Characterization of Photothermal Desorption-Compatible Diffusive Samplers for Volatile Organic Compounds.

Products and starting materials containing volatile organic compounds (VOCs) can easily be found in a variety of businesses, making them a common source of occupational exposure. To prevent negative impacts on employee health, field industrial hygienists must conduct regular sampling to ensure exposures remain below the regulatory limits set by governmental and professional associations. As such, the need for sensitive and reliable exposure assessment techniques becomes evident. Over the preceding decade, the industrial hygiene research group at the University of Alabama at Birmingham (UAB) has been working on the development of an emerging, preanalytical technique known as photothermal desorption (PTD) to improve upon the analytical sensitivity of currently employed methods. PTD's novel design uses pulses of high-energy light to desorb analytes from thermally conductive, carbonaceous sorbents, to be delivered to downstream analytical detectors. Since PTD's conception, the theoretical framework and advances in sorbent fabrication have been investigated; however, further work is needed to produce a field-ready sampling device for use with PTD. As such, objectives of the present work were to design a PTD-compatible diffusive sampler prototype and characterize the prototype's sampling efficiencies for toluene, n-hexane, trichloroethylene, and isopropyl alcohol. In pursuit of these objectives, the study empirically quantified the sampled masses of toluene, n-hexane, trichloroethylene, and isopropyl alcohol, at occupationally relevant air concentrations, to be 12.17 ± 0.06, 8.2 ± 0.1, 3.97 ± 0.06, and 8.0 ± 0.1 mg, respectively. Moreover, the analyte sampling efficiencies were found to be 2.2 ± 0.1, 1.7 ± 0.1, 1.2 ± 0.1, and 0.51 ± 0.05 (unitless) when comparing empirically (i.e., laboratory observed) sample mass values to theoretically predicted values. The sampling efficiencies and collected sample masses reported herein demonstrate the promising design of PTD-compatible diffusive samplers. When used in conjunction with the PTD method, the prototype samplers present strong evidence for improving analytical sensitivity in exposure assessments of VOCs in the workplace.

Laboratory evaluation of occupational exposure to hand-arm vibration (HAV) during grounds maintenance equipment operations.

INTRODUCTION AND OBJECTIVE: About 2.5 million workers in the USA are exposed to hand-arm vibration (HAV) from power tools. The aims of the study were to evaluate occupational exposure to HAV during grounds maintenance equipment operations and the effect of general work gloves on vibration magnitude under controlled laboratory conditions. MATERIAL AND METHODS: A simulation of grass trimmer, backpack blower, and chainsaw operations was conducted by two participants to measure vibration total value (ahv) using vibration dosimeters wearing gloves. ahv was also measured on the bare hands during grass trimmer and backpack blower operations. RESULTS: ahv of the gloved hand was 3.5-5.8, 1.1-2.0, and 3.0-3.6 m/s2 during the grass trimmer, backpack blower, and chainsaw operations, respectively. ahv of the bare hand was 4.5-7.2 and 1.2-2.3 m/s2 for the grass trimmer and blower operations, respectively. CONCLUSIONS: The highest HAV exposure was observed during the grass trimmer operation which showed higher vibration attenuation of the gloves.

Six new epigean species of the genus Falcileptoneta Komatsu, 1970 (Araneae: Leptonetidae) from South Korea.

Six new leptonetid species belonging to Falcileptoneta Komatsu, 1970 are described from South Korea: F. alboclavata sp. nov., F. decemspina sp. nov., F. innuta sp. nov., F. jindoensis sp. nov., F. stilla sp. nov., and F. triformis sp. nov. All newly described species were sampled from epigean habitats (e.g. leaf litter or under the stone). Based on both male and female (except F. jindoensis sp. nov.), diagnostic characteristics, microscopic images of adult specimens and reproductive structures, and distribution records are provided. Additionally, morphological details to diagnose Falcileptoneta is also discussed.

DNA barcodes reveal population-dependent cryptic diversity and various cases of sympatry of Korean leptonetid spiders (Araneae: Leptonetidae).

Leptonetidae are tiny, rarely encountered spiders that mainly inhabit moist environments, such as caves, leaf litter, and rock piles. Because they are microhabitat specialists, most leptonetid species have short-range endemism, and rarely occur in sympatry. Their small size, relatively simple habitus features and reproductive organ structure increase the difficulty of identification. The identification of leptonetids and other spiders may also be time-consuming due to their sexual dimorphism, polymorphism, and lack of diagnostic characteristics in juveniles. DNA barcoding has been used as an effective tool for species identification to overcome these obstacles. Herein, we conducted a test of DNA barcoding based on 424 specimens of Korean Leptonetidae representing 76 morphospecies. A threshold of 4.2% based on maximum intraspecific genetic divergence was estimated to efficiently differentiate the morphospecies. The species assignments tested by five species delimitation methods (ABGD, ASAP, GMYC, PTP, and bPTP) were consistent with the morphological identifications for only 47 morphospecies (61.8%), indicating many cases of cryptic diversity among the remaining morphospecies. Furthermore, sympatry in leptonetids, which are known to be rare, was revealed to be common in South Korea, especially in epigean species. Our results showed that sympatries within families, congeners, and intraclades potentially occur throughout the entire region of Korea.

Photothermal Desorption of Toluene from Carbonaceous Substrates Using Light Flash.

Millions of workers are occupationally exposed to volatile organic compounds (VOCs) annually. Current exposure assessment techniques primarily utilize sorbent based preconcentrators to collect VOCs, with analysis performed using chemical or thermal desorption. Chemical desorption typically analyzes 1 µL out of a 1 mL (0.1%) extraction volume providing limited sensitivity. Thermal desorption typically analyzes 100% of the sample which provides maximal sensitivity, but does not allow repeat analysis of the sample and often has greater sensitivity than is needed. In this study we describe a novel photothermal desorption (PTD) technique to bridge the sensitivity gap between chemical desorption and thermal desorption. We used PTD to partially desorb toluene from three carbonaceous substrates; activated carbon powder (AC-p), single-walled carbon nanotube (SWNT) powder (SWNT-p) and SWNT felts (SWNT-f). Sorbents were loaded with 435 ug toluene vapour and irradiated at four light energies. Desorption ranged from <0.007% to 0.86% with a single flash depending on substrate and flash energy. PTD was significantly greater and more consistent in SWNT-f substrates compared to AC-p or SWNT-p at all irradiation energies. We attribute the better performance of SWNT-f to greater utilization of its unique nanomaterials properties: high thermal conductivity along the nanotube axis, and greater interconnection within the felt matrix compared to the powdered form.

Evaluating the Effects of Modified Windscreens on Organic Vapor Monitor Performance.

Passive sampling using diffusive samplers has become popular as a convenient means of occupational compliance sampling for volatile organic compounds (VOCs). However, diffusive samplers possess sensitivity limitations when sampling low concentrations and for short durations. To reduce these limitations, our research team has been developing a novel method of sample recovery called photothermal desorption (PTD), which uses high energy visible light pulses to desorb analytes from sampling media. Newly designed passive samplers that will use PTD will be equipped with windscreens in a similar design with the 3M OVM. In a preliminary design effort, the present work sought to find a suitable, windscreen for future use in a PTD-compatible diffusive sampler prototype that would be similar to those found in commercially available diffusive samplers. To do so, 2 stainless steel windscreens (wire diameters 0.015″ and 0.0055″ respectively) were compared to a standard windscreen by exposing modified (ie, steel mesh installed) and non-modified 3M OVM samplers to 3 analytes. To mimic in-field conditions, each sampler was exposed to analyte concentrations at their short-term and personal exposure limits (STELs and PELs). From these comparisons, it was determined that the 0.0055″ mesh was most similar to the standard windscreen in contributing to sample collection based on the uptake and concentration determinations for each analyte and concentration.

Determination of activated carbon fiber adsorption capacity for several common organic vapors: applications for respiratory protection.

In the context of workplace safety, activated carbon in the fiber form (i.e., activated carbon fiber, ACF) represents an alternative adsorbent to granular activated carbon (GAC) for use in organic vapor respiratory protection devices. ACFs are high surface area carbonaceous materials that are often available in a self-supporting non-woven form. The physical form of ACF suggests the potential for a filtration medium that is capable of supporting both organic vapor adsorption and particulate filtration. To study the application of these materials in respiratory protection devices, ACFs (ACFF 1200 m2/g, ACFF 1800 m2/g, and ACFF 2000 m2/g) were challenged with representative organic vapors (toluene, hexane, and methyl ethyl ketone (MEK)) at an occupationally relevant concentration (200 ppm). Breakthrough curves were generated for at least three different bed weights of adsorbent. Pressure drop (i.e., the resistance across the filtration media) was also measured to determine maximum ACF bed depths for use in respiratory protection devices. Breakthrough experiments indicate that ACFF 2000 has the highest adsorption capacity for toluene (381 mg/g), followed by ACFF 1800 and ACFF 1200 (344 mg/g and 239 mg/g, respectively). A similar trend was observed for hexane: 221 mg/g, 196 mg/g, and 146 mg/g for ACFF 2000, ACFF 1800, and ACFF 1200, respectively. ACFF 1200 showed the highest adsorption capacity for the polar adsorbate MEK (168 mg/g), followed by ACFF 1800 and ACFF 2000 (166 mg/g and 147 mg/g, respectively). Based on the constraints of pressure drop, it seems unlikely the exclusive use of ACF in a filtering facepiece respirator can provide an adsorbent mass sufficient for full shift protection against organic vapor contaminants at or above the legally enforceable permissible exposure level (PEL). Nevertheless, the incorporation of ACF into a facepiece respirator appears promising for "nuisance odor" applications; i.e., the further reduction of organic vapor concentrations when workplace exposures are already below PEL concentrations.Implications: This research brings innovation to the field of occupational health and air pollution control technology by investigating the adsorption performance of activated carbon fiber (ACF) media in the context of worker respiratory protection. ACF properties such as high specific surface area (m2/g), high permeability to airflow, and rapid adsorption kinetics make it ideal for use in thin, N95-style respirators for organic vapors. Respiratory protection is an exciting and relevant application for ACF media. A lightweight adsorbent such as ACF, if incorporated into an N95-style respirator, could potentially provide nuisance-level VOC protection in a physical form that is accessible to workers and consistent with OSHA's voluntary use provisions for facepiece respirators. The research presented in this manuscript represents one of several steps planned in the characterization of ACF media for this particular application.

Adsorption Characteristics of Activated Carbon Fibers in Respirator Cartridges for Toluene.

Respirator use has been shown to be associated with overall discomfort. Activated carbon fiber (ACF) has potential as an alternative adsorbent for developing thinner, lightweight, and efficient respirators due to its larger surface area, microporosity, and fabric form. The purpose of this pilot study was to determine the adsorption characteristics of commercially available ACF in respirator cartridges with varying ACF composition for toluene protection. Seven ACF types (one cloth, six felt) with varying properties were tested. Seven ACF cartridge configurations with varying ACF composition were challenged with five toluene concentrations (20-500 ppm) at constant air temperature (23 °C), relative humidity (50%), and air flow (32 LPM). Breakthrough curves were obtained using photoionization detectors. Breakthrough times (10%, 50%, and 5 ppm) and adsorption capacities were compared among ACF cartridge configurations to determine their suitable application in respiratory protection. Results showed that ACF cartridges containing the densest ACF felt types had the longest average breakthrough times (e.g., ~250-270 min to reach 5 ppm breakthrough time) and those containing ACF felt types with the highest specific surface areas had the highest average adsorption capacity (~450-470 mg/g). The ACF cartridges demonstrated breakthrough times of <1 h for 500 ppm toluene and 8-16 h for 20 ppm toluene. The ACF cartridges are more reliable for use at low ambient toluene concentrations but still have potential for use at higher concentrations for short-term protection. ACF felt forms with appropriate properties (density of ~0.07 g/cm3; specific surface area of ~2000 m2/g) have shown promising potential for the development of lighter and thinner respirators for protection against toluene.

Decontamination of respirators amid shortages due to SARS-CoV-2.

The pandemic created by SARS-CoV-2 has caused a shortage in the supplies of N95 filtering facepiece respirators (FFRs), disposable respirators with at least 95% efficiency to remove non-oily airborne particles, due to increasing cases all over the world. The current article reviewed various possible decontamination methods for FFR reuse including ultraviolet germicidal irradiation (UVGI), hydrogen peroxide vapor (HPV), microwave-generated steam (MGS), hydrogen peroxide gas plasma (HPGP), and 70% or higher ethanol solution. HPV decontamination was effective against bacterial spores (6 log10 reduction of Geobacillus stearothermophilus spores) on FFRs and viruses (> 4 log10 reduction of various types of viruses) on inanimate surfaces, and no degradation of respirator materials and fit has been reported. 70% or higher ethanol decontamination showed high efficacy in inactivation of coronaviruses on inanimate surfaces (> 3.9 log10 reduction) but it was lower on FFRs which filtration efficiency was also decreased. UVGI method had good biocidal efficacy on FFRs (> 3 log10 reduction of H1N1 virus) combined with inexpensive, readily available equipment; however, it was more time-consuming to ensure sufficient reduction in SARS-CoV-2. MGS treatment also provided good viral decontamination on FFRs (> 4 log10 reduction of H1N1 virus) along with less time-intensive process and readily available equipment while inconsistent disinfection on the treated surfaces and deterioration of nose cushion of FFRs were observed. HPGP was a good virucidal system (> 6 log10 reduction of Vesicular stomatitis virus) but filtration efficiency after decontamination was inconsistent. Overall, HPV appeared to be one of the most promising methods based on the high biocidal efficacy on FFRs, preservation of respirator performance after multiple cycles, and no residual chemical toxicity. Nonetheless, equipment cost and time of the HPV process and a suitable operating room need to be considered.

Determining the Thermal Properties of Buckypapers Used in Photothermal Desorption.

Volatile organic compounds (VOCs) pose an occupational exposure risk due to their commonplace usage across industrial and vocational sectors. With millions of workers annually exposed, monitoring personal VOC exposures becomes an important task. As such, there is a need to improve current monitoring techniques by increasing sensitivity and reducing analysis costs. Recently, our lab developed a novel, preanalytical technique known as photothermal desorption (PTD). PTD uses pulses of high-energy, visible light to thermally desorb analytes from carbonaceous sorbents, with single-walled carbon nanotube buckypapers (BPs) having the best overall performance. To apply this new technology most effectively for chemical analysis, a better understanding of the theoretical framework of the thermal phenomena behind PTD must be gained. The objectives of the present work were 3-fold: measure the thermal response of BPs during irradiation with light; determine the best method for conducting such measurements; and determine the thermal conductivity of BPs. BPs were exposed to four energy densities, produced by light pulses, ranging from 0.28 to 1.33 J/cm2, produced by a xenon flash lamp. The resulting temperature measurements were obtained via fast response thermocouple (T/C) mounted to BPs by three techniques (pressing, adhering, and embedding). Temperature increase measured by T/C using the adhering and pressing techniques resulted in similar values, 29.2 ± 0.8 to 56 ± 3 °C and 29.1 ± 0.9 to 50 ± 5 °C, respectively, while temperature increase measured by embedding the T/C into the BP showed statistically larger increases ranging from 35.2 ± 0.9 to 76 ± 4 °C. Peak BP temperatures for each mounting technique were also compared with the temperatures generated by the light source, which resulted in embedded BPs demonstrating the most temperature conversion among the techniques (74-86%). Based on these results, embedding T/Cs into the BP was concluded to be the best way to measure BP thermal response during PTD. Additionally, the present work modeled BP thermal conductivity using a steady-state comparative technique and found the material's conductivity to be 10.6 ± 0.6 W/m2. The present work's findings will help pave the way for future developments of the PTD method by allowing calculation of the energy density necessary to attain a desired sorbent temperature and providing a means for comparing BP fabrication techniques and evaluating BP suitability for PTD before conducting PTD trials with analytes of interest. Sorbents with greater thermal conductivity are expected to desorb more evenly and withstand higher energy density exposures.

Evaluation of Aldehydes, Polycyclic Aromatic Hydrocarbons, and PM2.5 Levels in Food Trucks: A Pilot Study.

Background: The food truck industry has rapidly expanded in the United States and kitchen environments can contain harmful contaminants from cooking emissions. The objective of this study was to examine the levels of aldehydes, polycyclic aromatic hydrocarbons (PAHs), and Particulate Matter (PM)2.5 generated from cooking process in food trucks. Methods: Area sampling was performed twice at two participating food trucks during work shifts. Nine aldehydes and eighteeen PAHs were analyzed according to the relevant standard methods while PM2.5 was measured with a real time monitor. Ventilation performance of the food truck exhaust hoods was also investigated using a thermal anemometer. Findings: Formaldehyde was the only aldehyde detected in all samples with a concentration range of 7.16 to 53.68 µg/m3. No PAHs were detected above the limit of quantification. Average PM2.5 concentrations ranged from 0.65 to 7.03 mg/m3. Food Trucks 1 and 2 have an average exhaust flow rate of 211 and 215 L/s per linear meter of hood, respectively. Conclusions/Application to practice: Overall, Food Truck 2 had consistently higher levels of aldehydes and PM2.5 with comparable ventilation performance as Food Truck 1. The higher exposure levels of Food Truck 2 could possibly be attributed to a larger volume of food orders and the heavy duty cooking equipment with an exhaust flow rate below the American Society of Heating, Refrigerating and Air-Conditioning Engineers (ASHRAE) recommendations. Although more investigations need to be performed, the findings could be used to raise awareness of food truck workers and health practitioners to reduce potential exposure risks.

Laboratory Estimation of Occupational Exposures to Volatile Organic Compounds During Nail Polish Application.

In the United States, there are more than 120,000 nail salons in which workers could be potentially exposed to a number of volatile organic compounds (VOCs) used in various procedures. Measuring workers exposure in the field is time-consuming and could be very expensive. The purpose of this study was to estimate the VOC levels in the proximity of workers in nail salons through simulating the application process of some popular nail polishes in a laboratory chamber. The worst-case scenario was defined as a worker's exposure during nail polish application to one set of fingernails every 15 minutes for an 8-hour shift (total nail sets = 32). Nail polish was applied on paper plates in a flow-controlled test chamber. Air was sampled during the application of five different nail polishes for 8 hours using passive air samplers and the experiment was triplicated. Passive samplers were used for VOCs and formaldehyde. In this worst-case scenario setting, a total of 17 VOCs were detected, with eight that were found in all the samples. The mean concentration of butyl acetate (161-330 ppm, parts per million) and ethyl acetate (440 ppm) exceeded the threshold limit value (TLV) of 150 ppm and 400 ppm, respectively. Formaldehyde was analyzed separately and the mean concentrations exceeded the TLV of 0.10 ppm in all types of nail polish, ranging from 0.12 ppm to 0.22 ppm. Occupational safety and health professionals could use these data to increase awareness of workers' potential exposure to high levels of VOCs in nail salons and recommend practical measures to reduce potential exposures.

Photothermal desorption of single-walled carbon nanotubes and coconut shell-activated carbons using a continuous light source for application in air sampling.

Many techniques exist to measure airborne volatile organic compounds (VOCs), each with differing advantages; sorbent sampling is compact, versatile, has good sample stability, and is the preferred technique for collecting VOCs for hygienists. Development of a desorption technique that allows multiple analyses per sample (similar to chemical desorption) with enhanced sensitivity (similar to thermal desorption) would be helpful to field hygienists. In this study, activated carbon (AC) and single-walled carbon nanotubes (SWNT) were preloaded with toluene vapor and partially desorbed with light using a common 12-V DC, 50-W incandescent/halogen lamp. A series of experimental chamber configurations were explored starting with a 500-ml chamber under static conditions, then with low ventilation and high ventilation, finally a 75-ml high ventilation chamber was evaluated. When preloaded with toluene and irradiated at the highest lamp setting for 4min, AC desorbed 13.9, 18.5, 23.8, and 45.9% of the loaded VOC mass, in each chamber configuration, respectively; SWNT desorbed 25.2, 24.3, 37.4, and 70.5% of the loaded VOC mass, respectively. SWNT desorption was significantly greater than AC in all test conditions (P = 0.02-<0.0001) demonstrating a substantial difference in sorbent performance. When loaded with 0.435mg toluene and desorbed at the highest lamp setting for 4min in the final chamber design, the mean desorption for AC was 45.8% (39.7, 52.0) and SWNT was 72.6% (68.8, 76.4) (mean represented in terms of 95% confidence interval). All desorption measurements were obtained using a field grade photoionization detector; this demonstrates the potential of using this technique to perform infield prescreening of VOC samples for immediate exposure feedback and in the analytical lab to introduce sample to a gas chromatograph for detailed analysis of the sample.

pH-responsive hydrogel cubes for release of doxorubicin in cancer cells.

We report on a novel type of shaped hydrogel microparticles which undergo large, rapid, and reversible volume changes in response to solution pH. The cubic hydrogels are produced as interconnected poly(methacrylic acid) (PMAA) network replicas of mesoporous manganese oxide templates by sequential infiltration of (PMAA) and poly(N-vinylpyrrolidone) (PVPON), followed by cross-linking of PMAA and template dissolution. The integrated advantages of the porous cubic sacrificial templates and responsive PMAA matrix enable synthesis of monodisperse and pH-sensitive hydrogel cubes in a rapid, facile, and reproducible manner. These hydrogel cubes display a reversible 2-fold change in size while maintaining their shape in response to pH variations. The swelling behavior of cubic and spherical hydrogel particles is controlled by the network structure which is regulated by the PMAA molecular weight. These networks maintain their three-dimensional shapes in the dry state. No cytotoxicity is found for cubic and spherical hydrogels upon their interactions with human cancer cells for various time intervals. Finally, pH-triggered loading and release of doxorubicin to and from the cubic hydrogels is shown and their anticancer effect is demonstrated. The viability of A549 and HeLa cancer cells was significantly decreased upon interaction with doxorubicin-loaded cubic hydrogels. The approach presented here provides a new platform of multi-functional particles with highly-controlled geometry, size, composition, and responsive properties to be potentially used in targeted drug delivery for cancer therapy.

Expression of dynamin II in odontoblast during mouse tooth development.

Odontoblasts secrete a collagen-based matrix and release numerous membrane-bound matrix vesicles, which are involved in dentin formation during tooth development. Dynamin II is a GTPase protein that contributes a variety of vesicular budding events, such as endocytotic membrane fission, caveolae internalization and protein trafficking in the Golgi apparatus. However, the expression and function of dynamin II in odontoblasts has not been reported. Therefore, this study examined the expression and possible role of dynamin II in odontoblasts during tooth development and mineralization. The levels of mRNA and protein expression in MDPC23 cells were significantly high at the early stages of differentiation and then decreased gradually thereafter. Immunohistochemistry showed that dynamin II was not expressed near the region of the odontoblasts at embryonic day 17 (E17) and E21. However, dynamin II was expressed strongly in the odontoblast layer at postnatal day 1 (PN1) and decreased gradually at PN3 and PN5. In addition, at PN15 in the functional stage, the dynamin II protein was also expressed in the odontoblast process as well as adjacent to the nuclear region. In conclusion, dynamin II may be involved in the transport of vesicles containing collageneous and non-collageneous proteins for dentin formation in odontoblast, suggesting that it is a good nanomolecule as a candidate to regulate the secretion of collagen on the bone and other nano material.