During use of sodium hypochlorite bleach, gas-phase hypochlorous acid (HOCl) and chlorine (Cl2) are released, which can react with organic compounds present in indoor air. Reactivity between HOCl/Cl2 and limonene, a common constituent of indoor air, has been observed. The purpose of this study was to characterize the chemical species generated from gas-phase reactions between HOCl/Cl2 and limonene. Gas-phase reactions were prepared in Teflon chambers housing HOCl, Cl2, and limonene. The resulting chemical products were analyzed using gas-phase preconcentration, followed by gas chromatography and high-resolution mass spectrometry. Several chlorinated products were detected, including limonene species containing one, two, and three chlorines and limonene chlorohydrin. Product concentrations and yields were estimated for the most abundant products, and greater than 80% of transformed limonene was represented in the detected products. Temporal sampling of the reactions allowed time courses to be plotted for limonene decay and chlorinated limonene product generation under different conditions, including the treatments of HOCl/Cl2, Cl2 only, high vs low relative humidity, and +/- ozone. These experiments add product speciation, yield estimates, and an understanding of environmental factors affecting product formation to previous studies, further highlighting the chemical transformations initiated by sodium hypochlorite bleach in indoor air.

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 (CO(2)) concentrations were monitored in real-time. Particle emission rate values (no./min) were as follows: ABS (1.7 × 10(11) to 7.7 × 10(13)), PC (5.2 × 10(11) to 3.6 × 10(13)), Ultem (5.7 × 10(12) to 3.1 × 10(13)), PPS (4.6 × 10(11) to 6.2 × 10(12)), PSU (1.5 × 10(12) to 3.4 × 10(13)), and PESU (2.0 to 5.0 × 10(13)). For print jobs where the mass of extruded polymer was known, particle yield values (g(-1) extruded) were as follows: ABS (4.5 × 10(8) to 2.9 × 10(11)), PC (1.0 × 10(9) to 1.7 × 10(11)), PSU (5.1 × 10(9) to 1.2 × 10(11)), and PESU (0.8 × 10(11) to 1.7 × 10(11)). 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 CO(2) 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.

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/m(3) 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/m(3)). BPA and BPS (also an endocrine disruptor) were released into air during extrusion of PESU (BPA, 2.0-8.7 μg/m(3); BPS, 0.03-0.07 μg/m(3)). Work surfaces and printed parts were contaminated with BPA (<8-587 ng/100 cm(2)) and BPS (<0.22-2.5 ng/100 cm(2)). Gas-phase sampling quantified low levels of respiratory irritants (phenol, SO(2), 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.

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. © 2022 Elsevier Inc.. All rights reserved.

Objectives. To assess SARS-CoV-2 transmission within a correctional facility and recommend mitigation strategies.Methods. From April 29 to May 15, 2020, we established the point prevalence of COVID-19 among incarcerated persons and staff within a correctional facility in Arkansas. Participants provided respiratory specimens for SARS-CoV-2 testing and completed questionnaires on symptoms and factors associated with transmission.Results. Of 1647 incarcerated persons and 128 staff tested, 30.5% of incarcerated persons (range by housing unit = 0.0%-58.2%) and 2.3% of staff tested positive for SARS-CoV-2. Among those who tested positive and responded to symptom questions (431 incarcerated persons, 3 staff), 81.2% and 33.3% were asymptomatic, respectively. Most incarcerated persons (58.0%) reported wearing cloth face coverings 8 hours or less per day, and 63.3% reported close contact with someone other than their bunkmate.Conclusions. If testing remained limited to symptomatic individuals, fewer cases would have been detected or detection would have been delayed, allowing transmission to continue. Rapid implementation of mass testing and strict enforcement of infection prevention and control measures may be needed to mitigate spread of SARS-CoV-2 in this setting. (Am J Public Health. Published online ahead of print March 18, 2021: e1-e10. https://doi.org/10.2105/AJPH.2020.306117).

There is a paucity of data on additive manufacturing process emissions and personal exposures in real-world workplaces. Hence, we evaluated atmospheres in four workplaces utilizing desktop &quot;3-dimensional&quot; (3-d) printers [fused filament fabrication (FFF) and sheer] for production, prototyping, or research. Airborne particle diameter and number concentration and total volatile organic compound concentrations were measured using real-time instruments. Airborne particles and volatile organic compounds were collected using time-integrated sampling techniques for off-line analysis. Personal exposures for metals and volatile organic compounds were measured in the breathing zone of operators. All 3-d printers that were monitored released ultrafine and fine particles and organic vapors into workplace air. Particle number-based emission rates (#/min) ranged from 9.4 times 109 to 4.4 times 1011 (n = 9 samples) for FFF 3-d printers and from 1.9 to 3.8 times 109 (n = 2 samples) for a sheer 3-d printer. The large variability in emission rate values reflected variability from the printers as well as differences in printer design, operating conditions, and feedstock materials among printers. A custom-built ventilated enclosure evaluated at one facility was capable of reducing particle number and total organic chemical concentrations by 99.7% and 53.2%, respectively. Carbonyl compounds were detected in room air; however, none were specifically attributed to the 3-d printing process. Personal exposure to metals (aluminum, iron) and 12 different organic chemicals were all below applicable NIOSH Recommended Exposure Limit values, but results are not reflective of all possible exposure scenarios. More research is needed to understand 3- d printer emissions, exposures, and efficacy of engineering controls in occupational settings.

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 m(3) 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 10(8) (SLA printers) and from 3.3 +/- 1.5 to 9.2 +/- 3.0 x 10(8) (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 10(10) and from 1.1 +/- 0.3 to 4.0 +/- 1.2 x 10(10) for SLA and DLP printers, respectively. TVOC yield values (microg/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.

Background Emerging reports suggest the potential for adverse health effects from exposure to emissions from some additive manufacturing (AM) processes. There is a paucity of real-world data on emissions from AM machines in industrial workplaces and personal exposures among AM operators. Methods Airborne particle and organic chemical emissions and personal exposures were characterized using real-time and time-integrated sampling techniques in four manufacturing facilities using industrial-scale material extrusion and material jetting AM processes. Results Using a condensation nuclei counter, number-based particle emission rates (ERs) (number/min) from material extrusion AM machines ranged from 4.1 x 1010 (Ultem filament) to 2.2 x 1011 [acrylonitrile butadiene styrene and polycarbonate filaments). For these same machines, total volatile organic compound ERs (microg/min) ranged from 1.9 x 104 (acrylonitrile butadiene styrene and polycarbonate) to 9.4 x 104 (Ultem). For the material jetting machines, the number-based particle ER was higher when the lid was open (2.3 x 1010 number/min) than when the lid was closed (1.5-5.5 x 109 number/min); total volatile organic compound ERs were similar regardless of the lid position. Low levels of acetone, benzene, toluene, and m,p-xylene were common to both AM processes. Carbonyl compounds were detected; however, none were specifically attributed to the AM processes. Personal exposures to metals (aluminum and iron) and eight volatile organic compounds were all below National Institute for Occupational Safety and Health (NIOSH)-recommended exposure levels. Conclusion Industrial-scale AM machines using thermoplastics and resins released particles and organic vapors into workplace air. More research is needed to understand factors influencing real-world industrial-scale AM process emissions and exposures.

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 10(10) ultrafine (d <100 nm) particles/g printed and 10(6) to 10(8) respirable (d ~0.5 to 2 mum) 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. This article is protected by copyright. All rights reserved.

Formaldehyde allergic contact dermatitis (ACD) may be due to products with free formaldehyde or formaldehyde-releasing agents, however, assessment of formaldehyde levels in such products is infrequently conducted. The present study quantifies total releasable formaldehyde from "in-use" products associated with formaldehyde ACD and tests the utility of commercially available formaldehyde spot test kits. Personal care products from 2 patients with ACD to formaldehyde were initially screened at the clinic for formaldehyde using a formaldehyde spot test kit. Formaldehyde positive products were sent to the laboratory for confirmation by gas chromatography-mass spectrometry. In addition, 4 formaldehyde spot test kits were evaluated for potential utility in a clinical setting. Nine of the 10 formaldehyde spot test kit positive products obtained from formaldehyde allergic patients had formaldehyde with total releasable formaldehyde levels ranging from 5.4 to 269.4 microg/g. Of these, only 2 shampoos tested listed a formaldehyde-releasing agent in the ingredients or product literature. Subsequently, commercially available formaldehyde spot test kits were evaluated in the laboratory for ability to identify formaldehyde in personal care products. Chemical based formaldehyde spot test were more reliable than the enzymatic based test in identifying product releasable formaldehyde content. It is concluded that product labeled ingredient lists and available information are often inadequate to confirm the potential for formaldehyde exposure and chemical based spot test kits may have utility for identification of potential formaldehyde exposure from personal care products.

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 alpha-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 alpha-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.

The chemical composition of indoor air changes due to the reactive nature of the indoor environment. Historically, only the stable parent compounds were investigated due to their ease of measurement by conventional methods. Today, however, scientists can better characterize oxidation products (gas and particulate-phase) formed by indoor chemistry. An understanding of occupant exposure can be developed through the investigation of indoor oxidants, the use of derivatization techniques, atmospheric pressure detection, the development of real-time technologies, and improved complex modeling techniques. Moreover, the connection between exposure and health effects is now receiving more attention from the research community. Nevertheless, a need still exists for improved understanding of the possible link between indoor air chemistry and observed acute or chronic health effects and long-term effects such as work-related asthma.

The yields of carbonyl-containing reaction products from the ozonolysis of alpha-pinene have been investigated using concentrations of ozone found in the indoor environment ([O3] ≤ 100 ppb). An impinger was used to collect gas-phase oxidation products in water, where the derivatization agent O-tert-butylhydroxylamine hydrochloride (TBOX) and gas chromatography-mass spectrometry were used to identify carbonyl-containing species. Seven carbonyl-containing products were observed. The yield of the primary product, pinonaldehyde was measured to be 76 %. Using cyclohexane as a hydroxyl radical (OH) scavenger, the yield of pinonaldehyde decreased to 46 %, indicating the influence secondary OH radicals have on alpha-pinene ozonolysis products. Furthermore, the use of TBOX, a small molecular weight derivatization agent, allowed for the acquisition of the first mass spectral data of oxopinonaldehyde, a tricarbonyl reaction product of alpha-pinene ozonolysis. The techniques described herein allow for an effective method for the collection and identification of terpene oxidation products in the indoor environment.

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 + O3reaction 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.

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 + O3reaction. 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 O3was 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.

Sesquiterpenes are constituents of a variety of essential oils that are used in flavorings, perfumes, personal care, and cleaning products. Two sesquiterpenes that are commonly used as indoor fragrances are valencene and farnesol. Knowing the reaction rate constants of these chemicals with ozone (O3) and nitrate radical (NO3&bull) is an important factor in determining their fate indoors. In this study, the bimolecular rate constants of kO3+valencene (0.350.9) 10 -16, kO3+farnesol (215.2) 10 -16, kNO3&bull+valencene (7.92.0) 10 -12, and kNO3&bull+farnesol (4411) 10-12 cm3 molecule-1 s-1 were measured using the relative rate technique at 297 3 K and 1 atm total pressure. Using the rate constants reported here and measured/modeled indoor concentrations of O3 and NO3&bull (20 ppb and 1 ppt, respectively), pseudo-first-order-rate lifetimes k'O3+valencene (0.06), k'O3+farnesol (3.8), k'NO3+valencene (0.7), and k'NO3&middot+farnesol (3.9)h-1 were determined.

Nitrate radical (NO(3)) surface chemistry of indoor environments has not been well studied due to the difficulty in generating and maintaining NO(3) at low concentrations for long term exposures. This article presents the Surface Chemistry Reactant Air Delivery and Experiment System (SCRADES), a novel feedback controlled system developed to deliver nitrate radicals at specified concentrations (50-500 ppt, +/-30 ppt) and flow rates (500-2000 ml min(-1)) to a variety of indoor surfaces to initiate reaction chemistry for periods of up to 72 h. The system uses a cavity ring-down spectrometer (CRDS), with a detection limit of 1.7 ppt, to measure the concentration of NO(3) supplied to a 24 l experiment chamber. Nitrate radicals are introduced via thermal decomposition of N(2)O(5) and diluted with clean dry air until the desired concentration is achieved. Additionally, this article addresses details concerning NO(3) loss through the system, consistency of the NO(3) concentration delivered, and stability of the CRDS cavity over long exposure durations (72 h).

Over the last two decades, there has been an increasing awareness regarding the potential impact of indoor air pollution on human health. People working in an indoor environment often experience symptoms such as eye, nose and throat irritation. Investigations into these complaints have ascribed the effects, in part, to compounds emitted from building materials, cleaning/consumer products, and indoor chemistry. One suspect indoor air contaminant that has been identified is the dicarbonyl 4-oxopentanal (4-OPA). 4-OPA is generated through the ozonolysis of squalene and several high volume production compounds that are commonly found indoors. Following preliminary workplace sampling that identified the presence of 4-OPA, these studies examined the inflamatory and allergic responses to 4-OPA following both dermal and pulmonary exposure using a murine model. 4-OPA was tested in a combined local lymph node assay (LLNA) and identified to be an irritant and sensitizer. A Th1-mediated hypersensitivity response was supported by a positive response in the mouse ear swelling test (MEST). Pulmonary exposure to 4-OPA caused a significant elevation in nonspecific airway hyperreactivity, increased numbers of lung associated lymphocytes and neutrophils and increased interferon-gamma production by lung associated lymph nodes. These results suggest that both dermal and pulmonary exposure to 4-OPA may elicit irritant and allergic responses and may help to explain some of the adverse health effects associated with poor indoor air quality.

Indoor environments are dynamic reactors where consumer products (such as cleaning agents, deodorants, and air fresheners) emit volatile organic compounds (VOCs) that can subsequently interact with indoor oxidants such as ozone (O(3)), hydroxyl radicals, and nitrate radicals. Typically, consumer products consist of mixtures of VOCs and semi-VOCs which can react in the gas-phase or on surfaces with these oxidants to generate a variety of oxygenated products. In this study, the reaction of a pine-oil cleaner (POC) with O(3) (100ppb) on a urethane-coated vinyl flooring tile was investigated at 5% and 50% relative humidity. These results were compared to previous alpha-terpineol+O(3) reactions on glass and vinyl surfaces. Additionally, other terpene and terpene alcohol mixtures were formulated to understand the emission profiles as seen in the POC data. Results showed that the alpha-terpineol+O(3) reaction products were the prominent species that were also observed in the POC/O(3) surface experiments. Furthermore, alpha-terpineol+O(3) reactions generate the largest fraction of oxygenated products even in equal mixtures of other terpene alcohols. This finding suggests that the judicial choice of terpene alcohols for inclusion in product formulations may be useful in reducing oxidation product emissions.

Terpenes and terpene alcohols are prevalent compounds found in a wide variety of consumer products including soaps, flavorings, perfumes, and air fresheners used in the indoor environment. Knowing the reaction rate of these chemicals with the nitrate radical is an important factor in determining their fate indoors. In this study, the bimolecular rate constants of k[NO3+geraniol] (16.6 +/- 4.2) × 10(−12), k[NO3+citronellol] 12.1 +/- 3) × 10(−12), and k[NO3+dihydromyrcenol] (2.3 +/- 0.6) × 10(−14) cm(3) molecule(−1) s(−1) were measured using the relative rate technique for the reaction of the nitrate radical (NO3) with 2,6-dimethyl-2,6-octadien-8-ol (geraniol), 3,7-dimethyl-6-octen-1-ol (citronellol), and 2,6-dimethyl-7-octen-2-ol (dihydromyrcenol) at (297 +/- 3) K and 1 atmosphere total pressure. Using the geraniol, citronellol, or dihydromyrcenol + NO3 rate constants reported here, pseudo-first-order rate lifetimes (k') of 1.5, 1.1, and 0.002 h(−1) were determined, respectively. © 2010 Wiley Periodicals, Inc.

The bimolecular rate constant of k(NO3 center dot+beta-ionone) (9.4 +/- 2.4 x 10(-12) cm(3) molecule(-1) s(-1) was measured using the relative rate technique for the reaction of the nitrate radical (NO3 center dot) with 4-(2,6,6-trimethyl-1-cyclohexen-1-yl)-3-buten-2-one (beta-ionone) at (297 +/- 3) K and I atmosphere total pressure. in addition, the products of beta-ionone + NO3 center dot reaction were also investigated. The identified reaction products were glyoxal (HC(=O)C(=O)H), and methylglyoxal (CH3C(=O)C(=O)H). Derivatizing agents O-(2,3,4,5,6-pentafluorobenzyl)hydroxylamine and N,O-bis(trimethylsilyl)trifluoroacetamide were used to propose the other major reaction products: 3-oxobutane-1,2-diyl nitrate, 2,6,6-trimethylcyclohex-1-ene-carbaldehyde, 2-oxo-1-(2,6,6-trimethylcyclohex-i-en-1-yl)ethyl nitrate, pentane-2,4-dione, 3-oxo-1-(2,6,6-trimethylcyclohex-1-en-1-yl)butane-1,2-diyl dinitrate, 3,3-dimethylcyclohexane-1,2-dione, and 4-oxopent-2-enal. The elucidation of these products was facilitated by mass spectrometry of the derivatized reaction products coupled with plausible beta-ionone + NO3 center dot reaction mechanisms based on previously published volatile organic compound + NO3 center dot gas-phase mechanisms. The additional gas-phase products 5-acetyl-2-ethylidene-3-methyicyclopentyl nitrate, 1-(1-hydroxy-7,7-dimetliyl-2,3,4,5,6,7-hexahydro-1H-inden-2-yl)ethanone, 1-(1-hydroxy-3a,7-dimethyl-2,3,3a,4,5,6,-hexahydro-1H-inden-2-yl)ethanon e, and 5-acetyl-2-ethylidene-3-methylcyclopenta none are proposed to be the result of cyclization through a reaction intermediate. (c) 2009 Wiley Periodicals, Inc.* Int J Chem Kinet 41: 629-641, 2009

The surface-phase reaction products of dihydromyrcenol (2,6-dimethyl-7-octen-2-ol) with ozone (O-3), air, or nitrogen (N-2) on silanized glass, glass and vinyl flooring tile were investigated using the recently published FACS (FLEC (Field and Laboratory Emission Cell) Automation and Control System). The FACS was used to deliver ozone (100 ppb), air, or N-2 to the surface at a specified flow rate (300 mL min(-1)) and relative humidity (50%) after application of a 2.0% dihydromyrcenol solution in methanol. Oxidation products were detected using the derivatization agents: O-(2,3,4,5,6-pentafluorobenzyl)hydroxylamine hydrochloride (PFBHA) and N,O-bis(trimethysilyl)trifluoroacetamide (BSTFA). The positively identified reaction products were glycolaldehyde, 2,6-dimethyl-5-heptenal, and glyoxal. The proposed oxidation products based on previously published VOC/O-3 reaction mechanisms were: 2,6-dimethyl-4-heptenal, 6-methyl-7-octen-2-one and the surface-specific reaction products: 6-methyl-6-hepten-2-one, 6-methyl-5-hepten-2-one, and 6-hydroxy-6-methylheptan-2-one. Though similar products were observed in gasphase dihydromyrcenol/O-3 reactions, the ratio, based on peak area, of the reaction products was different suggesting stabilization of larger molecular weight species by the surface. Emission profiles of these oxidation products over 72 h are also reported. Published by Elsevier Ltd.