 10 ±7 14 ±26 Metal Laminate Carpet " Lower limit value; recovered VX amount in treated sample is below method quantification limit due to the combined effect of aging and decontamination procedure b Only one sample out of five yielded a measurable result (n = 1) c Non-determinant because both the positive control and the treated samples were below detection limit. Figure 4-8. Average VX recovery (jig) from 21-day aging and Decontamination of controls (POS) and test coupons of metal, laminate, and carpet. 4.5 Decontamination Efficacy The decontamination efficacy of the KFS and ZEP® Industrial Purple on the three substrates is summarized in Table 4-5. Note that KFS decontamination slightly improved upon VX aging, and achieved greater than 99% efficacy after 1 day aging for metal, at 7 days for laminate, and at 14 days for carpet. However, the analysis is complicated by the effects of aging, since there are significant losses of VX after extended periods of time beyond one day (see positive control results in Table 4-3). The ZEP®-treated coupons showed the most decontamination efficacy after 1-day aging for metal and laminate. In addition, a decrease in ZEP® decontamination efficacy was observed after aging VX for greater than 7 days for metal and laminate coupons. and there was no apparent difference between the decontamination efficacies based on VX aging duration for the carpet samples. ------- ------- 5.0 Summary Key findings: • KFS can be effective for both porous and non- porous materials and decontamination efficacy may be more dependent on initial level of contamination than on surface characteristics • ZEP® is much less effective than KFS for all aging periods and material types • The surface decontamination efficacy using commercially available cleaning products is marginally dependent on the aging periods Samples of building materials were exposed to a known amount of VX and allowed to age for periods of 1, 7, 14, and 21 days, after which they were decontaminated for 30 minutes with either full-strength K-O-K bleach (KFS) or a 25 % solution of ZEP® Industrial Purple in water. After decontamination, the test coupons were extracted in hexane using a sequential method for up to three cycles with sonic assistance. Each extract was isolated and analyzed separately by GC/MS to determine the remaining VX recovered from the surface of each respective coupon. After analysis, the results were summarized to provide the total amount of VX recovered from the test coupons. The VX recovery efficiency is summarized in Table 5-1. Table 5-1. VX Recovery Efficiency for Contaminated and Decontaminated Building Materials after Aging VX Recovery Efficiency, (% ±SD) (n=5) 1 7 Metal 14 21 1 7 Laminate 14 21 1 7 Carpet 14 21 VJ without decontamination 66 ± 16 0.7±0.1 0.8 <0.5 74 ±20 3±3 2 ±0.5 0.9 ±0.1 99 ± 12 20 ±3 8±1 2 ±0.7 KFS <0.5 <0.5 <0.5 <0.5 2 <0.5 <0.5 <0.5 16 ± 11 0.8 <0.5 <0.5 ZEP8 41 ± 10 0.8 ±0.2 0.6 <0.5 45 ±13 3± 1 2 ±0.4 0.8 ±0.1 84 ± 13 17±3 7 ±0.6 2 ±0.6 Aging of VX on these materials suggests that VX loss is occurring, and gives the appearance of assisting in decontamination efforts. The rate of loss appears to follow the order metal ~ laminate > carpet. The extent to which the loss in VX upon aging is due to evaporation or other mechanisms, (perhaps, hydrolysis) is unknown. Analysis of degradation products was beyond the scope of this effort. However, based on the ambient conditions of the test and the physical properties of VX, evaporation is likely to be a major factor in the VX loss over such extended time periods. The test results clearly show that full-strength K-O-K® Liquid Bleach is a better decontaminant for VX than diluted ZEP® Industrial Purple, regardless of the aging period and regardless of the substrate being decontaminated. In the case of ZEP® decontamination, more hydrolysis is presumed to occur, since ZEP® Industrial Purple is a caustic cleaning solution (pH ~ 14). ZEP® Industrial Purple showed only a slight decrease in VX for 1-day aged samples, but for subsequently aged materials, there was no improvement in decontamination efficacy, as shown in Table 5-2. In the carpet samples decontaminated with ZEP®, where there is little apparent difference in the efficacy based on analysis of 1-, 7-, 14- or 21-day samples; this lack of improvement is most notable. Note that the decontamination efficacy for full-strength bleach continues to be high on aged samples. A combination of the low VX recovery on ------- the aged coupons and the relatively high method quantification limit prevents the calculation of an exact value for the decontamination efficacy. Consequently, most decontamination efficacies are calculated as "better than" a specific percentage which does not exclude the possibility that such efficacy is as high as the decontamination efficacy for, e.g., a one day aged sample. Table 5-2. Decontamination Efficacy of Residual VX on Building Materials Material Metal Laminate Carpet Aging Period (Day) 1 7 14 21 1 7 14 21 1 7 14 21 VX Recovery, % ± SD (n=5) 66 ±16 0.7±0.1 0.8" <0.5 74 ±20 3±3 2 ±0.5 0.9 ±0.1 99 ±12 20 ±3 8±1 2 ±0.7 Decontamination Efficacy, % ± SD (n=5) K-O-K® Full Strength ZEP8 Industrial Purple Liquid Bleach1 (25 % in water) >99' >29' >38' NDC 97" >86' >72' >44' 84 ± 11 96" >93' >80' 38 ± 15 0±24 29" NDC 40 ± 17 1±35 4±21 9±8 16 ± 13 18 ± 17 10 ±7 14 ±26 "Lower limit values; recovered VX amount in treated sample is below method quantification limit due to the combined effect of aging and decontamination procedure b Only one sample out of five yielded a measurable result (n = 1) 0 Non-determinant because both the positive control and the treated samples were below detection limit This study demonstrated the significant loss of VX by natural attenuation over 3 week period. It will be beneficial to investigate the fate and transport of VX by evaporation and degradation to develop an optimized decontamination strategy. ------- 1. Evaluation of Household or Industrial Cleaning Products for Remediation of Chemical Agents, EPA report in clearance as of November 18th, 2010. 2. Battelle. (2010). Evaluation Report: Evaluation of Commercially Available Liquid Decontamination Technologies for Chemical Agents, Prepared by Battelle for the U.S. EPA National Homeland Security Research Center. EPA 600/R-06/146. Draft currently under review with publication expected in 2010. 3. Battelle. (2009). Technology Investigation Report: Decontamination of Toxic Industrial Chemicals and Chemical Warfare Agents On Building Materials Using Chlorine Dioxide Fumigant and Liquid Oxidant Technologies, Battelle, Columbus, OH, February 2009. 4. Bizzigotti, G. O., Castelly, H., Hafez, A. M, Smith, W. H. B, and Whitmire, M. T., Parameters for Evaluation of the Fate, Transport and Environmental Impacts of Chemical Agents in Marine Environments, Chem. Rev. 2009,109, 236-256. 5. Quality Management Plan (QMP) for the Technology Testing and Evaluation Program (TTEP); Version 3. Battelle, Columbus, OH, January 2008. 6.0 References ------- ------- This appendix contains all GC/MS concentration data by trial name, with associated dates of activity. Table A-l. Table Key for Appendix GC/MS Raw Data Trial Name EPAAge-Dl EPAAge-D7 EPAAge-Dl 4 EPAAge-D21 Date 3/11/2010 3/12/2010 3/2/2010 3/9/2010 3/16/2010 3/30/2010 3/11/2010 4/1/2010 Trial 1 Day IDay 7 Day 7 Day 14 Day 14 Day 21 Day 21 Day Activity Spike Decon/extract Spike Decon/extract Spike Decon/extract Spike Decon/extract Appendix A Table A-2. Environmental Conditions for Activities During VX Aging Studies Date 3/2/2010 3/9/2010 3/11/2010 3/11/2010 3/12/2010 3/16/2010 3/30/2010 4/1/2010 Trial 7 Day 7 Day 1 Day 21 Day IDay 14 Day 14 Day 21 Day Activity Spike Decon/extract Spike Spike Decon/extract Spike Decon/extract Decon/extract Temp i°rY 21.9 NMb 21.7 21.7 21.7 21.7 21.6 21.5 %RH 23 NM 41 41 41 29 27 32 " Temperatures were recorded in degrees Fahrenheit (°F) 'Temperature and relative humidity were not measured during this activity ------- Trial EPAAge-Dl. Spike 3/11/10, Decontaminate and Extract 3/12/10 Sample Type Pos Control Test Proc Control Test Proc Control Material Metal Laminate Carpet Metal Laminate Sample ID EA10001 EA10011 EA10021 EA10031 EA10041 EA10051 EA10061 EA10071 EA10081 EA10091 EA10101 EA10111 EA10121 EA10131 EA10141 EA10151 EA10161 EA10171 EA10181 EA10191 EA10201 EA10211 EA10221 EA10231 EA10241 EA10251 EA10261 EA10271 EA10281 EA10291 EA10301 EA10311 EA10321 EA10331 EA10341 EA10351 EA10361 EA10371 EA10381 EA10391 EA10401 EA10411 VX(ng/mL) 1st ext 65.70 68.60 73.50 39.60 77.30 69.60 84.70 91.60 64.70 43.80 80.50 65.90 72.10 54.30 94.60 64.30 110.90 53.90 63.60 105.60 108.90 82.40 99.00 79.70 94.00 91.00 72.60 98.40 93.30 85.80 <0.5 <0.5 <0.5 <0.5 <0.5 <0.5 <0.5 <0.5 <0.5 <0.5 <0.5 <0.5 2nd ext <0.5 <0.5 <0.5 <0.5 <0.5 <0.5 <0.5 <0.5 <0.5 <0.5 <0.5 0.72 0.56 0.66 <0.5 0.50 <0.5 0.75 <0.5 0.58 7.59 5.93 8.96 15.17 5.99 13.80 8.94 18.43 8.51 6.28 <0.5 <0.5 <0.5 <0.5 <0.5 <0.5 0.73 <0.5 <0.5 <0.5 <0.5 <0.5 3rd ext <0.5 <0.5 <0.5 <0.5 <0.5 <0.5 <0.5 <0.5 <0.5 <0.5 <0.5 <0.5 <0.5 <0.5 <0.5 <0.5 <0.5 <0.5 <0.5 <0.5 1.43 1.05 1.80 6.92 1.19 3.41 2.20 5.30 2.07 1.28 <0.5 <0.5 <0.5 <0.5 <0.5 <0.5 1.34 <0.5 <0.5 <0.5 <0.5 <0.5 Total VX (\igl mL) 65.70 68.60 73.50 39.60 77.30 69.60 84.70 91.60 64.70 43.80 80.50 66.62 72.66 54.96 94.60 64.80 110.90 54.65 63.60 106.18 117.92 89.38 109.76 101.79 101.18 108.21 83.74 122.13 103.88 93.36 BDL1 BDL BDL BDL BDL BDL 2.07 BDL BDL BDL BDL BDL Comments ------- Sample Type Test Proc Control Test Proc Control Test Proc Control Test Proc Control Lab Blank Material Carpet Metal Laminate Carpet Metal Laminate Carpet Sample ID EA10421 EA10431 EA10441 EA10451 EA10461 EA10471 EA10481 EA10491 EA10501 EA10511 EA10521 EA10531 EA10541 EA10551 EA10561 EA10571 EA10581 EA10591 EA10601 EA10611 EA10621 EA10631 EA10641 EA10651 EA10661 EA10671 EA10681 EA10691 EA10701 EA10711 VX(ng/mL) 1st ext 8.10 4.23 19.14 30.80 0.52 <0.5 42.30 55.20 38.90 47.20 28.20 <0.5 60.50 33.30 24.80 52.00 48.50 <0.5 90.70 80.50 71.90 73.40 54.30 <0.5 <0.5 <0.5 <0.5 <0.5 <0.5 <0.5 2nd ext 0.70 0.94 1.54 1.51 7.45 <0.5 <0.5 <0.5 <0.5 <0.5 <0.5 <0.5 0.54 4.13 1.97 <0.5 1.06 <0.5 11.08 6.38 12.04 11.02 8.94 <0.5 <0.5 <0.5 <0.5 <0.5 <0.5 <0.5 3rd ext <0.5 2.45 0.91 0.79 2.39 <0.5 <0.5 <0.5 <0.5 <0.5 <0.5 <0.5 0.56 1.39 0.79 <0.5 1.4 <0.5 3.29 1.70 3.47 3.81 3.36 <0.5 <0.5 <0.5 <0.5 <0.5 <0.5 <0.5 Total VX (\igl mL) BDL 7.62 21.59 33.1 10.36 BDL 42.30 55.20 38.90 47.20 28.20 BDL 61.60 38.82 27.56 52.00 50.96 BDL 105.07 88.58 87.41 88.23 66.60 BDL BDL BDL BDL BDL BDL BDL Comments soaked in to coupon soaked in to coupon soaked in to coupon soaked in to coupon soaked in to coupon did not soak soaked in to coupon soaked in to coupon soaked in to coupon soaked in to coupon soaked in to coupon soaked in to coupon Samples decontaminated with full strength KOK Bleach Samples decontaminated with diluted ZEP* Industrial Purple BDL: below detection limit ------- Trial EPAAge-D7: Spike 3/2/10, Decontaminate and Extract 3/9/10 Sample Type Pos Control Test Proc Control Test Proc Control Material Metal Laminate Carpet Metal Laminate Sample ID EA10721 EA10731 EA10741 EA10751 EA10761 EA10771 EA10781 EA10791 EA10801 EA10811 EA10821 EA10831 EA10841 EA10851 EA10861 EA10871 EA10881 EA10891 EA10901 EA10911 EA10921 EA10931 EA10941 EA10951 EA10961 EA10971 EA10981 EA10991 EA11001 EA11011 EA11021 EA11031 EA11041 EA11051 EA11061 EA11071 EA11081 EA11091 EA11101 EA11111 EA11121 EA11131 VX(ng/mL) 1st ext 0.83 0.93 0.70AS 0.72 0.70 0.77 0.92 0.59 0.61 0.64 0.99 1.23 1.59 1.47 1.62 2.74 9.47 3.57 4.60 9.57 13.63 14.63 21.42 16.53 16.91 19.71 12.43 18.07 17.87 11.33 <0.5 <0.5 <0.5 <0.5 <0.5 <0.5 <0.5 <0.5 <0.5 <0.5 <0.5 <0.5 2nd ext 3.45 3.12 3.63 4.70 3.45 3.54 3.43 2.89 2.96 4.45 3rd ext 1.31 2.23 1.66 1.56 1.59 1.59 1.92 1.38 1.17 2.46 Total VX (\igl mL) 0.83 0.93 0.70 0.72 0.70 0.77 0.92 0.59 0.61 0.64 0.99 1.23 1.59 1.47 1.62 2.74 9.47 3.57 4.60 9.57 18.39 19.98 26.71 22.79 21.95 24.84 17.78 22.34 22.00 18.24 BDL BDL BDL BDL BDL BDL BDL BDL BDL BDL BDL BDL Comments ------- Sample Type Test Proc Control Test Proc Control Test Proc Control Test Proc Control Lab Blank Material Carpet Metal Laminate Carpet Metal Laminate Carpet Sample ID EA11141 EA11151 EA11161 EA11171 EA11181 EA11191 EA11201 EA11211 EA11221 EA11231 EA11241 EA11251 EA11261 EA11271 EA11281 EA11291 EA11301 EA11311 EA11321 EA11331 EA11341 EA11351 EA11361 EA11371 EA11381 EA11391 EA11401 EA11411 EA11421 EA11431 VX(ng/mL) 1st ext <0.5 <0.5 <0.5 <0.5 <0.5 <0.5 0.72 0.96 1.15 0.86 0.73 <0.5 4.11 3.99 5.28 1.92 2.92 <0.5 10.72 13.04 17.95 11.42 12.66 1.08 <0.5 <0.5 <0.5 <0.5 <0.5 <0.5 2nd ext <0.5 <0.5 <0.5 <0.5 <0.5 <0.5 2.36 3.27 3.96 4.53 2.52 <0.5 <0.5 <0.5 3rd ext <0.5 1.04 <0.5 0.59 <0.5 <0.5 1.08 0.90 1.73 1.37 0.96 <0.5 <0.5 <0.5 Total VX (\igl mL) BDL 1.04 BDL 0.59 BDL BDL 0.72 0.96 1.15 0.86 0.73 BDL 4.11 3.99 5.28 1.92 2.92 BDL 14.16 17.21 23.64 17.32 16.14 1.08 BDL BDL BDL BDL BDL BDL Comments Decon did not soak in to coupon Decon did not soak in to coupon Decon did not soak in to coupon Decon did not soak in to coupon Decon did not soak in to coupon Decon did not soak in to coupon Decon soaked in to coupon Decon soaked in to coupon Decon did not soak in to coupon Decon soaked in to coupon Decon soaked in to coupon Decon soaked in to coupon Samples decontaminated with full strength KOK Bleach Samples decontaminated with diluted ZEP* Industrial Purple BDL: below detection limit ------- Trial EPAAge-D14: Spike 3/16/10, Decontaminate and Extract 3/30/10 Sample Type Pos Control Test Proc Control Material Metal Laminate Carpet Metal Sample ID EA11441 EA11451 EA11461 EA11471 EA11481 EA11491 EA11501 EA11511 EA11521 EA11531 EA11541 EA11551 EA11561 EA11571 EA11581 EA11591 EA11601 EA11611 EA11621 EA11631 EA11641 EA11651 EA11661 EA11671 EA11681 EA11691 EA11701 EA11711 EA11721 EA11731 EA11741 EA11751 EA11761 EA11771 EA11781 EA11791 VX(ng/mL) 1st ext <0.5 0.50 <0.5 0.52 0.99 <0.5 <0.5 <0.5 <0.5 <0.5 1.46 1.47 1.69 1.53 1.48 1.55 1.70 2.61 2.35 2.10 5.16 4.46 3.55 5.43 6.81 4.70 6.98 5.06 5.30 7.33 <0.5 <0.5 <0.5 <0.5 <0.5 <0.5 2nd ext 0.98 1.12 1.85 0.98 1.36 0.72 1.11 1.34 0.83 1.42 3rd ext <0.5 1.07 0.64 0.5 0.96 <0.5 0.73 0.65 <0.5 <0.5 Total VX (\igl mL) BDL 0.50 BDL 0.52 0.99 BDL BDL BDL BDL BDL 1.46 1.47 1.69 1.53 1.48 1.55 1.70 2.61 2.35 2.10 6.14 6.65 6.04 6.41 9.13 5.42 8.82 7.05 6.13 8.75 BDL BDL BDL BDL BDL BDL Comments ------- Sample Type Test Proc Control Test Proc Control Test Proc Control Test Proc Control Test Proc Control Lab Blank Material Laminate Carpet Metal Laminate Carpet Metal Laminate Carpet Sample ID EA11801 EA11811 EA11821 EA11831 EA11841 EA11851 EA11861 EA11871 EA11881 EA11891 EA11901 EA11911 EA11921 EA11931 EA11941 EA11951 EA11961 EA11971 EA11981 EA11991 EA12001 EA12011 EA12021 EA12031 EA12041 EA12051 EA12061 EA12071 EA12081 EA12091 EA12101 EA12111 EA12121 EA12131 EA12141 EA12151 VX(ng/mL) 1st ext <0.5 <0.5 <0.5 <0.5 <0.5 <0.5 <0.5 <0.5 <0.5 <0.5 <0.5 <0.5 0.50 <0.5 0.50 0.54 <0.5 <0.5 2.35 1.73 1.64 1.31 1.60 <0.5 5.03 4.75 4.45 4.29 4.61 <0.5 <0.5 <0.5 <0.5 <0.5 <0.5 <0.5 2nd ext <0.5 <0.5 <0.5 <0.5 <0.5 <0.5 1.58 0.87 0.93 1.75 0.9 <0.5 <0.5 <0.5 3rd ext <0.5 <0.5 <0.5 <0.5 <0.5 <0.5 0.57 0.56 0.56 0.52 0.52 <0.5 <0.5 <0.5 Total VX (\igl mL) BDL BDL BDL BDL BDL BDL BDL BDL BDL BDL BDL BDL 0.50 BDL 0.50 0.54 BDL BDL 2.35 1.73 1.64 1.31 1.60 BDL 7.18 6.18 5.94 6.56 6.03 BDL BDL BDL BDL BDL BDL BDL Comments Decon did not soak in to coupon Decon did not soak in to coupon Decon did not soak in to coupon Decon did not soak in to coupon Decon did not soak in to coupon Decon did not soak in to coupon Decon soaked in to coupon Decon soaked in to coupon Decon soaked in to coupon Decon soaked in to coupon Decon soaked in to coupon Decon soaked in to coupon Samples decontaminated with full strength KOK Bleach J Samples decontaminated with diluted ZEP* Industrial Purple BDL: below detection limit ------- Trial EPAAge-D21: Spike 3/11/10, Decontaminate and Extract 4/1/10 Sample Type Pos Control Test Proc Control Material Metal Laminate Carpet Metal Sample ID EA12161 EA12171 EA12181 EA12191 EA12201 EA12211 EA12221 EA12231 EA12241 EA12251 EA12261 EA12271 EA12281 EA12291 EA12301 EA12311 EA12321 EA12331 EA12341 EA12351 EA12361 EA12371 EA12381 EA12391 EA12401 EA12411 EA12421 EA12431 EA12441 EA12451 EA12461 EA12471 EA12481 EA12491 EA12501 EA12511 VX(ng/mL) 1st ext <0.5 <0.5 <0.5 <0.5 <0.5 <0.5 <0.5 <0.5 <0.5 <0.5 0.78 0.76 0.99 0.87 0.85 0.91 0.96 0.93 1.11 1.07 1.79 2.47 2.52 2.09 3.35 2.02 1.67 2.00 1.95 2.01 <0.5 <0.5 <0.5 <0.5 <0.5 <0.5 2nd ext <0.5 1.05 0.53 0.51 0.55 <0.5 0.67 <0.5 <0.5 <0.5 3rd ext <0.5 <0.5 <0.5 <0.5 <0.5 <0.5 <0.5 <0.5 <0.5 <0.5 Total VX (\igl mL) BDL BDL BDL BDL BDL BDL BDL BDL BDL BDL 0.78 0.76 0.99 0.87 0.85 0.91 0.96 0.93 1.11 1.07 1.79 3.52 3.05 2.60 3.90 2.02 2.34 2.00 1.95 2.01 BDL BDL BDL BDL BDL BDL Comments ------- Sample Type Test Proc Control Test Proc Control Test Proc Control Test Proc Control Test Proc Control Lab Blank Material Laminate Carpet Metal Laminate Carpet Metal Laminate Carpet Sample ID EA12521 EA12531 EA12541 EA12551 EA12561 EA12571 EA12581 EA12591 EA12601 EA12611 EA12621 EA12631 EA12641 EA12651 EA12661 EA12671 EA12681 EA12691 EA12701 EA12711 EA12721 EA12731 EA12741 EA12751 EA12761 EA12771 EA12781 EA12791 EA12801 EA12811 EA12821 EA12831 EA12841 EA12851 EA12861 EA12871 VX(ng/mL) 1st ext <0.5 <0.5 <0.5 <0.5 <0.5 <0.5 <0.5 <0.5 <0.5 <0.5 <0.5 <0.5 <0.5 <0.5 <0.5 <0.5 <0.5 <0.5 0.79 0.93 0.87 0.86 0.73 <0.5 2.96 1.58 2.03 1.29 1.81 <0.5 <0.5 <0.5 <0.5 <0.5 <0.5 <0.5 2nd ext <0.5 <0.5 <0.5 <0.5 <0.5 <0.5 <0.5 0.53 0.63 <0.5 <0.5 <0.5 <0.5 <0.5 3rd ext <0.5 <0.5 <0.5 <0.5 <0.5 <0.5 <0.5 <0.5 <0.5 <0.5 <0.5 <0.5 <0.5 <0.5 Total VX (\igl mL) BDL BDL BDL BDL BDL BDL BDL BDL BDL BDL BDL BDL BDL BDL BDL BDL BDL BDL 0.79 0.93 0.87 0.86 0.73 BDL 2.96 2.11 2.66 1.29 1.81 BDL BDL BDL BDL BDL BDL BDL Comments Decon did not soak in to coupon Decon did not soak in to coupon Decon did not soak in to coupon Decon did not soak in to coupon Decon did not soak in to coupon Decon did not soak in to coupon Decon soaked in to coupon Decon soaked in to coupon Decon soaked in to coupon Decon soaked in to coupon Decon soaked in to coupon Decon soaked in to coupon Samples decontaminated with full strength KOK Bleach J Samples decontaminated with diluted ZEP* Industrial Purple BDL: below detection limit ------- Total Residual Agent (Sum of Three Extractions) Sample Type Pos Control Test Proc Control Material Metal Laminate Carpet Metal Position 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 Total Residual VX (ng/mL) Dayl 65.70 68.60 73.50 39.60 77.30 69.60 84.70 91.60 64.70 43.80 80.50 66.62 72.66 54.96 94.60 64.80 110.9 54.65 63.60 106.18 117.92 89.38 109.76 101.79 101.18 108.21 83.74 122.13 103.88 93.36 BDL BDL BDL BDL BDL BDL Day? 0.83 0.93 0.70 0.72 0.70 0.77 0.92 0.59 0.61 0.64 0.99 1.23 1.59 1.47 1.62 2.74 9.47 3.57 4.60 9.57 18.39 19.98 26.71 22.79 21.95 24.84 17.78 22.34 22.00 18.24 BDL BDL BDL BDL BDL BDL Day 14 BDL 0.50 BDL 0.52 0.99 BDL BDL BDL BDL BDL 1.46 1.47 1.69 1.53 1.48 1.55 1.70 2.61 2.35 2.10 6.14 6.65 6.04 6.41 9.13 5.42 8.82 7.05 6.13 8.75 BDL BDL BDL BDL BDL BDL Day 21 BDL BDL BDL BDL BDL BDL BDL BDL BDL BDL 0.78 0.76 0.99 0.87 0.85 0.91 0.96 0.93 1.11 1.07 1.79 3.52 3.05 2.60 3.90 2.02 2.34 2.00 1.95 2.01 BDL BDL BDL BDL BDL BDL ------- Sample Type Test Proc Control Test Proc Control Test Proc Control Test Proc Control Test Proc Control Lab Blank Material Laminate Carpet Metal Laminate Carpet Metal Laminate Carpet Position 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60 61 62 63 64 65 66 67 68 69 70 71 72 Total Residual VX (ng/mL) Day 1 2.07 BDL BDL BDL BDL BDL BDL 7.62 21.59 33.10 10.36 BDL 42.30 55.20 38.90 47.20 28.20 BDL 61.60 38.82 27.56 52.00 50.96 BDL 105.07 88.58 87.41 88.23 66.60 BDL BDL BDL BDL BDL BDL BDL Day? BDL BDL BDL BDL BDL BDL BDL 1.04 BDL 0.59 BDL BDL 0.72 0.96 1.15 0.86 0.73 BDL 4.11 3.99 5.28 1.92 2.92 BDL 14.16 17.21 23.64 17.32 16.14 1.08 BDL BDL BDL BDL BDL BDL Day 14 BDL BDL BDL BDL BDL BDL BDL BDL BDL BDL BDL BDL 0.50 BDL 0.50 0.54 BDL BDL 2.35 1.73 1.64 1.31 1.60 BDL 7.18 6.18 5.94 6.56 6.03 BDL BDL BDL BDL BDL BDL BDL Day 21 BDL BDL BDL BDL BDL BDL BDL BDL BDL BDL BDL BDL BDL BDL BDL BDL BDL BDL 0.79 0.93 0.87 0.86 0.73 BDL 2.96 2.11 2.66 1.29 1.81 1.08 BDL BDL BDL BDL BDL BDL Samples decontaminated with full strength KOK Bleach Samples decontaminated with diluted ZEP* Industrial Purple BDL: below detection limit ------- Trial EPAAge-Dl: TBP Spiked Immediately Prior to Extraction Sample Type Pos Control Test Proc Control Material Metal Laminate Carpet Metal Sample ID EA10001 EA10011 EA10021 EA10031 EA10041 EA10051 EA10061 EA10071 EA10081 EA10091 EA10101 EA10111 EA10121 EA10131 EA10141 EA10151 EA10161 EA10171 EA10181 EA10191 EA10201 EA10211 EA10221 EA10231 EA10241 EA10251 EA10261 EA10271 EA10281 EA10291 EA10301 EA10311 EA10321 EA10331 EA10341 EA10351 VX(ng/mL) 1st ext 83.30 83.90 83.40 81.70 81.60 77.10 84.60 83.80 81.20 88.50 85.50 77.50 85.20 78.00 82.40 77.60 100.20 78.80 85.30 114.30 98.20 80.90 82.60 85.00 82.60 81.70 85.80 85.70 87.30 81.70 84.70 84.50 88.20 86.00 94.20 91.30 2nd ext <0.5 <0.5 <0.5 <0.5 <0.5 <0.5 <0.5 <0.5 <0.5 <0.5 <0.5 <0.5 <0.5 <0.5 <0.5 <0.5 <0.5 <0.5 <0.5 <0.5 5.51 5.82 5.61 7.16 7.31 6.55 4.80 6.17 5.81 6.58 <0.5 <0.5 <0.5 <0.5 <0.5 <0.5 3rd ext <0.5 <0.5 <0.5 <0.5 <0.5 <0.5 <0.5 <0.5 <0.5 <0.5 <0.5 <0.5 <0.5 <0.5 <0.5 <0.5 <0.5 <0.5 <0.5 <0.5 0.92 1.00 1.05 1.75 1.63 1.58 0.80 1.06 1.07 1.47 <0.5 <0.5 <0.5 <0.5 <0.5 <0.5 Total VX (\igl mL) 83.30 83.90 83.40 81.70 81.60 77.10 84.60 83.80 81.20 88.50 85.50 77.50 85.20 78.00 82.40 77.60 100.20 78.80 85.30 114.30 104.63 87.72 89.26 93.91 91.54 89.83 91.40 92.93 94.18 89.75 84.70 84.50 88.20 86.00 94.20 91.30 Comments ------- Sample Type Test Proc Control Test Proc Control Test Proc Control Test Proc Control Test Proc Control Lab Blank Material Laminate Carpet Metal Laminate Carpet Metal Laminate Carpet Sample ID EA10361 EA10371 EA10381 EA10391 EA10401 EA10411 EA10421 EA10431 EA10441 EA10451 EA10461 EA10471 EA10481 EA10491 EA10501 EA10511 EA10521 EA10531 EA10541 EA10551 EA10561 EA10571 EA10581 EA10591 EA10601 EA10611 EA10621 EA10631 EA10641 EA10651 EA10661 EA10671 EA10681 EA10691 EA10701 EA10711 VX(ng/mL) 1st ext 91.80 88.90 93.80 85.10 90.80 91.30 92.10 79.30 87.00 86.00 89.00 88.50 60.20 85.20 88.40 90.80 84.60 89.10 95.60 90.60 85.20 88.50 90.70 91.30 92.20 85.90 79.60 81.70 75.90 96.10 86.90 76.60 92.10 86.70 95.00 92.20 2nd ext <0.5 <0.5 <0.5 <0.5 <0.5 <0.5 5.50 4.07 4.39 5.96 5.96 5.39 <0.5 <0.5 <0.5 <0.5 <0.5 <0.5 <0.5 <0.5 <0.5 <0.5 <0.5 <0.5 5.48 4.49 4.93 9.58 5.19 7.61 <0.5 <0.5 <0.5 <0.5 5.52 5.58 3rd ext <0.5 <0.5 <0.5 <0.5 <0.5 <0.5 1.05 0.66 0.53 0.97 1.12 0.70 <0.5 <0.5 <0.5 <0.5 <0.5 <0.5 <0.5 <0.5 <0.5 <0.5 <0.5 <0.5 0.76 0.63 1.01 2.77 1.07 1.65 <0.5 <0.5 <0.5 <0.5 0.85 1.15 Total VX (\igl mL) 91.80 88.90 93.80 85.10 90.80 91.30 98.65 84.03 91.92 92.93 96.08 94.59 60.20 85.20 88.40 90.80 84.60 89.10 95.60 90.60 85.20 88.50 90.70 91.30 98.44 91.02 85.54 94.05 82.16 105.36 86.90 76.60 92.10 86.70 101.37 98.93 Comments ------- Trial EPAAge-D7: TBP Spiked Immediately Prior to Extraction Sample Type Pos Control Test Proc Control Material Metal Laminate Carpet Metal Sample ID EA10721 EA10731 EA10741 EA10751 EA10761 EA10771 EA10781 EA10791 EA10801 EA10811 EA10821 EA10831 EA10841 EA10851 EA10861 EA10871 EA10881 EA10891 EA10901 EA10911 EA10921 EA10931 EA10941 EA10951 EA10961 EA10971 EA10981 EA10991 EA11001 EA11011 EA11021 EA11031 EA11041 EA11051 EA11061 EA11071 VX(ng/mL) 1st ext 96.40 95.80 93.30 89.20 99.20 86.40 90.30 92.90 88.90 95.30 83.80 92.30 90.70 90.20 102.30 77.00 93.20 92.10 89.40 103.40 85.80 94.50 75.00 86.40 89.20 95.70 88.70 92.60 81.10 93.10 61.00 91.70 93.40 94.20 90.90 90.70 2nd ext 4.90 5.27 5.01 5.39 7.21 5.18 5.10 5.41 6.16 5.46 3rd ext 0.82 1.09 0.84 0.95 1.76 0.84 0.89 0.88 1.69 1.02 Total VX (\igl mL) 96.40 95.80 93.30 89.20 99.20 86.40 90.30 92.90 88.90 95.30 83.80 92.30 90.70 90.20 102.30 77.00 93.20 92.10 89.40 103.40 91.52 100.86 80.85 92.74 98.17 101.72 94.69 98.89 88.95 99.58 61.00 91.70 93.40 94.20 90.90 90.70 Comments ------- Sample Type Test Proc Control Test Proc Control Test Proc Control Test Proc Control Test Proc Control Lab Blank Material Laminate Carpet Metal Laminate Carpet Metal Laminate Carpet Sample ID EA11081 EA11091 EA11101 EA11111 EA11121 EA11131 EA11141 EA11151 EA11161 EA11171 EA11181 EA11191 EA11201 EA11211 EA11221 EA11231 EA11241 EA11251 EA11261 EA11271 EA11281 EA11291 EA11301 EA11311 EA11321 EA11331 EA11341 EA11351 EA11361 EA11371 EA11381 EA11391 EA11401 EA11411 EA11421 EA11431 VX(ng/mL) 1st ext 98.50 85.90 93.10 92.10 95.90 89.20 95.80 91.10 89.10 85.90 88.00 98.90 91.10 61.40 91.70 94.70 90.90 86.50 89.70 96.60 90.10 96.20 94.90 95.40 92.50 83.10 91.70 76.80 86.50 89.60 75.60 91.80 94.90 91.70 97.60 82.90 2nd ext 5.84 5.35 4.81 4.76 5.73 5.98 5.33 6.65 5.92 5.22 4.47 5.98 5.92 3.71 3rd ext 0.99 1.02 0.9 0.9 1.08 0.96 0.99 2.47 0.85 0.96 0.69 0.90 1.09 0.52 Total VX (\igl mL) 98.50 85.90 93.10 92.10 95.90 89.20 102.63 97.47 94.81 91.56 94.81 105.84 91.10 61.40 91.70 94.70 90.90 86.50 89.70 96.60 90.10 96.20 94.90 95.40 98.82 92.22 98.47 82.98 91.66 96.48 75.60 91.80 94.90 91.70 104.61 87.13 Comments ------- Trial EPAAge-D14: TBP Spiked Immediately Prior to Extraction Sample Type Pos Control Test Proc Control Material Metal Laminate Carpet Metal Sample ID EA11441 EA11451 EA11461 EA11471 EA11481 EA11491 EA11501 EA11511 EA11521 EA11531 EA11541 EA11551 EA11561 EA11571 EA11581 EA11591 EA11601 EA11611 EA11621 EA11631 EA11641 EA11651 EA11661 EA11671 EA11681 EA11691 EA11701 EA11711 EA11721 EA11731 EA11741 EA11751 EA11761 EA11771 EA11781 EA11791 VX(ng/mL) 1st ext 85.10 87.90 90.00 87.70 90.50 87.60 89.80 90.40 91.70 45.70 90.80 89.20 88.80 92.60 95.50 86.40 88.20 92.20 94.50 88.60 74.90 106.10 78.00 87.30 91.20 88.80 93.30 93.90 88.40 99.80 86.90 87.30 89.10 89.10 90.50 89.40 2nd ext 5.77 4.92 6.53 6.23 5.08 4.66 4.23 5.65 4.15 4.50 3rd ext 1.61 0.81 1.19 1.83 1.25 0.86 0.75 1.20 0.68 0.72 Total VX (fig/ mL) 85.10 87.90 90.00 87.70 90.50 87.60 89.80 90.40 91.70 45.70 90.80 89.20 88.80 92.60 95.50 86.40 88.20 92.20 94.50 88.60 82.28 111.83 85.72 95.36 97.53 94.32 98.28 100.75 93.23 105.02 86.90 87.30 89.10 89.10 90.50 89.40 Comments ------- Sample Type Test Proc Control Test Proc Control Test Proc Control Test Proc Control Test Proc Control Lab Blank Material Laminate Carpet Metal Laminate Carpet Metal Laminate Carpet Sample ID EA11801 EA11811 EA11821 EA11831 EA11841 EA11851 EA11861 EA11871 EA11881 EA11891 EA11901 EA11911 EA11921 EA11931 EA11941 EA11951 EA11961 EA11971 EA11981 EA11991 EA12001 EA12011 EA12021 EA12031 EA12041 EA12051 EA12061 EA12071 EA12081 EA12091 EA12101 EA12111 EA12121 EA12131 EA12141 EA12151 VX(ng/mL) 1st ext 85.60 97.30 89.20 89.80 89.30 87.40 92.50 101.90 91.90 85.20 94.40 90.40 82.30 88.50 86.20 95.20 89.30 87.20 89.20 79.80 91.70 88.60 92.30 93.80 90.30 91.30 83.80 83.30 77.90 79.10 86.40 92.00 84.30 86.90 86.30 92.90 2nd ext 3.24 6.47 3.81 4.16 4.49 4.75 4.32 4.36 3.74 4.10 4.82 7.88 3.38 5.50 3rd ext 0.56 1.71 0.76 0.64 0.83 0.97 0.65 0.90 0.59 0.54 1.29 2.64 0.57 0.98 Total VX (\igl mL) 85.60 97.30 89.20 89.80 89.30 87.40 96.3 110.08 96.47 90 99.72 96.12 82.30 88.50 86.20 95.20 89.30 87.20 89.20 79.80 91.70 88.60 92.30 93.80 95.27 96.56 88.13 87.94 84.01 89.62 86.40 92.00 84.30 86.90 90.25 99.38 Comments ------- Trial EPAAge-D21: TBP Spiked Immediately Prior to Extraction Sample Type Pos Control Test Proc Control Material Metal Laminate Carpet Metal Sample ID EA12161 EA12171 EA12181 EA12191 EA12201 EA12211 EA12221 EA12231 EA12241 EA12251 EA12261 EA12271 EA12281 EA12291 EA12301 EA12311 EA12321 EA12331 EA12341 EA12351 EA12361 EA12371 EA12381 EA12391 EA12401 EA12411 EA12421 EA12431 EA12441 EA12451 EA12461 EA12471 EA12481 EA12491 EA12501 EA12511 VX(ng/mL) 1st ext 87.10 122.00 86.30 85.70 83.60 81.00 84.60 87.10 83.80 83.90 84.80 83.80 86.40 83.90 84.90 83.40 75.30 82.40 68.40 84.20 91.30 91.10 83.30 87.40 88.60 81.50 95.70 80.90 80.70 75.90 86.10 76.10 84.30 80.00 85.90 80.40 2nd ext 4.88 4.55 4.78 6.09 4.96 5.69 5.60 5.44 4.49 5.24 3rd ext 0.91 0.75 0.88 1.26 0.94 0.98 1.05 1.16 0.79 0.90 Total VX (\igl mL) 87.10 122.00 86.30 85.70 83.60 81.00 84.60 87.10 83.80 83.90 84.80 83.80 86.40 83.90 84.90 83.40 75.30 82.40 68.40 84.20 97.09 96.40 88.96 94.75 94.50 88.17 102.35 87.50 85.98 82.04 86.10 76.10 84.30 80.00 85.90 80.40 Comments ------- Sample Type Test Proc Control Test Proc Control Test Proc Control Test Proc Control Test Proc Control Lab Blank Material Laminate Carpet Metal Laminate Carpet Metal Laminate Carpet Sample ID EA12521 EA12531 EA12541 EA12551 EA12561 EA12571 EA12581 EA12591 EA12601 EA12611 EA12621 EA12631 EA12641 EA12651 EA12661 EA12671 EA12681 EA12691 EA12701 EA12711 EA12721 EA12731 EA12741 EA12751 EA12761 EA12771 EA12781 EA12791 EA12801 EA12811 EA12821 EA12831 EA12841 EA12851 EA12861 EA12871 VX(ng/mL) 1st ext 82.60 86.30 79.60 82.70 84.30 80.40 92.30 56.40 79.60 75.30 83.40 85.70 84.60 84.50 80.90 82.30 82.80 78.40 83.20 82.40 85.50 80.50 83.00 85.30 92.80 75.50 80.70 78.50 79.80 80.40 82.80 78.10 80.20 65.40 87.60 87.70 2nd ext 5.57 2.94 5.07 5.14 5.05 5.97 5.84 4.62 4.94 5.22 4.99 4.1 4.19 4.19 3rd ext 1.16 0.65 0.85 0.93 0.91 1.15 0.96 1.14 0.75 1.11 0.91 0.76 0.77 0.6 Total VX (\igl mL) 82.60 86.30 79.60 82.70 84.30 80.40 99.03 59.99 85.52 81.37 89.36 92.82 84.60 84.50 80.90 82.30 82.80 78.40 83.20 82.40 85.50 80.50 83.00 85.30 99.60 81.26 86.39 84.83 85.70 85.26 82.80 78.10 80.20 65.40 92.56 92.49 Comments ------- Table A-3. TBP Recovery (%) for Residual VX Decontamination Trials Material Aging '. Period (Day) TBP Recovery, % ± SD, Positive Control KFS Test Metal Laminate Carpet 1 85 ±3 7 95 ±4 14 87 ±14 21 91 ±12 1 89 ±12 7 94 ±8 14 93 ±3 21 84 ±6 1 95 ±5 7 98 ±7 14 99 ±9 21 94 ±6 Table A-4. TBP Recovery (%) for Procedural and Laboratory Material Aging Trial 1 7 Metal 14 21 1 7 Laminate 14 21 1 7 Carpet 14 21 /T)av"l KFS Test 94 93 92 83 94 92 90 83 97 109 99 95 91±4 89 ±13 91 ± 1 84 ±4 93 ±3 95 ±5 92 ±4 85 ±3 96 ±5 101 ±6 101 ±7 87 ± 14 Blanks TBP Recovery, % (n=2) ZEP8 Test 92 89 90 81 94 98 96 88 108 99 92 88 (n=5) ZEP8 Test 85 ± 12 89 ±13 91±4 85 ±2 93 ±4 96 ±3 92 ±5 86 ±2 95 ±9 96 ±6 93 ±5 90 ±7 Laboratory Blank 84 86 92 83 92 96 88 75 103 99 97 95 ------- ------- United States Environmental Protection Agency PRESORTED STANDARD POSTAGE & FEES PAID EPA PERMIT NO. G-35 Office of Research and Development (8101R) Washington, DC 20460 Official Business Penalty for Private Use $300 ------- |