Development and validation of a questionnaire to assess owner and canine quality-of-life and treatment satisfaction in canine allergic dermatitis.

BACKGROUND: Animal and owner quality-of-life (QoL) is pivotal in treatment decisions. Accurate measurement of owner-reported QoL and treatment satisfaction (TS) supports disease burden and treatment benefit evaluation. OBJECTIVES: Develop and evaluate an owner-completed canine dermatitis QoL and TS questionnaire (CDQoL-TSQ) in allergic dogs. MATERIALS AND METHODS: The CDQoL-TSQ was drafted following review of existing measures and expert input. Content validity was assessed through interviews with owners of allergic dogs. Psychometric properties of the QoL domains (Canine QoL, Owner QoL) were evaluated. Score interpretation was derived. RESULTS: Twenty dog owners were interviewed. Item wording was amended following the first 10 interviews. Data from 211 owners were used in the psychometric evaluation. The Canine QoL domain demonstrated strong internal consistency (α = 0.89), test-retest reliability (ICC2,1 = 0.844), moderate convergent validity (r = 0.41) and moderate-high known-groups validity (effect size 0.37-0.64). The Owner QoL domain demonstrated strong internal consistency (α = 0.73), high convergent validity (r = 0.63) and moderate-high known-groups validity (0.43-0.63). Test-retest reliability approached moderate strength (ICC2,1 = 0.490). Group-level interpretation analysis showed minimal important difference of 7.0-13.6 points for dogs and 13.0-13.6 for owners. For individual dogs a change of 6.3 or 12.5 points for dogs, and 12.5 or 18.8 for owners indicates a response. CONCLUSIONS AND CLINICAL RELEVANCE: The CDQOL-TSQ is a two-part assessment to evaluate QoL and TS in canine allergic dermatitis. The QoL questionnaire demonstrated validity and reliability, and interpretation of scores was derived, making it suitable for use in research and practice. The TS module is suitable for clinical setting use to improve owner-veterinarian communication.

Exploring the science, safety, and benefits of air care products: perspectives from the inaugural air care summit.

Seventy-one percent of US households purchase air care products. Air care products span a diverse range of forms, including scented aerosol sprays, pump sprays, diffusers, gels, candles, and plug-ins. These products are used to eliminate indoor malodors and to provide pleasant scent experiences. The use of air care products can lead to significant benefits as studies have shown that indoor malodor can cause adverse effects, negatively impacting quality of life, hygiene, and the monetary value of homes and cars, while disproportionately affecting lower income populations. Additionally, studies have also shown that scent can have positive benefits related to mood, stress reduction, and memory enhancement among others. Despite the positive benefits associated with air care products, negative consumer perceptions regarding the safety of air care products can be a barrier to their use. During the inaugural Air Care Summit, held on 18 May 2018 in the Washington, DC, metropolitan area, multidisciplinary experts including industry stakeholders, academics, and scientific and medical experts were invited to share and assess the existing data related to air care products, focusing on ingredient and product safety and the benefits of malodor removal and scent. At the Summit's completion, a panel of independent experts representing the fields of pulmonary medicine, medical and clinical toxicology, pediatric toxicology, basic science toxicology, occupational dermatology and experimental psychology convened to review the data presented, identify potential knowledge gaps, and suggest future research directions to further assess the safety and benefits of air care products.

Particle and vapor emissions from vat polymerization desktop-scale 3-dimensional printers.

Little is known about emissions and exposure potential from vat polymerization additive manufacturing, a process that uses light-activated polymerization of a resin to build an object. Five vat polymerization printers (three stereolithography (SLA) and two digital light processing (DLP) were evaluated individually in a 12.85 m3 chamber. Aerosols (number, size) and total volatile organic compounds (TVOC) were measured using real-time monitors. Carbonyl vapors and particulate matter were collected for offline analysis using impingers and filters, respectively. During printing, particle emission yields (#/g printed) ranged from 1.3 ± 0.3 to 2.8 ± 2.6 x 108 (SLA printers) and from 3.3 ± 1.5 to 9.2 ± 3.0 x 108 (DLP printers). Yields for number of particles with sizes 5.6 to 560 nm (#/g printed) were 0.8 ± 0.1 to 2.1 ± 0.9 x 1010 and from 1.1 ± 0.3 to 4.0 ± 1.2 x 1010 for SLA and DLP printers, respectively. TVOC yield values (µg/g printed) ranged from 161 ± 47 to 322 ± 229 (SLA printers) and from 1281 ± 313 to 1931 ± 234 (DLP printers). Geometric mean mobility particle sizes were 41.1-45.1 nm for SLA printers and 15.3-28.8 nm for DLP printers. Mean particle and TVOC yields were statistically significantly higher and mean particle sizes were significantly smaller for DLP printers compared with SLA printers (p < 0.05). Energy dispersive X-ray analysis of individual particles qualitatively identified potential occupational carcinogens (chromium, nickel) as well as reactive metals implicated in generation of reactive oxygen species (iron, zinc). Lung deposition modeling indicates that about 15-37% of emitted particles would deposit in the pulmonary region (alveoli). Benzaldehyde (1.0-2.3 ppb) and acetone (0.7-18.0 ppb) were quantified in emissions from four of the printers and 4-oxopentanal (0.07 ppb) was detectable in the emissions from one printer. Vat polymerization printers emitted nanoscale particles that contained potential carcinogens, sensitizers, and reactive metals as well as carbonyl compound vapors. Differences in emissions between SLA and DLP printers indicate that the underlying technology is an important factor when considering exposure reduction strategies such as engineering controls.

Three-dimensional printing with nano-enabled filaments releases polymer particles containing carbon nanotubes into air.

Fused deposition modeling (FDM™) 3-dimensional printing uses polymer filament to build objects. Some polymer filaments are formulated with additives, though it is unknown if they are released during printing. Three commercially available filaments that contained carbon nanotubes (CNTs) were printed with a desktop FDM™ 3-D printer in a chamber while monitoring total particle number concentration and size distribution. Airborne particles were collected on filters and analyzed using electron microscopy. Carbonyl compounds were identified by mass spectrometry. The elemental carbon content of the bulk CNT-containing filaments was 1.5 to 5.2 wt%. CNT-containing filaments released up to 1010 ultrafine (d < 100 nm) particles/g printed and 106 to 108 respirable (d ~0.5 to 2 µm) particles/g printed. From microscopy, 1% of the emitted respirable polymer particles contained visible CNTs. Carbonyl emissions were observed above the limit of detection (LOD) but were below the limit of quantitation (LOQ). Modeling indicated that, for all filaments, the average proportional lung deposition of CNT-containing polymer particles was 6.5%, 5.7%, and 7.2% for the head airways, tracheobronchiolar, and pulmonary regions, respectively. If CNT-containing polymer particles are hazardous, it would be prudent to control emissions during use of these filaments.

A chamber study of alkyl nitrate production formed by terpene ozonolysis in the presence of NO and alkanes.

Organic nitrates are relatively long-lived species and have been shown to have a potential impact on atmospheric chemistry on local, regional, and even global scales. However, the significance of these compounds in the indoor environment remains to be seen. This work describes an impinger-based sampling and analysis technique for organic nitrate species, focusing on formation via terpene ozonolysis in the presence of nitric oxide (NO). Experiments were conducted in a Teflon film environmental chamber to measure the formation of alkyl nitrates produced from α-pinene ozonolysis in the presence of NO and alkanes using gas chromatography with an electron capture detector. For the different concentrations of NO and O3 analyzed, the concentration ratio of [O3]/[NO] around 1 was found to produce the highest organic nitrate concentration, with [O3] = 100 ppb & [NO] = 105 ppb resulting in the most organic nitrate formation, roughly 5 ppb. The experiments on α-pinene ozonolysis in the presence of NO suggest that organic nitrates have the potential to form in indoor air between infiltrated ozone/NO and terpenes from household and consumer products.

Limonene ozonolysis in the presence of nitric oxide: Gas-phase reaction products and yields.

The reaction products from limonene ozonolysis were investigated using the new carbonyl derivatization agent, O-tert-butylhydroxylamine hydrochloride (TBOX). With ozone (O3) as the limiting reagent, five carbonyl compounds were detected. The yields of the carbonyl compounds are discussed with and without the presence of a hydroxyl radical (OH•) scavenger, giving insight into the influence secondary OH radicals have on limonene ozonolysis products. The observed reaction product yields for limonaketone (LimaKet), 7-hydroxyl-6-oxo-3-(prop-1-en-2-yl)heptanal (7H6O), and 2-acetyl-5-oxohexanal (2A5O) were unchanged suggesting OH• generated by the limonene + O3 reaction does not contribute to their formation. The molar yields of 3-isopropenyl-6-oxo-heptanal (IPOH) and 3-acetyl-6-oxoheptanal (3A6O) decreased by 68% and >95%; respectively, when OH• was removed. This suggests that OH• radicals significantly impact the formation of these products. Nitric oxide (NO) did not significantly affect the molar yields of limonaketone or IPOH. However, NO (20 ppb) considerably decreased the molar reaction product yields of 7H6O (62%), 2A5O (63%), and 3A6O (47%), suggesting NO reacted with peroxyl intermediates, generated during limonene ozonolysis, to form other carbonyls (not detected) or organic nitrates. These studies give insight into the transformation of limonene and its reaction products that can lead to indoor exposures.

Diacetyl and 2,3-pentanedione exposure of human cultured airway epithelial cells: Ion transport effects and metabolism of butter flavoring agents.

Inhalation of butter flavoring by workers in the microwave popcorn industry may result in "popcorn workers' lung." In previous in vivo studies rats exposed for 6 h to vapor from the flavoring agents, diacetyl and 2,3-pentanedione, acquired flavoring concentration-dependent damage of the upper airway epithelium and airway hyporeactivity to inhaled methacholine. Because ion transport is essential for lung fluid balance,we hypothesized that alterations in ion transport may be an early manifestation of butter flavoring-induced toxicity.We developed a system to expose cultured human bronchial/tracheal epithelial cells (NHBEs) to flavoring vapors. NHBEs were exposed for 6 h to diacetyl or 2,3-pentanedione vapors (25 or ≥ 60 ppm) and the effects on short circuit current and transepithelial resistance (Rt) were measured. Immediately after exposure to 25 ppm both flavorings reduced Na+ transport,without affecting Cl- transport or Na+,K+-pump activity. Rt was unaffected. Na+ transport recovered 18 h after exposure. Concentrations (100-360 ppm) of diacetyl and 2,3-pentanedione reported earlier to give rise in vivo to epithelial damage, and 60 ppm, caused death of NHBEs 0 h post-exposure. Analysis of the basolateral medium indicated that NHBEs metabolize diacetyl and 2,3-pentanedione to acetoin and 2-hydroxy-3-pentanone, respectively. The results indicate that ion transport is inhibited transiently in airway epithelial cells by lower concentrations of the flavorings than those that result in morphological changes of the cells in vivo or in vitro.

Gas-phase reaction products and yields of terpinolene with ozone and nitric oxide using a new derivatization agent.

The new derivatization agent, O-tert-butylhydroxylamine hydrochloride (TBOX) was used to investigate the carbonyl reaction products from terpinolene ozonolysis. With ozone (O3) as the limiting reagent, four carbonyl compounds were detected: methylglyoxal (MG), 4-methylcyclohex-3-en-1-one, (4MCH), 6-oxo-3-(propan-2-ylidene) heptanal (6OPH), and 3,6-dioxoheptanal (36DOH). The tricarbonyl 36DOH has not been previously observed. Using cyclohexane as a hydroxyl radical (OH•) scavenger, the yields of 6OPH and 36DOH were reduced indicating the influence secondary OH• radicals have on terpinolene ozonolysis products. However, the MG yield increased and the 4MCH yield was unchanged when OH•radicals were scavenged suggesting they are only made by the terpinolene + O3 reaction. The detection of 36DOH using TBOX highlights the advantages of a smaller molecular weight derivatization agent for the detection of multi-carbonyl compounds. The product yields from terpinolene ozonolysis experiments conducted in the presence of 20 ppb nitric oxide (NO) remained unchanged except for MG which decreased. However, in experiments where O3 was kept constant at 50 ppb and NO was varied (20, 50, 100 ppb) MG, 6OPH, 36DOH decreased with increasing NO while 4MCH increased with increasing NO. The use of TBOX derivatization if combined with other derivatization agents may address a recurring need to simply and accurately detect multi-functional oxygenated species in air.

A new agent for derivatizing carbonyl species used to investigate limonene ozonolysis.

A new method for derivatizing carbonyl compounds is presented. The conversion of a series of dicarbonyls to oximes in aqueous solution and from gas-phase sampling was achieved using O-tert-butyl-hydroxylamine hydrochloride (TBOX). Some advantages of using this derivatization agent include: aqueous reactions, lower molecular weight oximes, and shortened oxime-formation reaction time. Additionally, the TBOX derivatization technique was used to investigate the carbonyl reaction products from limonene ozonolysis. With ozone (O3) as the limiting reagent, four carbonyl compounds were detected: 7-hydroxy-6-oxo-3-(prop-1-en-2-yl)heptanal; 3-Isopropenyl-6-oxoheptanal (IPOH), 3-acetyl-6-oxoheptanal (3A6O) and one carbonyl of unknown structure. Using cyclohexane as a hydroxyl (OH•) radical scavenger, the relative yields (peak area) of the unknown carbonyl, IPOH, and 3A6O were reduced indicating the influence secondary OH radicals have on limonene ozonolysis products. The relative yield of the hydroxy-dicarbonyl based on the chromatogram was unchanged suggesting it is only made by the limonene + O3 reaction. The detection of 3A6O using TBOX highlights the advantages of a smaller molecular weight derivatization agent for the detection of multi-carbonyl compounds. The use of TBOX derivatization if combined with other derivatization agents may address a recurring need to simply and accurately detect multi-functional oxygenated species in air.

Investigation of terpinolene + ozone or terpinolene + nitrate radical reaction products using denuder/filter apparatus.

Terpinolene's (1-methyl-4-(propan-2-ylidene)cyclohexene) reaction with ozone or the nitrate radical was investigated using a denuder/filter apparatus in order to characterize gas-phase and particulate reaction products. Identification of the reaction products (i.e., aldehydes, ketones, dicarbonyls and carboxylic acids) was made using two derivatization methods; O-(2,3,4,5,6-pentafluorobenzyl)hydroxylamine (PFBHA) to derivatize the carbonyl products or 3-Ethyl-1-[3-(dimethylamino)propyl]carbodiimide hydrochloride (EDC) and 2,2,2-trifluoroethylamine hydrochloride (TFEA) to derivatize the carboxylic acid products. Proposed carbonyl products for ozonolysis of terpinolene are: 4-methylcyclohex-3-en-1-one, 2-hydroxy-4-methylcyclohex-3-en-1-one, glyoxal, methyl glyoxal, 3-oxobutanal, and 6-oxo-3-(propan-2-ylidene)heptanal. Proposed carbonyl products for nitrate radical reaction of terpinolene are: 2-hydroxy-4-methylcyclohex-3-en-1-one, glyoxal, methyl glyoxal, and 4-oxopentanal. No carboxylic acid products were detected with either oxidizing reactant.

Use of the European Organisation for Research and Treatment of Cancer multiple myeloma module (EORTC QLQ-MY20): a review of the literature 25 years after development.

The European Organisation for Research and Treatment of Cancer Quality of Life Multiple Myeloma Questionnaire (EORTC QLQ-MY20) was developed in 1996 to assess health-related quality of life (HRQoL) in patients with multiple myeloma. Since its development new therapies have prolonged survival in patients with myeloma and new combination agents are likely to impact HRQoL outcomes and its measurement.The aim of this review was to explore the use of the QLQ-MY20 and reported methodological issues.An electronic database search was conducted (1996-June 2020) to identify clinical studies/research that used the QLQ-MY20 or assessed its psychometric properties. Data were extracted from full-text publications/conference abstracts and checked by a second rater.The search returned 65 clinical and 9 psychometric validation studies. The QLQ-MY20 was used in interventional (n = 21, 32%) and observational (n = 44, 68%) studies and the publication of QLQ-MY20 data in clinical trials increased over time. Clinical studies commonly included relapsed patients with myeloma patients (n = 15, 68%) and assessed a range of combinations therapies.QLQ-MY20 subscales (disease symptoms [DS], side effects of treatment [SE], future perspectives [FP], body image [BI]) were defined as secondary (n = 12, 55%) or exploratory (n = 7, 32%) trial endpoints, particularly DS (n = 16, 72%) and SE (n = 16, 72%). Validation articles demonstrated that all domains performed well regarding internal consistency reliability (>0.7), test-reset reliability (intraclass correlation coefficient > =0.85), internal and external convergent and discriminant validity. Four articles reported a high percentage of ceiling effects in the BI subscale; all other subscales performed well regarding floor and ceiling effects.The EORTC QLQ-MY20 remains a widely used and psychometrically robust instrument. While no specific problems were identified from the published literature, qualitative interviews are ongoing to ensure new concepts and side effects are included that may arise from patients receiving novel treatments or from longer survival with multiple lines of treatment.

Use of denuder/filter apparatus to investigate terpene ozonolysis.

A denuder/filter apparatus was used to collect the gaseous and particulate reaction products from ozonlysis of α-pinene, limonene and α-terpineol in an effort to develop sampling techniques for characterizing indoor environment chemistry. Carboxylic acids found in the particulate phase were derivatized to 2,2,2-trifuoroethylamides by reaction with 3-ethyl-1-[3-(dimethylamino)propyl]carbodiimide hydrochloride (EDC) and 2,2,2-trifluoroethylamine hydrochloride (TFEA). Carbonyl compounds collected in both gas phase and particulate phase were derivatized to their respective oximes by reaction with O-(2,3,4,5,6-pentafluoro-benzyl)hydroxylamine hydrochloride (PFBHA). The ozonolysis of α-pinene yielded the carboxylic acids: cis-pinonic acid and pinic acid and the proposed carboxylic acids methanetricarboxylic acid and terpenylic acid; the carbonyls: 4-oxopentanal, norpinonaldehyde, pinon aldehyde and the proposed carbonyl methylidenepropanedial. The ozonolysis of limonene yielded the carboxylic acids: limonic acid and pinic acid and the carbonyls: 1-(4-methylcyclohex-3-en-1-yl)ethanone (4AMCH), glyoxal, methyl glyoxal, 4-oxopentanal and 6-oxo-3-(prop-1-en-2-yl)heptanal (IPOH). The ozonolysis of α-terpineol yielded the proposed carboxylic acids: terpenylic acid and homoterpenylic acid and the carbonyls: (5E)-6-hydroxyhept-5-en-2-one, methyl glyoxal and 4-oxopentanal.

[Clinico-pathological correlations: posterior compartment of the eye and orbit]. / Klinisch-pathologische Korrelationen: Befunde des hinteren Augenabschnitts und der Orbita.

Diseases of the posterior compartment and the orbit are characterised by histological findings, most of which can be reproduced clinically. Examples are the examination of calcifications in retinoblastoma by ultrasonography. In the present review, histological findings of tumour and other diseases of the posterior ocular compartment and the orbit are presented and correlated with the clinical pictures and imaging techniques: uveal melanoma, choroidal nevus, choroidal metastases, choroidal hemangioma, retinoblastoma, Coat's disease, sympathetic ophthalmia, pleomorphic adenoma (benign mixed tumour) of the lacrimal gland, dacryoadenitis, lymphoma, rhabdomyosarcoma, Langerhans cell histiocytosis, orbital metastases, and phthisical eyes. Histopathology is usually the gold standard for a definitive diagnosis. It is very important for residents and those in training to become familiar with clinico-pathological correlations as these provide insight in pathophysiological processes. Regarding ophthalmic surgery, ophthalmic pathology offers the possibility to study wound healing and complications. A close collaboration between clinicians and ocular pathologists allows for an optimised processing of the submitted tissue and diagnosis. Thus, pre- and postoperative care can also be improved. This outstanding knowledge that ophthalmologists have gained over the last decades and beyond, should be preserved and passed on to the next generations in order to maintain a high standard in ophthalmological care.

Feasibility of a Selective Epoxidation Technique for Use in Quantification of Peracetic Acid in Air Samples Collected on Sorbent Tubes.

Peracetic acid is a disinfection agent used in medical and food processing facilities, and occupational exposures have been documented. To facilitate characterization of daily occupational exposures, the current work describes the development of a personal sampling technique to quantify the peracetic acid concentration in air samples. Peracetic acid atmospheres were generated in 100 L Teflon chambers, and samples were collected on 350 mg XAD-7 solid sorbent tubes for 4 h at a flow rate of 250 mL/min using a personal sampling pump. Indirect measurement of peracetic acid was achieved by desorption from the sorbent and subsequent treatment with cyclohexene to initiate an epoxidation reaction, formally known as the Prilezhaev reaction. The epoxidation product, cyclohexene oxide, was quantified by gas chromatography-mass spectrometry. The reaction enabled quantification of peracetic acid with high specificity over the common co-contaminants hydrogen peroxide and acetic acid, which were introduced in 10-fold and 100-fold excess to challenge the reaction. The technique also demonstrated an overall estimate of bias and precision of 11 and 8%, respectively, and a limit of detection of 60 ppbv was estimated. Preliminary storage experiments indicate that unreacted peracetic acid is stable on the sorbent tubes for 72 h when stored at -20 °C following collection. Overall, the specificity of the reaction and capability to sample for longer time periods than current methods, in addition to the use of safer personal sampling materials, demonstrate the utility of this technique for peracetic acid measurement in air.

Reaction rates of ozone and terpenes adsorbed to model indoor surfaces.

UNLABELLED: Reaction rates and reaction probabilities have been quantified on model indoor surfaces for the reaction of ozone with two monoterpenes (Δ(3) -carene and d-limonene). Molar surface loadings were obtained by performing breakthrough experiments in a plug-flow reactor (PFR) packed with beads of glass, polyvinylchloride or zirconium silicate. Reaction rates and probabilities were determined by equilibrating the PFR with both the terpene and the ozone and measuring the ozone consumption rate. To mimic typical indoor conditions, temperatures of 20, 25, and 30°C were used in both types of experiments along with a relative humidity ranging from 10% to 80%. The molar surface loading decreased with increased relative humidity, especially on glass, suggesting that water competed with the terpenes for adsorption sites. The ozone reactivity experiments indicate that higher surface loadings correspond with higher ozone uptake. The reaction probability for Δ(3) -carene with ozone ranged from 2.9 × 10(-6) to 3.0 × 10(-5) while reaction probabilities for d-limonene ranged from 2.8 × 10(-5) to 3.0 × 10(-4) . These surface reaction probabilities are roughly 10-100 times greater than the corresponding gas-phase values. Extrapolation of these results to typical indoor conditions suggests that surface conversion rates may be substantial relative to gas-phase rates, especially for lower volatility terpenoids. PRACTICAL IMPLICATIONS: At present, it is unclear how important heterogeneous reactions will be in influencing indoor concentrations of terpenes, ozone and their reaction products. We observe that surface reaction probabilities were 10 to 100 times greater than their corresponding gas-phase values. Thus indoor surfaces do enhance effective reaction rates and adsorption of terpenes will increase ozone flux to otherwise low-reactivity surfaces. Extrapolation of these results to typical indoor conditions suggests that surface conversion rates may be substantial relative to gas-phase rates, especially for lower volatility terpenoids.

Hydroxyl radical yields from reactions of terpene mixtures with ozone.

UNLABELLED: Chamber studies were conducted to quantify hydroxyl radical (OH·) yields and to determine whether water vapor affected OH· formation in the reactions of ozone (O(3)) with a single terpene, two-component terpene mixtures, and a commercial pine oil cleaning product (POC). Solid-phase microextraction fibers (SPME) were used for sampling the terpenes and the 2-butanone formation from the hydroxyl reaction with 2-butanol as a measure of OH· yields. Analyses were performed using gas chromatography with flame ionization detection. The individual terpenes' OH· yields from α-terpineol, limonene, and α-pinene were 64 ± 8%, 64 ± 6%, and 76 ± 6%, respectively. OH· yields were also measured from two-component mixtures of these terpenes. In each mixture that contained α-terpineol, the overall OH· yield was lower than the modeled OH· yields of the individual components that comprised the reaction mixture. Reactions of a commercial POC with O(3) were also studied to determine how the individual terpenes react in a complex mixture system, and an OH· formation yield of 51 ± 6% was measured. Relative humidity did not have a significant effect on the OH· formation in the mixtures studied here. PRACTICAL IMPLICATIONS: The data presented here demonstrate that mixtures may react differently than the sum of their individual components. By investigating the chemistry of mixtures of chemicals in contrast to the chemistry of individual compounds, a better assessment can be made of the overall impact cleaning products have on indoor environments.

Large-Format Additive Manufacturing and Machining Using High-Melt-Temperature Polymers. Part I: Real-Time Particulate and Gas-Phase Emissions.

The literature on emissions during material extrusion additive manufacturing with 3-D printers is expanding; however, there is a paucity of data for large-format additive manufacturing (LFAM) machines that can extrude high-melt-temperature polymers. Emissions from two LFAM machines were monitored during extrusion of six polymers: acrylonitrile butadiene styrene (ABS), polycarbonate (PC), high-melt-temperature polysulfone (PSU), poly(ether sulfone) (PESU), polyphenylene sulfide (PPS), and Ultem (poly(ether imide)). Particle number, total volatile organic compound (TVOC), carbon monoxide (CO), and carbon dioxide (CO2) concentrations were monitored in real-time. Particle emission rate values (no./min) were as follows: ABS (1.7 × 1011 to 7.7 × 1013), PC (5.2 × 1011 to 3.6 × 1013), Ultem (5.7 × 1012 to 3.1 × 1013), PPS (4.6 × 1011 to 6.2 × 1012), PSU (1.5 × 1012 to 3.4 × 1013), and PESU (2.0 to 5.0 × 1013). For print jobs where the mass of extruded polymer was known, particle yield values (g-1 extruded) were as follows: ABS (4.5 × 108 to 2.9 × 1011), PC (1.0 × 109 to 1.7 × 1011), PSU (5.1 × 109 to 1.2 × 1011), and PESU (0.8 × 1011 to 1.7 × 1011). TVOC emission yields ranged from 0.005 mg/g extruded (PESU) to 0.7 mg/g extruded (ABS). The use of wall-mounted exhaust ventilation fans was insufficient to completely remove airborne particulate and TVOC from the print room. Real-time CO monitoring was not a useful marker of particulate and TVOC emission profiles for Ultem, PPS, or PSU. Average CO2 and particle concentrations were moderately correlated (r s = 0.76) for PC polymer. Extrusion of ABS, PC, and four high-melt-temperature polymers by LFAM machines released particulate and TVOC at levels that could warrant consideration of engineering controls. LFAM particle emission yields for some polymers were similar to those of common desktop-scale 3-D printers.

Large-Format Additive Manufacturing and Machining Using High-Melt-Temperature Polymers. Part II: Characterization of Particles and Gases.

Extrusion of high-melt-temperature polymers on large-format additive manufacturing (LFAM) machines releases particles and gases, though there is no data describing their physical and chemical characteristics. Emissions from two LFAM machines were monitored during extrusion of acrylonitrile butadiene styrene (ABS) and polycarbonate (PC) polymers as well as high-melt-temperature Ultem (poly(ether imide)), polysulfone (PSU), poly(ether sulfone) (PESU), and polyphenylene sulfide (PPS) polymers. Filter samples of particles were collected for quantification of elements and bisphenol A and S (BPA, BPS) and visualization of morphology. Individual gases were quantified on substance-specific media. Aerosol sampling demonstrated that concentrations of elements were generally low for all polymers, with a maximum of 1.6 mg/m3 for iron during extrusion of Ultem. BPA, an endocrine disruptor, was released into air during extrusion of PC (range: 0.4 ± 0.1 to 21.3 ± 5.3 µg/m3). BPA and BPS (also an endocrine disruptor) were released into air during extrusion of PESU (BPA, 2.0-8.7 µg/m3; BPS, 0.03-0.07 µg/m3). Work surfaces and printed parts were contaminated with BPA (<8-587 ng/100 cm2) and BPS (<0.22-2.5 ng/100 cm2). Gas-phase sampling quantified low levels of respiratory irritants (phenol, SO2, toluene, xylenes), possible or known asthmagens (caprolactam, methyl methacrylate, 4-oxopentanal, styrene), and possible occupational carcinogens (benzene, formaldehyde, acetaldehyde) in air. Characteristics of particles and gases released by high-melt-temperature polymers during LFAM varied, which indicated the need for polymer-specific exposure and risk assessments. The presence of BPA and BPS on surfaces revealed a previously unrecognized source of dermal exposure for additive manufacturing workers using PC and PESU polymers.

Investigating ozone-induced decomposition of surface-bound permethrin for conditions in aircraft cabins.

UNLABELLED: The reaction of ozone with permethrin can potentially form phosgene. Published evidence on ozone levels and permethrin surface concentrations in aircraft cabins indicated that significant phosgene formation might occur in this setting. A derivatization technique was developed to detect phosgene with a lower limit of detection of 2 ppb. Chamber experiments were conducted with permethrin-coated materials (glass, carpet, seat fabric, and plastic) exposed to ozone under cabin-relevant conditions (150 ppb O(3), 4.5/h air exchange rate, <1% relative humidity, 1700 ng/cm(2) of permethrin). Phosgene was not detected in these experiments. Reaction of ozone with permethrin appears to be hindered by the electron-withdrawing chlorine atoms adjacent to the double bond in permethrin. Experimental results indicate that the upper limit on the reaction probability of ozone with surface-bound permethrin is approximately 10(-7). Extrapolation by means of material-balance modeling indicates that the upper limit on the phosgene level in aircraft cabins resulting from this chemistry is approximately 1 microg/m(3) or approximately 0.3 ppb. It was thus determined that phosgene formation, if it occurs in aircraft cabins, is not likely to exceed relevant, health-based phosgene exposure guidelines. PRACTICAL IMPLICATIONS: Phosgene formation from ozone-initiated oxidation of permethrin in the aircraft cabin environment, if it occurs, is estimated to generate levels below the California Office of Environmental Health Hazard Assessment acute reference exposure level of 4 microg/m(3) or approximately 1 ppb.

Indoor secondary organic aerosols: Towards an improved representation of their formation and composition in models.

The formation of secondary organic aerosol (SOA) indoors is one of the many consequences of the rich and complex chemistry that occurs therein. Given particulate matter has well documented health effects, we need to understand the mechanism for SOA formation indoors and its resulting composition. This study evaluates some uncertainties that exist in quantifying gas-to-particle partitioning of SOA-forming compounds using an indoor detailed chemical model. In particular, we investigate the impacts of using different methods to estimate compound vapour pressures as well as simulating the formation of highly oxygenated organic molecules (HOM) via auto-oxidation on SOA formation indoors. Estimation of vapour pressures for 136 α-pinene oxidation species by six investigated methods led to standard deviations of 28-216%. Inclusion of HOM formation improved model performance across three of the six assessed vapour pressure estimation methods when comparing against experimental data, particularly when the NO2 concentration was relatively high. We also explored the predicted SOA composition using two product classification methods, the first assuming the molecule is dominated by one functionality according to its name, and the second accounting for the fractional weighting of each functional group within a molecule. The SOA composition was dominated by the HOM species when the NO2-to-α-terpineol ratio was high for both product classification methods, as these conditions promoted formation of the nitrate radical and hence formation of HOM monomers. As the NO2-to-α-terpineol ratio decreased, peroxides and acids dominated the simple classification, whereas for the fractional classification, carbonyl and alcohol groups became more important.