Factors controlling volatile organic compounds in dwellings in Melbourne, Australia.

This study characterized indoor volatile organic compounds (VOCs) and investigated the effects of the dwelling characteristics, building materials, occupant activities, and environmental conditions on indoor VOC concentrations in 40 dwellings located in Melbourne, Australia, in 2008 and 2009. A total of 97 VOCs were identified. Nine VOCs, n-butane, 2-methylbutane, toluene, formaldehyde, acetaldehyde, d-limonene, ethanol, 2-propanol, and acetic acid, accounted for 68% of the sum of all VOCs. The median indoor concentrations of all VOCs were greater than those measured outdoors. The occupant density was positively associated with indoor VOC concentrations via occupant activities, including respiration and combustion. Terpenes were associated with the use of household cleaning and laundry products. A petroleum-like indoor VOC signature of alkanes and aromatics was associated with the proximity of major roads. The indoor VOC concentrations were negatively correlated (P < 0.05) with ventilation. Levels of VOCs in these Australian dwellings were lower than those from previous studies in North America and Europe, probably due to a combination of an ongoing temporal decrease in indoor VOC concentrations and the leakier nature of Australian dwellings.

Risk in the mist? Deriving data to quantify microbial health risks associated with aerosol generation by water-efficient devices during typical domestic water-using activities.

The aim of this study was to address existing data gaps and to determine the size distribution of aerosols associated with water-efficient devices during typical domestic activities. This information is important to assist in understanding infection spread during water-using activities and in designing water regulations. Three water-using scenarios were evaluated: i) showering using a water-efficient showerhead; ii) use of a high pressure spray unit for cleaning cars and iii) toilet flushing using a dual flush low volume flush device. For each scenario a control condition (conventional lower efficiency device) was selected for benchmarking purposes. Shower module results highlighted the complexity of particle generation and removal processes and showed that more than 90% of total particle mass in the breathing zone was attributed to particle diameters greater than 6 mum. Conversely, results for car washing experiments showed that particle diameters up to 6 mum constituted the major part of the total mass generated by both water-efficient and conventional devices. Even under worse case scenario conditions for toilet flushing, particle measurements were at or below the level of detection of the measuring instrumentation. The data provide information that assists in health risk assessment and in determining future research directions, including methodological aspects.

Measurements of secondary organic aerosol from oxidation of cycloalkenes, terpenes, and m-xylene using an Aerodyne aerosol mass spectrometer.

The Aerodyne aerosol mass spectrometer (AMS) was used to characterize physical and chemical properties of secondary organic aerosol (SOA) formed during ozonolysis of cycloalkenes and biogenic hydrocarbons and photo-oxidation of m-xylene. Comparison of mass and volume distributions from the AMS and differential mobility analyzers yielded estimates of "effective" density of the SOA in the range of 0.64-1.45 g/cm3, depending on the particular system. Increased contribution of the fragment at m/z 44, C02+ ion fragment of oxygenated organics, and higher "delta" values, based on ion series analysis of the mass spectra, in nucleation experiments of cycloalkenes suggest greater contribution of more oxygenated molecules to the SOA as compared to those formed under seeded experiments. Dominant negative "delta" values of SOA formed during ozonolysis of biogenics indicates the presence of terpene derivative structures or cyclic or unsaturated oxygenated compounds in the SOA. Evidence of acid-catalyzed heterogeneous chemistry, characterized by greater contribution of higher molecular weight fragments to the SOA and corresponding changes in "delta" patterns, is observed in the ozonolysis of alpha-pinene. Mass spectra of SOA formed during photooxidation of m-xylene exhibit features consistent with the presence of furandione compounds and nitro organics. This study demonstrates that mixtures of SOA compounds produced from similar precursors result in broadly similar AMS mass spectra. Thus, fragmentation patterns observed for biogenic versus anthropogenic SOA may be useful in determining the sources of ambient SOA.

Secondary organic aerosol formation from the ozonolysis of cycloalkenes and related compounds.

The secondary organic aerosol (SOA) yields from the laboratory chamber ozonolysis of a series of cycloalkenes and related compounds are reported. The aim of this work is to investigate the effect of the structure of the hydrocarbon parent molecule on SOA formation for a homologous set of compounds. Aspects of the compound structures that are varied include the number of carbon atoms present in the cycloalkene ring (C5 to C8), the presence and location of methyl groups, and the presence of an exocyclic or endocyclic double bond. The specific compounds considered here are cyclopentene, cyclohexene, cycloheptene, cyclooctene, 1-methyl-1-cyclopentene, 1-methyl-1-cyclohexene, 1-methyl-1-cycloheptene, 3-methyl-1-cyclohexene, and methylenecyclohexane. The SOA yield is found to be a function of the number of carbons present in the cycloalkene ring, with an increasing number resulting in increased yield. The yield is enhanced by the presence of a methyl group located at a double-bonded site but reduced by the presence of a methyl group at a non-double-bonded site. The presence of an exocyclic double bond also leads to a reduced yield relative to that of the equivalent methylated cycloalkene. On the basis of these observations, the SOA yield for terpinolene relative to the other cyclic alkenes is qualitatively predicted, and this prediction compares well to measurements of the SOA yield from the ozonolysis of terpinolene. This work shows that relative SOA yields from ozonolysis of cyclic alkenes can be qualitatively predicted from properties of the parent hydrocarbons.

Secondary organic aerosol formation from cyclohexene ozonolysis: effect of OH scavenger and the role of radical chemistry.

To isolate secondary organic aerosol (SOA) formation in ozone-alkene systems from the additional influence of hydroxyl (OH) radicals formed in the gas-phase ozone-alkene reaction, OH scavengers are employed. The detailed chemistry associated with three different scavengers (cyclohexane, 2-butanol, and CO) is studied in relation to the effects of the scavengers on observed SOA yields in the ozone-cyclohexene system. Our results confirm those of Docherty and Ziemann that the OH scavenger plays a role in SOA formation in alkene ozonolysis. The extent and direction of this influence are shown to be dependent on the specific alkene. The main influence of the scavenger arises from its independent production of HO2 radicals, with CO producing the most HO2, 2-butanol an intermediate amount, and cyclohexane the least. This work provides evidence for the central role of acylperoxy radicals in SOA formation from the ozonolysis of alkenes and generally underscores the importance of gas-phase radical chemistry beyond the initial ozone-alkene reaction.

ACE-Asia intercomparison of a thermal-optical method for the determination of particle-phase organic and elemental carbon.

A laboratory intercomparison of organic carbon (OC) and elemental carbon (EC) measurements of atmospheric particulate matter samples collected on quartz filters was conducted among eight participants of the ACE-Asia field experiment The intercomparison took place in two stages: the first round of the intercomparison was conducted when filter samples collected during the ACE-Asia experiment were being analyzed for OC and EC, and the second round was conducted after the ACE-Asia experiment and included selected samples from the ACE-Asia experiment Each participant operated ECOC analyzers from the same manufacturer and utilized the same analysis protocol for their measurements. The precision of OC measurements of quartz fiber filters was a function of the filter's carbon loading but was found to be in the range of 4-13% for OC loadings of 1.0-25 microg of C cm(-2). For measurements of EC, the precision was found to be in the range of 6-21% for EC loadings in the range of 0.7-8.4 microg of C cm(-2). It was demonstrated for three ambient samples, four source samples, and three complex mixtures of organic compounds that the relative amount of total evolved carbon allocated as OC and EC (i.e., the ECOC split) is sensitive to the temperature program used for analysis, and the magnitude of the sensitivity is dependent on the types of aerosol particles collected. The fraction of elemental carbon measured in wood smoke and an extract of organic compounds from a wood smoke sample were sensitive to the temperature program used for the ECOC analysis. The ECOC split for the three ambient samples and a coal fly ash sample showed moderate sensitivity to temperature program, while a carbon black sample and a sample of secondary organic aerosol were measured to have the same split of OC and EC with all temperature programs that were examined.

Size distribution and sources of aerosol in Launceston, Australia, during winter 1997.

As part of a pilot study into the chemical and physical properties of Australian fine particles, a suite of aerosol samples was collected at Ti Tree Bend in Launceston, Tasmania, during June and July 1997. This period represents midwinter in the Southern Hemisphere, a period when aerosol sources in Launceston are dominated by smoke from domestic wood burning. This paper describes the results from this measurement campaign, with the aim of assessing the effect of wood smoke on the chemical and physical characteristics of ambient aerosol. A micro orifice uniform deposit impactor (MOUDI) was used to measure the size distributions of the aerosol from 0.05 to 20 microns aerodynamic diameter. Continuous measurements of fine particle mass were made using a PM2.5 tapered element oscillating microbalance (TEOM) and light scattering coefficients at 530 nm were measured with nephelometers. Mass size distributions tended to be bimodal, with the diameter of the dominant mode tending to smaller sizes with increases in total mass. Non-sea salt potassium and polycyclic aromatic hydrocarbons (PAHs) were used as chemical tracers for wood smoke. Wood smoke was found to increase absolute particle mass (enough to regularly exceed air quality standards), and to concentrate mass in a single mode below 1 micron aerodynamic diameter. The acid-base equilibrium of the aerosol was altered by the wood smoke source, with free acidity hydrogen ion, non-sea salt sulfate, and ammonium concentrations being higher and the concentration of all species, including nitrate (to differing extents), focused in the fine particle size ranges. The wood smoke source also heavily influenced the aerosol scattering efficiency, adding to a strong diurnal cycle in both mass concentration and light scattering.

Determination of nicotine in water by gradient ion chromatography.

A sensitive gradient ion chromatographic method has been demonstrated for determination of nicotine in aqueous solution. The method provides an improvement in detection limit, plus a reduction in analysis time, compared with a previously published ion chromatographic method.