Ozone reaction characteristics of indoor floor dust examined in the emission cell "FLEC".

Ozone reacts with C-C double bonds in common indoor VOCs and SVOCs contained in indoor dust and may be catalytically degraded on dust surfaces. The reaction between floor dust and ozone was investigated in the FLEC emission cell at different ozone concentrations and relative humidities (0%, 25%, and 50% RH). One gram of dust was spread on a clean stainless steel plate which was placed in the FLEC. Steady state reaction rate (kDust) at 2.2 ppm ozone was determined for four different floor dust samples collected in Danish homes and offices. This high concentration was necessary in order to measure and determine the consumption in the outlet air from the FLEC. Measurements were corrected for FLEC wall effects by subtraction of the steady state reaction rate between ozone and a FLEC on a stainless steel plate without dust (kFLEC). The composition of organic compounds in the dust was analyzed by pressurized liquid extraction and thermal desorption GC-MS before and after ozone exposure. kFLEC was independent of the ozone concentration and the reaction was treated as first order. The same was indicated for kDust since it remained unchanged at 2.2 and 1.6 ppm ozone for one dust sample. However, the measured kDust in the FLEC should be considered an average rate constant due to the FLEC geometry. kDust was in the range 0.039-0.14s(-1) pr. g dust at 50% RH. kDust was 3 times higher at 25% RH than at 50% RH and 6 times higher than at 0% RH. The inhomogeneity of the dust was assessed by experiments in triplicate with a new portion of dust each time. The relative standard deviation of kDust at 50% RH was 6-20%. The major identified compounds before and after ozone exposure included aldehydes, saturated and unsaturated linear alkanoic acids, benzoic acid and their methyl esters, dimethyl esters, phthalates and traces of α-pinene and limonene. Substantial increase of C7-C9 aldehydes was observed after ozone exposure.

Study of ozone-initiated limonene reaction products by low temperature plasma ionization mass spectrometry.

Limonene and its ozone-initiated reaction products were investigated in situ by low temperature plasma (LTP) ionization quadrupole time-of-flight (QTOF) mass spectrometry. Helium was used as discharge gas and the protruding plasma generated ~850 ppb ozone in front of the glass tube by reaction with the ambient oxygen. Limonene applied to filter paper was placed in front of the LTP afterglow and the MS inlet. Instantly, a wide range of reaction products appeared, ranging from m/z 139 to ca. 1000 in the positive mode and m/z 115 to ca. 600 in the negative mode. Key monomeric oxidation products including levulinic acid, 4-acetyl-1-methylcyclohexene, limonene oxide, 3-isopropenyl-6-oxo-heptanal, and the secondary ozonide of limonene could be identified by collision-induced dissociation. Oligomeric products ranged from the nonoxidized dimer of limonene (C20H30) and up to the hexamer with 10 oxygen atoms (C60H90O10). The use of LTP for in situ ozonolysis and ionization represents a new and versatile approach for the assessment of ozone-initiated terpene chemistry.

Effects of prenatal exposure to surface-coated nanosized titanium dioxide (UV-Titan). A study in mice.

BACKGROUND: Engineered nanoparticles are smaller than 100 nm and designed to improve or achieve new physico-chemical properties. Consequently, also toxicological properties may change compared to the parent compound. We examined developmental and neurobehavioral effects following maternal exposure to a nanoparticulate UV-filter (UV-titan L181). METHODS: Time-mated mice (C57BL/6BomTac) were exposed by inhalation 1h/day to 42 mg/m(3) aerosolized powder (1.7.10(6) n/cm(3); peak-size: 97 nm) on gestation days 8-18. Endpoints included: maternal lung inflammation; gestational and litter parameters; offspring neurofunction and fertility. Physicochemical particle properties were determined to provide information on specific exposure and deposition. RESULTS: Particles consisted of mainly elongated rutile titanium dioxide (TiO2) with an average crystallite size of 21 nm, modified with Al, Si and Zr, and coated with polyalcohols. In exposed adult mice, 38 mg Ti/kg was detected in the lungs on day 5 and differential cell counts of bronchoalveolar lavage fluid revealed lung inflammation 5 and 26-27 days following exposure termination, relative to control mice. As young adults, prenatally exposed offspring tended to avoid the central zone of the open field and exposed female offspring displayed enhanced prepulse inhibition. Cognitive function was unaffected (Morris water maze test). CONCLUSION: Inhalation exposure to nano-sized UV Titan dusts induced long term lung inflammation in time-mated adult female mice. Gestationally exposed offspring displayed moderate neurobehavioral alterations. The results are discussed in the light of the observed particle size distribution in the exposure atmosphere and the potential pathways by which nanoparticles may impart changes in fetal development.

Formation and stability of secondary ozonides from monoterpenes studied by mass spectrometry.

The secondary ozonide (SOZ) of limonene is a potential indoor pollutant from the gas-phase limonene/ozone-reaction. A screening in the liquid phase was performed to investigate the yield and stability of SOZs from ten cyclic monoterpenes. They were cryo-ozonolyzed in pentane, and the reaction mixtures were analyzed with GC-MS with negative and positive chemical ionization and electron ionization. The investigated terpenes were: limonene, 4-carene, 3-carene, 2-carene, terpinolene, (+)-alpha-pinene, (-)-beta-pinene, isolimonene, sabinene and camphene. The only identified endo-SOZs were from: limonene, 3-carene, 4-carene and possibly isolimonene. Collision induced dissociation (CID) of the quasi-molecular-ions as a proxy measure of the stability of the pristine SOZs was investigated. LimoneneSOZ and 3-careneSOZ were found to be more stable than 4-careneSOZ and isolimoneneSOZ, which corresponded well to their relative yields. 3-careneSOZ was found to be a major product from the gas-phase ozonolysis.