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ABSTRACT: 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).
The Review of scientific instruments 08/2012; 83(8):085103. · 1.52 Impact Factor
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ABSTRACT: 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 inflammatory 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 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. Pulmonary exposure to 4-OPA caused a significant elevation in nonspecific airway hyperreactivity, increased numbers of lung-associated lymphocytes and neutrophils, and increased interferon-γ 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.
Toxicological Sciences 03/2012; 127(2):371-81. · 4.65 Impact Factor
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ABSTRACT: 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 α-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 α-terpineol+O(3) reaction products were the prominent species that were also observed in the POC/O(3) surface experiments. Furthermore, α-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.
Chemosphere 01/2011; 83(3):327-33. · 3.21 Impact Factor
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ABSTRACT: Solid-phase microextraction (SPME) was evaluated for the detection and quantification of the gas-phase carbonyls: citronellal, glyoxal, methylglyoxal, and beta-ionone. Prepared air samples containing the carbonyl compounds were collected at a flow rate of 2.8 L min(-1) in an impinger containing a 25% reagent water/75% methanol collection liquid. The aqueous samples were then derivatized with O-(2,3,4,5,6-pentafluorobenzyl)hydroxylamine hydrochloride (PFBHA), extracted with a PDMS/DVB coated SPME fiber, and analyzed by GC-MS. Detection limits with a sample air volume of 76 L were calculated to be 0.03 ppbv, 0.34 ppbv, 0.12 ppbv, and 0.28 ppbv for citronellal, glyoxal, methylglyoxal, and beta-ionone, respectively.
Journal of Environmental Monitoring 08/2008; 10(7):853-60. · 1.99 Impact Factor
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ABSTRACT: Glyoxylic acid, a small dicarboxylic acid, has been detected at measurable levels in the atmosphere and is suspected to be present in indoor air environments. It is generated through the ozonolysis of several high volume production compounds that are commonly found indoors. Glyoxylic acid was tested in a combined irritancy and local lymph node assay (LLNA). It tested positive in the LLNA with an EC3 value of 5.05%. Significant increases were observed in the B220+cell population in the draining lymph nodes. No changes were identified in the IgE+B220+ cell population in the draining lymph nodes or total serum IgE levels; this suggests that glyoxylic acid functions as a T-cell-mediated contact sensitizer. Exposure to volatile organic compounds (VOC), similar to glyoxylic acid, emitted from building materials, cleaning formulations or other consumer products, and /or indoor chemistry have been linked to adverse health effects. These results may provide an explanation for some of adverse health effects associated with indoor air exposure.
Journal of Immunotoxicology 05/2008; 5(2):93-8. · 1.44 Impact Factor
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ABSTRACT: A novel system [field and laboratory emission cell (FLEC) automation and control system] has been developed to deliver ozone to a surface utilizing the FLEC to simulate indoor surface chemistry. Ozone, humidity, and air flow rate to the surface were continuously monitored using an ultraviolet ozone monitor, humidity, and flow sensors. Data from these sensors were used as feedback for system control to maintain predetermined experimental parameters. The system was used to investigate the chemistry of ozone with alpha-terpineol on a vinyl surface over 72 h. Keeping all other experimental parameters the same, volatile organic compound emissions from the vinyl tile with alpha-terpineol were collected from both zero and 100 ppb (parts per 10(9)) ozone exposures. System stability profiles collected from sensor data indicated experimental parameters were maintained to within a few percent of initial settings. Ozone data from eight experiments at 100 ppb (over 339 h) provided a pooled standard deviation of 1.65 ppb and a 95% tolerance of 3.3 ppb. Humidity data from 17 experiments at 50% relative humidity (over 664 h) provided a pooled standard deviation of 1.38% and a 95% tolerance of 2.77%. Data of the flow rate of air flowing through the FLEC from 14 experiments at 300 ml/min (over 548 h) provided a pooled standard deviation of 3.02 ml/min and a 95% tolerance range of 6.03 ml/min. Initial experimental results yielded long term emissions of ozone/alpha-terpineol reaction products, suggesting that surface chemistry could play an important role in indoor environments.
Review of Scientific Instruments 02/2007; 78(1):014101. · 1.37 Impact Factor
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ABSTRACT: Solid-phase microextraction (SPME) was evaluated for the detection and quantification of the gas-phase dicarbonyls, glyoxal (GLY) and methylglyoxal (MGLY). Additionally, polydimethylsiloxane (PDMS), polydimethylsiloxane/divinylbenzene (PDMS/DVB), and carbowax/divinylbenzene (CW/DVB) fibers were tested to determine the optimum fiber for detection of these species. GLY and MGLY were derivatized with O-(2,3,4,5,6-pentafluorobenzyl)-hydroxylamine hydrochloride (PFBHA), extracted with SPME from headspace or bag chamber and then analyzed by GC/MS. The PDMS/DVB SPME fiber for on-fiber derivatization and subsequent sampling for gas-phase methylglyoxal provided the optimum combination of analytical reproducibility and sensitivity. Linearity of the calibration curve was achieved across a range of 11-222 microg/m(3) (4-75 ppb).
Journal of Chromatography 11/2006; 1131(1-2):275-80. · 4.53 Impact Factor
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ABSTRACT: Electrospray ionization (ESI) is a proven method for introducing large intact molecules into the gas phase. However, the processes that occur within this ion source are poorly understood. We have developed instrumentation and methodology to probe the evolution of droplets within the electrospray plume. Using emission lifetime spectroscopy, excited-state lifetimes of [Ru(bpy)3]2+ with and without a known quencher, 2,3,5,6-tetramethyl-p-phenlyenediamine, present were observed. Lifetimes were shown to decrease as quencher concentration increased, as expected. Rate constants (with and without quencher present) were determined and correlated with quencher concentration using the Stern–Volmer relationship. Stern–Volmer plots reveal the linearity of the quenching reaction and can be used to determine the concentrations of species within the electrosprayed droplets. The evolution of the ESI droplets can be probed by comparing the concentration of a species at different locations within the plume.
Review of Scientific Instruments 12/2004; 76(1):014101-014101-6. · 1.37 Impact Factor
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ABSTRACT: Metal-bipyridine complexes are a vehicle for developing approaches for studying the fluorescence of gas-phase ions; however, conclusions regarding fluorescence behavior depend on explicitly identifying the ionic species in the gas phase. [Ru(bpy)(3)]X(2) and [Os(bpy(3))]X(2), (where bpy = 2,2'-bipyridine and X = Cl or PF(6)), were studied using direct laser desorption (LD) and matrix-assisted laser desorption/ionization (MALDI) using Fourier transform mass spectrometry (FTMS). LD spectra of the PF(6) salt of the Ru and Os complexes reveal counterion attachment, fluoride transfer, and significant losses of H for a number of peaks. LD of the chloride salt complexes produced loss of a single bpy ligand, chloride attachment, and losses of H. Spectra of [Ru(bpy(3)]X(2) where X = BF(4)(-), CF(3)SO(3)(-), and SCN(-) were also collected using LD and compared with the spectra for Cl(2) and PF(6) salts. Regardless of counterion, loss of H is observed in LD spectra. MALDI spectra of the trisbipyridyl complexes using 2,5-dihydroxybenzoic acid (DHB) and sinapinic acid (SA) as the matrix were also obtained. The spectra using SA as matrix show intact molecular ion peaks with very little fragmentation and no counterion attachment. Unlike SA, the spectra obtained using DHB look similar to LD spectra with significant losses of H. Our results are consistent with a reaction scheme for hydrogen loss from a carbon that also involves breaking of the metalz.sbnd;nitrogen bond, rotation of a pyridine ring, and re-formation of an ortho-metallated complex by a metalz.sbnd;C bond. These results demonstrate the importance of ion generation method and the utilization of FTMS for correct characterization of metal poly(pyridyl) complexes.
Journal of the American Society for Mass Spectrometry 05/2003; 14(4):393-400. · 4.00 Impact Factor
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ABSTRACT: A bimolecular rate constant, kOH+citronellol, of (170±43)×10−12 cm3 molecule−1 s−1 was measured using the relative rate technique for the reaction of the hydroxyl radical (OH) with 3,7-dimethyl-6-octen-1-ol (citronellol) at (297±3) K and 1 atmosphere total pressure. Additionally, a bimolecular rate constant, kO3+citronellol, of (2.4±0.1)×10−16 cm3 molecule−1 s−1, was measured by monitoring the decrease in ozone (O3) concentration in an excess of citronellol. To more clearly define part of citronellol's indoor environment degradation mechanism, the products of the citronellol+OH and citronellol+O3 reactions were also investigated. The positively identified citronellol/OH and citronellol/O3 reaction products were: acetone, ethanedial (glyoxal, HC(O)C(O)H), and 2-oxopropanal (methylglyoxal, CH3C(O)C(O)H). The use of derivatizing agents O-(2,3,4,5,6-pentafluorobenzyl)hydroxylamine (PFBHA) and N,O-bis(trimethylsilyl) trifluoroacetamide (BSTFA) were used to propose 6-hydroxy-4-methylhexanal as the other major citronellol/OH and citronellol/O3 reaction product. The elucidation of this other reaction product was facilitated by mass spectrometry of the derivatized reaction products coupled with plausible citronellol/OH and citronellol/O3 reaction mechanisms based on previously published volatile organic compound/OH and volatile organic compound/O3 gas-phase reaction mechanisms.
Atmospheric Environment.
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ABSTRACT: The surface-phase reaction products of dihydromyrcenol (2,6-dimethyl-7-octen-2-ol) with ozone (O3), air, or nitrogen (N2) 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 N2 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/O3 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 gas-phase dihydromyrcenol/O3 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.
Atmospheric Environment.
