Monitoring of Sulfur Mustard (HD) Vapor in the Presence of Absorptive Building Materials.

In the event of an accidental or intentional release of a chemical warfare agent (CWA), environmental samples must be collected and analyzed to assess the level of the contamination. Equally important is an understanding of the fate and transport of a CWA in the presence of porous materials, which may impact the ability to collect environmental samples. Air monitoring techniques may be used to rule in/out the presence of a CWA. Here, relationships between the CWA sulfur mustard (HD) surface contamination levels and the associated HD vapor concentration were investigated. Results indicate that absorption of HD into vinyl, concrete, and sealed concrete followed by slow diffusion out of these materials significantly prolonged the presence of HD vapor concentrations. The extracted material recovery data suggest that positive correlations can be established between residual material contamination and vapor concentration but also that surface wiping alone would fail to detect absorbed HD.

Evaluation of steam heat as a decontamination approach for SARS-CoV-2 when applied to common transit-related materials.

AIMS: The purpose of this study was to evaluate the efficacy of steam heat for inactivation of SARS-CoV-2 when applied to materials common in mass transit installations. METHODS AND RESULTS: SARS CoV-2 (USA-WA1/2020) was resuspended in either cell culture media or synthetic saliva, inoculated (∼1 × 106 TCID50) onto porous and nonporous materials and subjected to steam inactivation efficacy tests as either wet or dried droplets. The inoculated test materials were exposed to steam heat ranging from 70°C to 90°C. The amount of infectious SARS-CoV-2 remaining after various exposure durations ranging from 1 to 60 s was assessed. Higher steam heat application resulted in higher inactivation rates at short contact times. Steam applied at 1-inch distance (∼90°C at the surface) resulted in complete inactivation for dry inoculum within 2 s of exposure (excluding two outliers of 19 test samples at the 5-s duration) and within 2-30 s of exposure for wet droplets. Increasing the distance to 2 inches (∼70°C) also increased the exposure time required to achieve complete inactivation to 15 or 30 s for materials inoculated with saliva or cell culture media, respectively. CONCLUSIONS: Steam heat can provide high levels of decontamination (>3 log reduction) for transit-related materials contaminated with SARS-CoV-2 using a commercially available steam generator with a manageable exposure time of 2-5 s.

Passenger vehicle interior decontamination by low concentration hydrogen peroxide vapor following a wide area biological contamination incident.

AIMS: To assess low concentration hydrogen peroxide (LCHP) (H2O2) vapor dispersed with a home humidifier for its ability to decontaminate vehicle interiors contaminated with Bacillus anthracis surrogate Bacillus atrophaeus spores. METHODS AND RESULTS: Efficacy of a vaporized 3% H2O2 solution was evaluated for liquid volumes, on/off vehicle heating, ventilation, and air conditioning (HVAC) system operations, and temperatures that ranged from 5 to 27°C. Survival of the spores was assessed by quantification of remaining viable spores with efficacy quantified in terms of mean log10 reduction. Decontamination efficacy after the 6-day dwell time increased when the 3% H2O2 liquid volume was doubled, increasing from 4-of-10 to 10-of-10 nondetects (zero colonies counted using standard dilution and filter plating) inside the vehicle cabin. Recirculating cabin air through the HVAC system during decontamination decreased efficacy to 6-of-10 non-detects. While no 6-log10 reduction in viable spores was observed on the cabin filter with the cabin filter kept in place, a 6-log10 reduction was achieved after its removal and placement in the cabin during treatment. CONCLUSIONS: Results from this study allow for informed decisions on the use of LCHP vapor as an effective decontamination approach for vehicle interiors.

Evaluation of two methods for detection of viable Bacillus anthracis simulant spores in maritime environmental samples.

Analytical methods exist to detect biothreat agents in environmental samples during a response to biological contamination incidents. However, the coastal zone facilities and assets of the US Coast Guard (USCG), including response boats in diverse geographical areas and maritime environmental conditions, can pose complex and unique challenges for adapting existing analytical detection methods. The traditional culture (TC) and the rapid viability polymerase chain reaction (RV-PCR) methods were evaluated for their compatibility for maritime environmental surface and grab sample analysis to detect spores of Bacillus thuringiensis subspecies kurstaki (Btk), a surrogate for Bacillus anthracis. The representative samples collected from a USCG installation included surfaces, such as aluminum on boats, nonskid tread on decks of watercraft, computer touchscreens, and concrete piers, and grab samples of boat washdown water, soil, vegetation, and gravel from surrounding areas. Replicate samples were spiked with Btk spores at two to three tenfold increasing levels and analyzed. Out of a total of 150 samples collected and analyzed, the TC method gave 10 false-positive and 19 false-negative results, while the RV-PCR method-based analysis resulted in 0 false-positive and 26 false-negative results. An abundance of microbial background and particulates in some samples interfered with true results, while both methods gave similar results for samples with low microbial background and particulates. Improved and high-throughput sample processing methods are needed for analysis of complex environmental samples.

Large-scale evaluation of microorganism inactivation by bipolar ionization and photocatalytic devices.

The COVID-19 pandemic has raised awareness in the spread of disease via airborne transmission. As a result, there has been increasing interest in technologies that claim to reduce concentrations of airborne pathogens in indoor environments. The efficacy of many of these emerging technologies is not fully understood, and the testing that has been done is often conducted at a small scale and not representative of applied settings. There is currently no standard test method for evaluating air treatment technologies, making it difficult to compare results across studies or technology types. Here, a consistent testing approach in an operational-scale test chamber with a mock recirculating heating, ventilation, and air conditioning (HVAC) system was used to evaluate the efficacy of bipolar ionization and photocatalytic devices against the non-enveloped bacteriophage MS2 in the air and on surfaces. Statistically significant differences between replicate sets of technology tests and control tests (without technologies active) are apparent after 1 h, ranging to a maximum of 0.88 log10 reduction for the bipolar ionization tests and 1.8 log10 reduction for the photocatalytic device tests. It should be noted that ozone concentrations were elevated above background concentrations in the test chamber during the photocatalytic device testing. No significant differences were observed between control and technology tests in terms of the amount of MS2 deposited or inactivated on surfaces during testing. A standardized, large-scale testing approach, with replicate testing and time-matched control conditions, is necessary for contextualizing laboratory efficacy results, translating them to real-world conditions, and for facilitating technology comparisons.

Impact of test methodology on the efficacy of triethylene glycol (Grignard Pure) against bacteriophage MS2.

The COVID-19 pandemic has raised interest in using chemical air treatments as part of a strategy to reduce the risk of disease transmission, but more information is needed to characterize their efficacy at scales translatable to applied settings and to develop standardized test methods for characterizing the performance of these products. Grignard Pure, a triethylene glycol (TEG) active ingredient air treatment, was evaluated using two different test protocols in a large bioaerosol test chamber and observed to inactivate bacteriophage MS2 in air (up to 99.9% at 90 min) and on surfaces (up to 99% at 90 min) at a concentration of approximately 1.2 - 1.5 mg/m3. Introducing bioaerosol into a TEG-charged chamber led to overall greater reductions compared to when TEG was introduced into a bioaerosol-charged chamber, although the differences in efficacy against airborne MS2 were only significant in the first 15 min. Time-matched control conditions (no TEG present) and replicate tests for each condition were essential for characterizing treatment efficacy. These findings suggest that chemical air treatments could be effective in reducing the air and surface concentrations of infectious pathogens in occupied spaces, although standard methods are needed for evaluating their efficacy and comparing results across studies. The potential health impacts of chronic exposure to chemicals should also be considered, but those were not evaluated here.

Evaluation of Malathion, DIMP, and Strawberry Furanone as CWA Simulants for Consideration in Field-Level Interior Building Remediation Exercises.

Field-level exercises with the purpose to assess remediation following the deliberate release of a highly toxic chemical in an indoor environment can be conducted using low(er) toxicity simulants if they are closely linked to the behavior of the toxic chemical itself. Chemical warfare agent (CWA) simulants have been identified on their suitability based on chemical structural similarities and associated physical and chemical properties. However, there are no reported studies that combine measurement of simulant parameters like persistence on surfaces, ability to sample for, and capability to degrade during the decontamination phase such that the level of success of a field-level exercise can be quantified. Experimental research was conducted to assess these gaps using a select number of CWA simulants. The organophosphate pesticide malathion was found to be a suitable simulant for use in field-level exercises that simulate the release of the highly persistent nerve agent VX based on its high persistence, effective surface sampling and analysis using standard analytical equipment, and the in situ degradation in the presence of different oxidizing decontaminants.

Decontamination efficacy of common liquid disinfectants against non-spore-forming biological agents in soil matrices.

AIMS: The purpose of this study was to evaluate decontamination efficacy, within three soil types, against Yersinia pestis, Burkholderia pseudomallei, and the Venezuelan Equine Encephalitis virus (VEEV). METHODS AND RESULTS: One of three liquid disinfectants (dilute bleach, Virkon-S or Klozur One) was added to three soil types (sand, loam, or clay) and allowed contact for four pre-spike durations: 0, 15, 30 and 60 min. Y. pestis, B. pseudomallei, or VEEV was then spiked into the soil (10 microliters or approx. 1 × 107  CFU or PFU into 1 g soil) and decontamination efficacy assessed at post-spike contact times of 10 or 60 min at ambient environmental conditions. Across all soil types, sandy soil resulted in the least quenching to all three disinfectants tested as shown by sustained decontamination efficacy across all pre-spike and post-spike timepoints. Clay and loam soil types exhibited quenching effects on the hypochlorite and peroxygen based disinfectants (dilute bleach and Virkon S) and in general resulted in decreased efficacy with increased pre-spike contact time. The sodium persulfate (Klozur One) performance was the most consistent across all soil types and pre-spike contact times, resulting in greater efficacy with increased post-spike time. CONCLUSIONS: Liquid disinfectants can provide high levels of decontamination in soil for both viral and non-spore-forming bacterial select agents. Hypochlorite and peroxygen based disinfectants used in soils containing higher organic content (loam or clay) may require extended contact times or re-application of liquid disinfectant, in as little as 15 min of application, to achieve a 6-log reduction. SIGNIFICANCE AND IMPACT OF THE STUDY: These results provide information for the performance of three disinfectants in soil against non-spore-forming select agents. These data may aid response decision makers following a biological contamination incident by informing the selection of disinfectant as well as the re-application time to achieve effective site remediation.

Decontamination options for indoor surfaces contaminated with realistic fentanyl preparations.

The significant increase in illegal use of the synthetic opioid fentanyl is leading to unintentional overdose fatalities. Spills of fentanyl where it is abused or prepared for illegal distribution can result in persistent contamination of areas. Remediation can be attempted through physical removal but may benefit greatly from application of decontamination solutions that provide in-situ degradation of fentanyl. This work investigates the efficacy of decontamination technologies for degradation of fentanyl-HCl on indoor surfaces. Decontamination studies were conducted to evaluate the oxidative degradation of fentanyl based on percarbonate, hydrogen peroxide, peracetic acid, and chlorine (bleach) chemistries. This study utilized an experimental design relevant to field operations to provide direct information to first or hazardous materials responders and providers of environmental fentanyl remediation services, who may otherwise rely on unverified approaches. Across a range of nonporous indoor surfaces, results suggest that water (with or without detergent) spraying alone can physically remove 70-90% of fentanyl (with all fentanyl recovered in runoff). In nearly all cases, the spray application of peracetic acid or acetified bleach oxidants resulted in statistically significant degradation of fentanyl (>95% reduction), with noticeably lower efficacy for other oxidants (e.g., pH neutral bleach and OxiClean™). The decontamination efficacy was significantly reduced upon the addition of cutting agents that competed for oxidant demand.

Remediating Indoor Pesticide Contamination from Improper Pest Control Treatments: Persistence and Decontamination Studies.

The improper and excessive use of pesticides in indoor environments can result in adverse human health effects, sometimes necessitating decontamination of residential or commercial buildings. A lack of information on effective approaches to remediate pesticide residues prompted the decontamination and persistence studies described in this study. Decontamination studies evaluated the effectiveness of liquid-based surface decontaminants against pesticides on indoor surfaces. Building materials were contaminated with 25-2,400 µg/100cm2 of the pesticides malathion, carbaryl, fipronil, deltamethrin, and permethrin. Decontaminants included both off-the-shelf and specialized solutions representing various chemistries. Pesticides included in this study were found to be highly persistent in a dark indoor environment with surface concentrations virtually unchanged after 140 days. Indoor light conditions degraded some of the pesticides, but estimated half-lives exceeded the study period. Decontamination efficacy results indicated that the application of household bleach or a hydrogen peroxide-based decontaminant offered the highest efficacy, reducing malathion, fipronil, and deltamethrin by >94-99% on some surfaces. Bleach effectively degraded permethrin (>94%), but not carbaryl (<70%) while the hydrogen peroxide containing products degraded carbaryl (>71-99%) but not permethrin (<54%). These results will inform responders, the general public and public health officials on potential decontamination solutions to remediate indoor surfaces.

Surface decontamination for blister agents Lewisite, sulfur mustard and agent yellow, a Lewisite and sulfur mustard mixture.

Sulfur mustard (HD) and Lewisite (L) are blister agents that have a high potential for terrorist use; Agent Yellow (HL) is the eutectic mixture of HD and L. Bench-scale testing was used to determine the residual amount of these chemical warfare agents remaining on three building materials (wood, metal and glass) after application of various decontaminants (household bleach, full strength and dilute; hydrogen peroxide 3% solution; and EasyDECON(®) DF200). All decontaminants reduced the amount of L recovered from coupons. Application of dilute bleach showed little or no difference compared to natural attenuation in the amount of HD recovered from coupons. Full-strength bleach was the most effective of four decontaminants at reducing the amount of HD from coupons. Hydrogen peroxide (3% solution) and DF200 did decrease the amount of HD recovered from coupons more than natural attenuation (except DF200 against HD on metal), but substantial amounts of HD remained on some materials. Toxic HD by-products were generated by hydrogen peroxide treatment. The effectiveness of decontaminants was found to depend on agent, material, and decontaminant. Increased decontaminant reaction time (60min rather than 30min) did not significantly increase effectiveness.

Semivolatile and volatile organic compound emissions from wood-fired hydronic heaters.

Emissions including polychlorinated dibenzo-p-dioxins (PCDDs) and polychlorinated dibenzofurans (PCDFs), polyaromatic hydrocarbons (PAHs), and volatile organic compounds (VOCs), were sampled from different wood-fired hydronic heater (HH) technologies. Four commercially available HH technologies were studied: a single-stage conventional combustor with natural updraft, a three-stage downdraft combustion system, a bottom-fed pellet burner, and a two-stage heater with both a combustion and gasification chamber. The fuel consisted of three wood types (red oak, white pine, and white ash), one hardwood pellet brand, and one fuel mixture containing 95% red oak and 5% residential refuse by weight. The various HHs and fuel combinations were tested in a realistic homeowner fuel-charging scenario. Differences in emission levels were found between HH technologies and fuel types. PCDD/PCDF emissions ranged from 0.004 to 0.098 ng toxic equivalency/MJ(input) and PAHs from 0.49 to 54 mg/MJ(input). The former was increased by the presence of 5% by weight refuse. The white pine fuel had the highest PAH emission factor, while the bottom fed pellet burner had the lowest. The major VOCs emitted were benzene, acetylene, and propylene. The highest emissions of PAHs, VOCs, and PCDDs/PCDFs were observed with the conventional unit, likely due to the rapid changes in combustion conditions effected by the damper opening and closing.

Near-real-time combustion monitoring for PCDD/PCDF indicators by GC-REMPI-TOFMS.

The boiler exit flue gas of a municipal waste combustor was sampled to evaluate an online monitoring system for chlorobenzene congeners as indicators of polychlorinated dibenzodioxin and dibenzofuran (PCDD/PCDF) concentrations. Continuous measurements of chlorobenzene congeners using gas chromatography coupled to a resonance-enhanced multiphoton ionization - time-of-flight mass spectrometry (GC-REMPI-TOFMS) system were compared over 5-min periods with conventional sampling methods for PCDD/PCDF. Three pairs of values were taken every hour over a period of three days to characterize the combustor's response to transient operating conditions (shutdowns and startups). Isolation of specific chlorobenzene congeners from other same-mass compounds was accomplished by using a GC column separator ahead of the REMPI-TOFMS. The 50-fold variation of PCDD/PCDF concentration was paralleled by similar changes in monitored compounds of 1,4-dichlorobenzene, 1,2,4-trichlorobenzene, 1,2,3-trichlorobenzene, and 1,2,4,5-tetrachlorobenzene. A correlation of R = 0.85 and 0.89 was established between 40 pairs of simultaneous 5-min GC-REMPI-TOFMS measurements of 1,2,4-trichlorobenzene and 5 min conventional sampling and analysis for the TEQ and Total measures of PCDD/PCDF, respectively. The GC-REMPI-TOFMS system can be used to provide frequent measures of correlative PCDD/PCDF concentration thereby allowing for an understanding of measures to minimize PCDD/PCDF formation and develop operational feedback to limit emissions.

Development of size-selective sampling of Bacillus anthracis surrogate spores from simulated building air intake mixtures for analysis via laser-induced breakdown spectroscopy.

Size-selective sampling of Bacillus anthracis surrogate spores from realistic, common aerosol mixtures was developed for analysis by laser-induced breakdown spectroscopy (LIBS). A two-stage impactor was found to be the preferential sampling technique for LIBS analysis because it was able to concentrate the spores in the mixtures while decreasing the collection of potentially interfering aerosols. Three common spore/aerosol scenarios were evaluated, diesel truck exhaust (to simulate a truck running outside of a building air intake), urban outdoor aerosol (to simulate common building air), and finally a protein aerosol (to simulate either an agent mixture (ricin/anthrax) or a contaminated anthrax sample). Two statistical methods, linear correlation and principal component analysis, were assessed for differentiation of surrogate spore spectra from other common aerosols. Criteria for determining percentages of false positives and false negatives via correlation analysis were evaluated. A single laser shot analysis of approximately 4 percent of the spores in a mixture of 0.75 m(3) urban outdoor air doped with approximately 1.1 x 10(5) spores resulted in a 0.04 proportion of false negatives. For that same sample volume of urban air without spores, the proportion of false positives was 0.08.

Real-time, on-line characterization of diesel generator air toxic emissions by resonance-enhanced multiphoton ionization time-of-flight mass spectrometry.

The laser-based resonance-enhanced multiphoton ionization time-of-flight mass spectrometry (REMPI-TOFMS) technique has been applied to the exhaust gas stream of a diesel generator to measure, in real time, concentration levels of aromatic air toxics. Volatile organic compounds, as well as several polycyclic aromatic hydrocarbons were detected in the concentration range of 10-200 ppb in the steady-state diesel generator exhaust. The results were verified and compared with conventional extractive sampling and analytical techniques using gas chromatography/mass spectrometry (GC/MS). The high isomer selectivity of the REMPI-TOFMS instrument provided data for individual xylene isomers that are otherwise (partially) coeluting in standard GC/MS analyses. Good agreement was observed between results for volatile and semivolatile organic compounds obtained with REMPI-TOFMS and conventional extractive sampling. Transient events, such as cold start-ups of the diesel generator, resulted in sharp (less than 15 s) peak emissions that were, for benzene, up to a factor of 90 higher than the predominately constant concentrations observed during steady-state operation; warm restarts resulted in lower peak concentrations by a factor of 2.5. These fast transient emissions are only detectable using a real-time approach (1-s resolution) as demonstrated here using REMPI-TOFMS.