We investigate source characteristics and emission dynamics of volatile organic compounds (VOCs) in a single‐family house in California utilizing time‐ and space‐resolved measurements. About 200 VOC signals, corresponding to more than 200 species, were measured during 8 weeks in summer and five in winter. Spatially resolved measurements, along with tracer data, reveal that VOCs in the living space were mainly emitted directly into that space, with minor contributions from the crawlspace, attic, or outdoors. Time‐resolved measurements in the living space exhibited baseline levels far above outdoor levels for most VOCs; many compounds also displayed patterns of intermittent short‐term enhancements (spikes) well above the indoor baseline. Compounds were categorized as “high‐baseline” or “spike‐dominated” based on indoor‐to‐outdoor concentration ratio and indoor mean‐to‐median ratio. Short‐term spikes were associated with occupants and their activities, especially cooking. High‐baseline compounds indicate continuous indoor emissions from building materials and furnishings. Indoor emission rates for high‐baseline species, quantified with 2‐hour resolution, exhibited strong temperature dependence and were affected by air‐change rates. Decomposition of wooden building materials is suggested as a major source for acetic acid, formic acid, and methanol, which together accounted for ~75% of the total continuous indoor emissions of high‐baseline species.

Abstract. Western US wildlands experience frequent and large-scale wildfires which are predicted to increase in the future. As a result, wildfire smoke emissions are expected to play an increasing role in atmospheric chemistry while negatively impacting regional air quality and human health. Understanding the impacts of smoke on the environment is informed by identifying and quantifying the chemical compounds that are emitted during wildfires and by providing empirical relationships that describe how the amount and composition of the emissions change based upon different fire conditions and fuels. This study examined particulate organic compounds emitted from burning common western US wildland fuels at the US Forest Service Fire Science Laboratory. Thousands of intermediate and semi-volatile organic compounds (I/SVOCs) were separated and quantified into fire-integrated emission factors (EFs) using a thermal desorption, two-dimensional gas chromatograph with online derivatization coupled to an electron ionization/vacuum ultraviolet high-resolution time-of-flight mass spectrometer (TD-GC × GC-EI/VUV-HRToFMS). Mass spectra, EFs as a function of modified combustion efficiency (MCE), fuel source, and other defining characteristics for the separated compounds are provided in the accompanying mass spectral library. Results show that EFs for total organic carbon (OC), chemical families of I/SVOCs, and most individual I/SVOCs span 2–5 orders of magnitude, with higher EFs at smoldering conditions (low MCE) than flaming. Logarithmic fits applied to the observations showed that log (EFs) for particulate organic compounds were inversely proportional to MCE. These measurements and relationships provide useful estimates of EFs for OC, elemental carbon (EC), organic chemical families, and individual I/SVOCs as a function of fire conditions.

Experiments were conducted at the California Air Resources Board Haagen-Smit Laboratory to understand changes in vehicle emissions in response to stricter emissions standards over the past 25 years. Measurements included a wide range of volatile organic compounds (VOCs) for a wide range of spark ignition gasoline vehicles meeting varying levels of emissions standards, including all certifications from Tier 0 up to Partial Zero Emission Vehicle. Standard gas chromatography (GC) and high performance liquid chromatography (HLPC) analyses were employed for drive-cycle phase emissions. A proton-transfer-reaction mass spectrometer measured time-resolved emissions for a wide range of VOCs. Cold-start emissions occur almost entirely in the first 30–60 s for newer vehicles. Cold-start emissions have compositions that are not significantly different across all vehicles tested and are markedly different from neat fuel. Hot-stabilized emissions have varying importance depending on species and may require a driving distance of 200 miles to equal the emissions from a single cold start. Average commute distances in the U.S. suggest the majority of in-use vehicles have emissions dominated by cold starts. The distribution of vehicle ages in the U.S. suggests that within several years only a few percent of vehicles will have significant driving emissions compared to cold-start emissions.

We present simultaneous fast, in-situ measurements of formaldehyde and glyoxal from two rural campaigns, BEARPEX 2009 and BEACHON-ROCS, both located in Pinus Ponderosa forests with emissions dominated by biogenic volatile organic compounds (VOCs). Despite considerable variability in the formaldehyde and glyoxal concentrations, the ratio of glyoxal to formaldehyde, R_GF, displayed a very regular diurnal cycle over nearly 2 weeks of measurements. The only deviations in R_GF were toward higher values and were the result of a biomass burning event during BEARPEX 2009 and very fresh anthropogenic influence during BEACHON-ROCS. Other rapid changes in glyoxal and formaldehyde concentrations have hardly any affect on R_GF and could reflect transitions between low and high NO regimes. The trend of increased R_GF from both anthropogenic reactive VOC mixtures and biomass burning compared to biogenic reactive VOC mixtures is robust due to the short timescales over which the observed changes in R_GF occurred. Satellite retrievals, which suggest higher R_GF for biogenic areas, are in contrast to our observed trends. It remains important to address this discrepancy, especially in view of the importance of satellite retrievals and in situ measurements for model comparison. In addition, we propose that R_GF represents a useful metric for biogenic or anthropogenic reactive VOC mixtures and, in combination with absolute concentrations of glyoxal and formaldehyde, furthermore represents a useful metric for the extent of anthropogenic influence on overall reactive VOC processing via NO_x. In particular, R_GF yields information about not simply the VOCs dominating reactivity in an airmass, but the VOC processing itself that is directly coupled to ozone and secondary organic aerosol production

Over the past two decades vehicle emission standards in the United States have been dramatically tightened with the goal of reducing urban air pollution. Secondary organic aerosol (SOA) is the dominant contributor to urban organic aerosol. Experiments were conducted at the California Air Resources Board Haagen-Smit Laboratory to characterize exhaust organics from 20 gasoline vehicles recruited from the California in-use fleet. The vehicles spanned a wide range of emission certification standards. We comprehensively characterized intermediate volatility and semivolatile organic compound emissions using thermal desorption two-dimensional gas-chromatography− mass-spectrometry with electron impact (GC × GC-EI-MS) and vacuumultraviolet (GC × GC-VUV-MS) ionization. Single-ring aromatic compounds with unsaturated C4 and C5 substituents contribute a large fraction of the intermediate volatility organic compound (IVOC) emissions in gasoline vehicle exhaust. The analyses of quartz filters used in GC × GC-VUV-MS show that primary organic aerosol emissions were dominated by motor oil. We combined our new emissions data with published SOA yield parametrizations to estimate SOA formation potential. After 24 h of oxidation, IVOC emissions contributed 45% of SOA formation; BTEX compounds (benzene, toluene, xylenes, and ethylbenzene), 40%; other VOC aromatics, 15%. The composition of IVOC emissions was consistent across the test fleet, suggesting that future reductions in vehicular emissions will continue to reduce SOA formation and ambient particulate mass levels.