Technical BRIEF INNOVATIVE RESEARCH FOR A SUSTAINABLE FUTURE Transport of Persistent Chemical Warfare Agents HD and VX into Porous Materials and Permeable Layers Practical data for remediation of contaminated building materials Purpose The Organisation for the Prohibition of Chemicai Weapons (OPCW) continues to investigate the alleged use of chemical weapons around the world. The use of chemical warfare agents (CWAs) on the battlefield has a long history. More recent (since 2012) use has occurred in Syria, Malaysia, the United Kingdom, and Russia [1-4]. Two CWAs, the nerve agent VX and blister agent sulfur mustard (HD), are of great concern due to their high toxicity and high persistence in the environment. This brief compiles data from several recent U.S. Environmental Protection Agency (EPA) bench-scale studies [5-10] that assessed the fate and transport of these two chemicals, each studied separately, into porous and/or permeable materials. This summary provides decision-makers with practical information on the expected degree of absorption/permeation of VX or l-ID (VX/HD) into several types of materials following a chemical incident resulting in the release of the CWA to the environment. This practical information will inform the remediation strategy for the reopening of contaminated buildings or infrastructure. Background EPA's Homeland Security Research Program conducts research to help on-scene coordinators and decision- makers minimize human health effects and environmental impacts following the release of a CWA. A release of a persistent CWA inside a building would result in its deposition onto a large variety of materials ranging from nonporous, impermeable materials to those with varying degrees of porosity leading to permeation of the agent into and potentially through the material. Definitions and Descriptions Permeation can occur in two main ways. First, a material may be porous, meaning that it contains void spaces (spaces not occupied by the atomic/molecular framework that make up the structure). Bulk VX/HD liquid can enter these pores by capillary action, just like a paper towel absorbs water. Second, for some materials like certain polymers, the large polymer molecules are close enough together that they do not form pores, but VX/HD molecules can move through them via forces of diffusion, i.e., to move from a place of high concentration to a place of low concentration, because the VX/HD are essentially soluble in the polymers. It is like a drop of food coloring as it dissolves in and spreads through a glass of water. Permeation of VX/HD into building materials can occur as a combination of these two processes, depending on the building material. For example, liquid VX/HD can enter the pore structure and move some depth into the material, all the while adsorbing onto the surface of the material and diffusing through it. To simplify resulting complexities, for purposes of discussion, designing experiments, and practically applying the resulting data, it is useful to group materials via common characteristics. Figure 1 illustrates such a grouping, including common materials falling into groups that need to be considered in a remediation strategy following a CWA incident. A brief description of each material group follows. U.S. Environmental Protection Agency EPA/6Q0/S-21/155 July 2021 ------- I. Nonporous, impermeable II. Nonporous, permeable • Glass • Metals • Glazed ceramic tiles Painted/sealed materials Vinyl, laminate Rubber, silicone Materials Porous, low adsorption IV. Porous, high adsorption Figure 1. Generic grouping of commonly used building materials based on their interaction with VX/HD, I. Nonporous, impermeable materials VX/HD present on materials such as glass and various metals are expected to remain on the nonporous, impermeable surface from which they (slowly) evaporate or possibly degrade via natural attenuation. II. Nonporous, permeable materials Painted and/or sealed surfaces fall in the category of nonporous materials. Such paints and sealants are intended to prevent water absorption into the porous material behind or below it (e.g., painted drywall or sealed concrete, wood). However, VX/HD, being oily substances, may behave differently than water because paint or sealant layers are permeable to VX/HD [5] via diffusion. Painted surfaces account for 60% to 70% of exposed surfaces in residences [11]. Once this occurs, VX/HD can slowly evaporate from these (painted) materials, remain in the permeable paint/sealant layers, or diffuse into the underlying porous and even more absorptive material. Organic materials such as rubber, silicone, vinyl or laminate also fall into this category, as VX/HD can diffuse into these materials, too. If these organic materials are thick enough and the VX/HD have permeated far enough into the material, it may take a very long time for them to diffuse back out. Then, these materials become reservoirs for VX/HD, potentially presenting long-term remediation challenges. U.S. Environmental Protection Agency III. Porous, low adsorption materials Liquid HD/VX can penetrate quickly (seconds, minutes) into porous materials such as unsealed concrete or limestone. The penetration depth into a porous material, movement across the substrate, and possible chemical degradation reactions with the surrounding matrix will impact the remediation strategy. In the absence of degradation processes, VX/HD may reside within a porous material for periods of time that can exceed the time they would be present on a nonporous surface. Hence, the materials become reservoirs of VX/HD, with associated remediation challenges. For materials in this category, the VX/HD are not expected to adsorb and diffuse through the material but remain on the interior surface of the pores, meaning that they potentially can be physically dislodged from the pores. IV. Porous, high adsorption materials Materials in this category may be the most difficult to remediate and may be candidates for disposal Namely, the VX/HD not only penetrates the porous structure but then diffuses into the material. Thus, remediation techniques must overcome both mechanisms, which can be technically complex or uneconomical. Many of the materials in this category are polymeric materials manufactured in a manner that they are also porous. For example, carpets and clothes can be composed of natural or synthetic polymer fibers, which are ------- processed to have desirable touch-and-feel properties, which coiricidentally can increase porosity of these materials. The fate and transport of VX/HD for this group of materials will be part of future studies. Experimental Methods EPA studied the transport of VX/HD when applied to several porous and to painted and sealed materials. VX (O-ethyl S-[2-(diisopropylamino)ethyl] methyl- phosphonothioate) is highly persistent [12] with a vapor pressure of 7 x 1CT4 mm Hg at 20 °C and oily appearance. HD [bis(2-ch!oroethyl)su!fide] is less persistent with a vapor pressure of 0.072 mm Hg at 25 °C [13], The experimental designs of the EPA studies are described briefly here. Contamination occurred in each study by application of a single droplet of chemical agent (typically 1 or 2 (iL volume across these studies) onto these materials. Study A [5] investigated the permeation of VX/HD into three different paint types and two types of sealants. This included measurement of the partitioning of the chemical into the permeable paints/sealants and underlying simulated porous material as function of time (up to 48 h for HD and 72 h for VX) (Figure 2). whether the amount of VX remained on the surface or whether it permeated or absorbed into the material. Instead, it provided information how much of VX remained with the coupon (the extracted sample of the material being tested) after specific time. Study E [10] was a decontamination study and was not designed to focus on the fate and transport of VX/HD. However, the positive controls that were part of this study provided insight in the fate and transport by measurement of the remaining VX/HD mass on the surface (surface wipe sample) and mass held by the porous or permeable material (extraction of the full material after the surface wipe sampling). Results Table 1 summarizes the expected percent of VX/HD that can be detected on the surface (as determined via surface wipe sampling) 24 h (unless noted otherwise) after the contamination occurs. Also noted, where applicable, is how much of the VX/HD migrated into the material (full material extraction) and how much was recovered from the underlying material (Studies A and E) or within the first 0.25-inch depth (Study B) or held by the material itself (Studies C and D). Table 2 provides additional information associated with the paints and sealants in Table 1. Prior to the fate and transport studies, surface wipe sampling methods and material extraction methods were verified, as applicable, on their high efficiency to sample VX/HD from all materials. Figure 2. Setup with paint layer and solid phase extraction disk below the layer. Study B [6] assessed the level of VX permeation into limestone as a porous inorganic material and into sealed concrete as a nonporous organic barrier to a porous inorganic material. Studies C [7] and D [8] (as summarized in [9]) addressed the persistence of VX as function of temperature and material. This study did not measure U.S. Environment!! Protec don Agency ------- Table 1. Surfaces, Materials, Function, Properties, and Percent Recoveries for VX and for Sulfur Mustard (HD) after 24 h. „ „ , Water Oil VX percent on surface and HD percent on surface „ „ Subsurface Study ID Surface Function Permeability Permeability in other layers or material and in other layers or Ref. 3 ena Top Layer Top Layer after 24 h material after 24 h 3 6 1. Nonporous, impermeable materials Glass Same None None 65% (coupon) Not included in test 7 Galvanized metal Same HVAC ductwork 48% (coupon) Not included in test 7 Glazed Ceramic Tile Wall, floors 18% (coupon) Not included in test 7 Glass 73% (coupon) Not included in test 8 Glazed Ceramic Tile Wall, floors 74% 120% [5 h], <0.5% [76 h] 9 Glass Same 94% 61% [5 h], <0.5% [76 h] 9 Stainless Steel Same 79% 57% 89% Not included in test 40%, 0.12% [48 h] 31%, 0.01% [48 h] 6 5 5 II. Nonporous, permeable materials Paint - Latex Flat [i] Paint - Latex Semi-Gloss [ii] Paint - Oil-Based [iii] Steel Surrogate for nonporous material Low-Medium Low 42%; 15% in latex flat 17%; 30% in latex semi- gloss 26%; 8% in oil-based layer 4%; 76% in latex flat 3%; 89% in latex semi- gloss 8%; 40% in oil-based layer A1 5 Paint - Latex Flat [i] SPE disk Surrogate for porous material 30%; 25%; 8% on surface; in paint; and in SPE 0.7%; 33%; 61% on surface; in paint; and in SPE A2 5 Paint -Latex Semi-Gloss [ii] SPE disk Surrogate for porous material 18%; 40%; 4% on surface; in paint; and in SPE 0.5%; 27%; 67% on surface; in paint; and in SPE A3 5 Paint - Oil Based [iii] SPE disk Surrogate for porous material 15%; 18%; 2% on surface; in paint; and in SPE 0.3%; 27%; 48% on surface; in paint; and in SPE A4 5 Paint - Primer & Oil- Based Steel Building material 58% (surface) Not included in test B1 6 Paint - Primer & Oil- Based Hardwood Building material 42% (surface) Not included in test B2 6 Paint - Primer & Latex Flat Dry wall Wall material NA; 69% (coupon) Not included in test CI 7 Sealant - Epoxy Sealant - Polyurethane Steel Surrogate for nonporous material None Low 23%; 37% in epoxy 16%; 35% in polyurethane 9%; 13% in epoxy 7%; 57% in polyurethane A5 5 Sealant - Epoxy SPE disk Surrogate for porous material 58%; 22%; 0% on surface; in sealant; and in SPE 1%; 14%;21% on surface; in sealant; and in SPE A6 5 II U.S. Environmental Protection Agency ------- _ , , Water Subsurface Surface Function Permeability IVIaLcilal Top Layer Oil VX percent on surface and HD percent on surface „ „ Study ID Permeability in other layers or material and in other layers or Ref. Top Layer after 24 h material after 24 h 3 6 Sealant - Polyurethane SPE disk Surrogate for porous material Low Low-Medium 11%; 57%; 10% on surface; in sealant; and in SPE 0.2%; 26%; 73% on surface; in sealant; and in SPE A7 5 Sealant- Silane/Siloxane Concrete Protective flooring material 0.3-0.8%; 8-14% in top 1/4" Not included in test B3 6 Sealant- Silane/Siloxane Concrete Protective flooring material NA; 6% (coupon) Not included in test C2 7 Sealant- Silane/Siloxane Sandstone Used as surrogate for porous material NA; 29% (coupon) 27% (coupon 5 h), 2.2% (coupon 76 h), El 10 Rubber Same Escalator handrail, wall base molding 56% (coupon) Not included in test 8 77% (coupon) 130% (coupon 5 h), 130% (coupon 76 h)* 10 HDPE Plastic Same Water pipes, liner Low Low 92% (coupon) Not included in test 8 III. Porous, low adsorption materials Limestone Same Building material High Medium-High Medium-High Medium-High 0.41% (surface) 0.2-0.4%; 11-43% in top 1/4" Not included in test 6 Unsealed Concrete Same Walls, floors 0.8% (surface) 13% (coupon) Not included in test 6 8 Plywood Same Subfloor material 62% (coupon) Not included in test 8 IV. Porous, high adsorption materials Ceiling Tile Same Dropped ceiling High Medium-High 81% (coupon) Not included in test 8 *: Recoveries biased high due to significant interferences in ion chromatograms coupon: the extracted sample of the material being tested, HDPE: high-density polyethylene, SPE: solid phase extraction m U.S. Environmental Protection Agency ------- Table 2. Additional Data for Paints and Sealants. Study ID Reference Top Surface Specifics Product Information Notes A1 5 Painted Steel Latex Flat Latex Semi-Gloss Paint - Oil-Based See info for specific paints below (A2, A3, and A4) A2 5 Paint Layer Latex Flat Behr® Premium Plus Ultra-Pure White Flat Zero VOC Interior Paint Free standing paint layer A3 5 Paint Layer Latex Semi-Gloss Behr® Premium Plus Ultra-Pure White Semi-Gloss Zero VOC Interior Paint Free standing paint layer A4 5 Paint Layer Paint - Oil-Based Rust-Oleum® Professional High Performance White Gloss Oil- Based Enamel Interior/Exterior Paint Free standing paint layer A5 5 Sealed Steel Epoxy-based Polyurethane-based See info for specific sealants below (A6, A7) A6 5 Sealant Layer Epoxy-based Rust-Oleum® 5300 System Water-Based Epoxy in White, Gloss Finish with Activator Free standing sealant layer A7 5 Sealant Layer Polyurethane-based Rust-Oleum® 6711 System Water-Based Polyurethane, Clear Free standing sealant layer B1 6 Painted steel Primer + Oil-based metal paint Latex White Interior/Exterior Multi-Surface Primer, Sealer, and Stain Blocker + High Performance Protective Enamel Gloss White Oil-Based Interior/Exterior Metal Paint B2 6 Painted hardwood Primer + Oil-based metal paint Latex White Interior/Exterior Multi-Surface Primer, Sealer, and Stain Blocker + High Performance Protective Enamel Gloss White Oil-Based Interior/Exterior Metal Paint Same paint was used for consistency with study ID B1 B3 6 Sealed concrete Siloxane Sealant Sure Klean® Weather Seal Siloxane PD (predilute) CI 7 Painted dry wall Latex primer + Latex Flat KILZ® latex primer + Behr® Premium Plus Interior Flat White Latex Paint C2 7 Sealed concrete Siloxane Sealant Sure Klean® Weather Seal Siloxane PD El 10 Sealed Sandstone Siloxane Sealant Sure Klean® Weather Seal Siloxane PD m U.S. Environmental Protection Agency ------- Impact of VX/HD Transport into Materials on Sampling, Decontamination and Waste Management The observed transport of VX/HD into porous and/or permeable materials will impact the environmental sampling of these agents during the consequence management phase following an incident. The impact described below on surface wipe sampling is derived from bench-scale surface wipe sampling approaches, which were effective in the experiments but are not fully verified field sampling methods. Further, most of the efficacious decontaminants that are capable to degrade VX/HD are water based. Hence, it is likely that any transport of decontaminants into a porous material that would degrade the agent within the material will differ significantly in magnitude and mechanism in comparison to the transport of these oily chemicals. Specific impacts on sampling, decontamination, and waste management are summarized here. I. Nonporous, impermeable materials VX/HD present on materials in the nonporous, impermeable group remain on the nonporous or impermeable surface. Wear and tear over time may make these materials porous. Cracks in glazed ceramic tile are known to result in the transport of chemicals into the clay material. The rate of evaporation will determine the amount of agent remaining [see reference 9 for VX], Sampling: Wipe sampling methods can recover agent on the surface. High surface wipe sampling efficiencies can be achieved that will lead to more accurate level of agent contamination characterization. Decontamination and Waste Management: These types of surfaces can be relatively straightforward to clean/decontaminate. They are expected to remain in place and would not enter the waste stream. II. Nonporous, permeable materials The observed transfer of VX/HD into a paint or sealant and into a potentially more porous material below or behind it (like drywall behind paint) complicates remediation of such material or such combination of materials. The degree to which this permeation occurs depends on the chemical and physical properties of both agents and the paint/sealant type and sheen. The rate of permeation may exceed the evaporation rate. No data have been collected for rubber to determine how much of the recovered agent in a coupon extract can be attributed to the amount on the surface versus the amount permeated into the material. High recoveries after 24 h suggest that VX may have substantially permeated the substrate. Sampling: Surface wipe sampling of these type of painted or sealed surfaces may not recover the actual amount of agent present and may even lead to false negatives on the presence of an agent. Surface wipe sampling of materials such as rubber is expected to recover the non-permeated agent remaining on the surface, but not VX/HD that has diffused into the material. Decontamination and Waste Management: Full decontamination of the permeable paint or sealant layers is expected to be complex considering the inability of water-based decontaminants to react with the agents in the paint or sealant layer. Modifications to decontamination approaches would be required to be confident that the agent in the paint or sealant has degraded. For bulk materials such as rubber, residual VX/HD post-decontamination may diffuse back to the surface from which it would volatilize and become an airborne and contact hazard. Currently, decontamination of these types of materials is difficult and often cost prohibitive. In many cases, they may become part of the waste stream. III. Porous, low adsorption materials Low recoveries of VX (no direct information for HD available) demonstrate the penetration into porous materials. Degradation (of VX) through interactions with the material should not be excluded either, especially for more materials known to be reactive with VX, such as concrete. Sampling: Surface wipe sampling of these surfaces may detect low or minimal VX/HD on the surface. Most of the VX/HD would not be accessible to a surface wipe. The VX/HD would slowly diffuse back to the surface and volatilize from the substrate. Decontamination and Waste Management: Applied decontaminants may not be able to reach deeper into pores because the pores are occupied by the VX/HD and will have limited efficacy. Physical removal of top layers containing the agent may be possible without loss in integrity of the material [10]. Currently, decontamination of these materials is difficult and U.S. Environmental Protection Agency ------- often cost prohibitive. In many cases, they may become part of the waste stream. Less waste would be generated if only layers of materials (containing the VX/HD) are removed. IV. Porous, high adsorption materials Transport studies for this group of materials have been limited. Impacts on sampling, decontamination and waste management are expected to be like those porous, low adsorption materials described under III) and are not repeated here. Limitations of Studies • All transport studies were conducted with representative, new, and clean surfaces and materials. Soiling, degradation, hardening, cracking or other deteriorations by wear and tear over time would impact the transport and permeation of the VX/HD into a material. For instance, deep cracks or fissures that might occur during normal wear and tear of originally less permeable surface (like a glazed ceramic tile) could result in unexpected transport of agent into the material. • Other paints or sealants are expected to behave differently than described here, based on the large variations between the limited numbers of these products investigated in these studies. • Unsealed concrete is an example of a frequently encountered porous and reactive material. The transport and observed degradation of VX/HD on/in unsealed concrete is complex and is not discussed in detail in this brief. The provided transport data for unsealed concrete complements information already in the literature. Contacts Technical Contacts • Lukas Oudejans, oudeians.lukas(a)epa.gov Communications Contact • Amelia McCall, mccall.amelia(5>epa.gov Disclaimer: This document is for informational purposes only. Any mention of or reference to commercial products, processes, or services by trade name, trademark, manufacturer, or otherwise does not imply an endorsement by the U.S. Government or the U.S. Environmental Protection Agency and shall not be used for advertising or product endorsement purposes. EPA does not endorse any commercial products, services, or enterprises. U.S. Environmental Protection Agency ------- References 1. Organisation for the Prohibition of Chemical Weapons (OPCW). "Syria and the OPCW." See https://www.opcw.org/media-centre/news/2019/03/opcw-issues-fact-finding-mission-report-chemical-weapons- use-allegation. Last accessed May 24, 2021. 2. Organisation for the Prohibition of Chemical Weapons (OPCW). "Malaysia. Statement by the Delegation of Malaysia at the eighty-sixth Session of the Executive Council." See https://www.opcw.org/fileadmin/OPCW/EC/86/en/ec86natl2 e .pdf. Last accessed May 24, 2021. 3. Organisation for the Prohibition of Chemical Weapons (OPCW). "Incident in Salisbury." See https://www.opcw.org/media-centre/featured-topics/incident-salisbury. Last accessed May 24, 2021. 4. Organisation for the Prohibition of Chemical Weapons (OPCW). "Case of Mr Alexei Navalny." See https://www.opcw.org/media-centre/featured-topics/case-mr-alexei-navalny. Last accessed May 24, 2021. 5. U.S. EPA. 2016. "Fate and Transport of Chemical Warfare Agents VX and HD across a Permeable Layer of Paint or Sealant into Porous Subsurfaces." EPA/600/R-16/173, Research Triangle Park, NC: U.S. Environmental Protection Agency. 6. U.S. EPA. 2020. "Physical and Chemical Removal Options for Porous/Permeable Materials Contaminated with the Persistent Chemical Warfare Agent VX." EPA/600/R-20/047, Research Triangle Park, NC: U.S. Environmental Protection Agency. 7. U.S. EPA. 2016. "Natural Attenuation of Persistent Chemical Warfare Agent VX on Selected Interior Building Surfaces." EPA/600/R-16/110, Research Triangle Park, NC: U.S. Environmental Protection Agency. 8. U.S. EPA. 2017. "Natural Attenuation of the Persistent Chemical Warfare Agent VX on Porous and Permeable Surfaces." EPA/600/R-17/186, Research Triangle Park, NC: U.S. Environmental Protection Agency. 9. U.S. EPA. 2019. "Technical Brief: Persistence of Chemical Warfare Agent VX on Building Material Surfaces." EPA/600/S-19/074, Research Triangle Park, NC: U.S. Environmental Protection Agency. 10. U.S. EPA 2017. "Remediation Options for Porous Materials Contaminated with Persistent Chemical Warfare Agents VXand HD." EPA/660/R-17/348, Research Triangle Park, NC: U.S. Environmental Protection Agency. 11. Manuja, A, J Ritchie, K Buch, Y Wu, CMA. Eichler, JC Little and LC Marr. 2019. Total surface area in indoor environments. Environ. Sci.: Processes & Impacts 21: 1384-1392. 13 National Response Team Quick Reference Guide VX, January 2015 Update. Available at https://nrt.Org/sites/2/files/NRT WMD CHEM UPDATE VX ORG FINAL 2015 01 22.pdf. Last accessed May 25, 2021. 14 National Response Team Quick Reference Guide HD, January 2015 Update. Available at https://www.nrt.Org/sites/2/files/NRT WMD CHEM UPDATE Sulfur Mustard HD ORG FINAL 2015 01 22.pdf. Last accessed May 25, 2021. H U.S. Environmental Protection Agency ------- |