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Science for Society Buildings account for a significant fraction of the land area in cities and actively exchange air with their proximate outdoor environments via mechanical ventilation systems. However, the direct impact of buildings on urban air pollution remains poorly characterized. Due to reductions in traffic-associated emissions of volatile organic compounds (VOCs), volatile chemical products, which are widely used inside buildings, have become a major VOC source in urban areas. Indoor-generated VOCs are likely to be an important contributor to the VOC burden of the urban atmosphere, and ventilation systems provide a pathway for VOCs to be released outdoors. Here, we show how modern buildings act as significant emission sources of VOCs for the outdoor environment. Our results demonstrate that future air quality monitoring efforts in cities need to account for direct VOC discharge from buildings in order to capture emerging sources of environmental pollution that can impact the climate and human health. Summary Urban air undergoes transformations as it is actively circulated throughout buildings via ventilation systems. However, the influence of air exchange between outdoor and indoor atmospheres on urban air pollution is not well understood. Here, we quantify how buildings behave as a dynamic source and sink for urban air pollutants via high-resolution online mass spectrometry measurements. During our field campaign in a high-performance office building, we observed that the building continually released volatile organic compounds (VOCs) into the urban air and removed outdoor ozone and fine particulate matter. VOC emissions from people, their activities, and surface reservoirs result in significant VOC discharge from the building to the outdoors. Per unit area, building emissions of VOCs are comparable to traffic, industrial, and biogenic emissions. The building source-sink behavior changed dynamically with occupancy and ventilation conditions. Our results demonstrate that buildings can directly influence urban air quality due to substantial outdoor-indoor air exchange. 

The dominant fraction of anthropogenic volatile organic compound (VOC) emissions shifted from transportation fuels to volatile chemical products (VCP) in Los Angeles (LA) in 2010. This shift in VOC composition raises the question about the importance of VCP emissions for ozone (O₃) formation. In this study, O₃chemistry during the CalNex 2010 was modeled using the Master Chemical Mechanism (MCM) version 3.3.1 and a detailed representation of VCP emissions based on measurements combined with inventory estimates. The model calculations indicate that VCP emissions contributed to 23% of the mean daily maximum 8‐hr average O₃(DMA8 O₃) during the O₃episodes. The simulated OH reactivity, including the contribution from VCP emissions, aligns with observations. Additionally, this framework was employed using four lumped mechanisms with simplified representations of emissions and chemistry. RACM2‐VCP showed the closest agreement with MCM, with a slight 4% increase in average DMA8 O₃(65 ± 13 ppb), whereas RACM2 (58 ± 13 ppb) and SAPRC07B (59 ± 14 ppb) exhibited slightly lower levels. CB6r2, however, recorded reduced concentrations (37 ± 10 ppb). Although emissions of O₃precursors have declined in LA since 2010, O₃levels have not decreased significantly. Model results ascribed this trend to the rapid reduction in NO_Xemissions. Moreover, given the impact of COVID‐19, an analysis of 2020 reveals a shift to a NO_X‐limited O₃formation regime in LA, thereby diminishing the influence of VCPs. This study provides new insights into the impact of VCP emissions on O₃pollution from an in‐depth photochemical perspective. 

Scented wax products, such as candles and wax warmers/melts, are popular fragranced consumer products that are commonly used in residential buildings. As scented wax products are intentionally fragranced to produce pleasant smellscapes for occupants, they may represent an important source of volatile organic compounds (VOCs) to indoor atmospheres. The aim of this study is to evaluate terpene emission factors (EFs) and inhalation intake fractions (iFs) for scented wax products to better understand their impact on indoor chemistry and chemical exposures. Full-scale emission experiments were conducted in the Purdue zEDGE Test House using a variety of scented candles (n = 5) and wax warmers/melts (n = 14) under different outdoor air exchange rates (AERs). Terpene concentrations were measured in real-time using a proton transfer reaction time-of-flight mass spectrometer (PTR-TOF-MS). PTR-TOF-MS measurements revealed that scented candle and wax warmer/melt products emit a variety of monoterpenes (C10H16) and oxygen-containing monoterpenoids (C10H14O, C10H16O, C10H18O, C10H20O), with peak concentrations in the range of 10^−1 to 10^2 ppb. Monoterpene EFs were much greater for scented wax warmers/melts (C10H16 EFs ~ 10^2 mg per g wax consumed) compared to scented candles (C10H16 EFs ~ 10^−1 to 100 mg per g wax consumed). Significant emissions of reactive terpenes from both products, along with nitrogen oxides (NO, NO2) from candles, depleted indoor ozone (O3) concentrations. Terpene iFs were similar between the two products (iFs ~ 10^3 ppm) and increased with decreasing outdoor AER. Terpene iFs during concentration decay periods were similar to, or greater than, iFs during active emission periods for outdoor AERs ≤ 3.0 h^−1. Overall, scented wax warmers/melts were found to release greater quantities of monoterpenes compared to other fragranced consumer products used in the home, including botanical disinfectants, hair care products, air fresheners, and scented sprays. 

Abstract. The hydroxyl (OH), hydroperoxy (HO2), and organic peroxy (RO2)radicals play important roles in atmospheric chemistry. In the presence ofnitrogen oxides (NOx), reactions between OH and volatile organiccompounds (VOCs) can initiate a radical propagation cycle that leads to theproduction of ozone and secondary organic aerosols. Previous measurements ofthese radicals under low-NOx conditions in forested environmentscharacterized by emissions of biogenic VOCs, including isoprene andmonoterpenes, have shown discrepancies with modeled concentrations. During the summer of 2016, OH, HO2, and RO2 radical concentrationswere measured as part of the Program for Research on Oxidants:Photochemistry, Emissions, and Transport – Atmospheric Measurements ofOxidants in Summer (PROPHET-AMOS) campaign in a midlatitude deciduousbroadleaf forest. Measurements of OH and HO2 were made by laser-inducedfluorescence–fluorescence assay by gas expansion (LIF-FAGE) techniques,and total peroxy radical (XO2) mixing ratios were measured by the Ethane CHemical AMPlifier (ECHAMP) instrument. Supporting measurements ofphotolysis frequencies, VOCs, NOx, O3, and meteorological datawere used to constrain a zero-dimensional box model utilizing either theRegional Atmospheric Chemical Mechanism (RACM2) or the Master ChemicalMechanism (MCM). Model simulations tested the influence of HOxregeneration reactions within the isoprene oxidation scheme from the LeuvenIsoprene Mechanism (LIM1). On average, the LIM1 models overestimated daytimemaximum measurements by approximately 40 % for OH, 65 % for HO2,and more than a factor of 2 for XO2. Modeled XO2 mixing ratioswere also significantly higher than measured at night. Addition of RO2 + RO2 accretion reactions for terpene-derived RO2 radicals tothe model can partially explain the discrepancy between measurements andmodeled peroxy radical concentrations at night but cannot explain thedaytime discrepancies when OH reactivity is dominated by isoprene. Themodels also overestimated measured concentrations of isoprene-derivedhydroxyhydroperoxides (ISOPOOH) by a factor of 10 during the daytime,consistent with the model overestimation of peroxy radical concentrations.Constraining the model to the measured concentration of peroxy radicalsimproves the agreement with the measured ISOPOOH concentrations, suggestingthat the measured radical concentrations are more consistent with themeasured ISOPOOH concentrations. These results suggest that the models maybe missing an important daytime radical sink and could be overestimating therate of ozone and secondary product formation in this forest. 

Abstract. A new instrument for the measurement of atmosphericnitrous acid (HONO) and hydroxyl radicals (OH) has been developed usinglaser photofragmentation (LP) of HONO at 355 nm after expansion into alow-pressure cell, followed by resonant laser-induced fluorescence (LIF) ofthe resulting OH radical fragment at 308 nm similar to the fluorescenceassay by gas expansion technique (FAGE). The LP/LIF instrument is calibratedby determining the photofragmentation efficiency of HONO andcalibrating the instrument sensitivity for detection of the OH fragment. Inthis method, a known concentration of OH from the photo-dissociation ofwater vapor is titrated with nitric oxide to produce a known concentrationof HONO. Measurement of the concentration of the OH radical fragmentrelative to the concentration of HONO provides a measurement of thephotofragmentation efficiency. The LP/LIF instrument has demonstrated a1σ detection limit for HONO of 9 ppt for a 10 min integration time.Ambient measurements of HONO and OH from a forested environment and an urbansetting are presented along with indoor measurements to demonstrate theperformance of the instrument. 

Abstract. Reactions of the hydroxyl (OH) and peroxy (HO2 and RO2) radicals playa central role in the chemistry of the atmosphere. In addition to controlling the lifetimes ofmany trace gases important to issues of global climate change, OH radical reactionsinitiate the oxidation of volatile organic compounds (VOCs) which can lead to the production ofozone and secondary organic aerosols in the atmosphere. Previous measurements of these radicalsin forest environments characterized by high mixing ratios of isoprene and low mixing ratios ofnitrogen oxides (NOx) (typically less than 1–2 ppb) have shown seriousdiscrepancies with modeled concentrations. These results bring into question our understanding ofthe atmospheric chemistry of isoprene and other biogenic VOCs under low NOxconditions. During the summer of 2015, OH and HO2 radical concentrations, as well as totalOH reactivity, were measured using laser-induced fluorescence–fluorescence assay by gasexpansion (LIF-FAGE) techniques as part of the Indiana Radical Reactivity and Ozone productioN InterComparison (IRRONIC). This campaign took place in a forested area near Indiana University's Bloomington campus which is characterized by high mixing ratios of isoprene (average daily maximum ofapproximately 4 ppb at 28 ∘C) and low mixing ratios of NO (diurnal averageof approximately 170 ppt). Supporting measurements of photolysis rates, VOCs,NOx, and other species were used to constrain a zero-dimensional box model basedon the Regional Atmospheric Chemistry Mechanism (RACM2) and the Master Chemical Mechanism (MCM 3.2),including versions of the Leuven isoprene mechanism (LIM1) for HOx regeneration(RACM2-LIM1 and MCM 3.3.1). Using an OH chemical scavenger technique, the study revealed thepresence of an interference with the LIF-FAGE measurements of OH that increased with bothambient concentrations of ozone and temperature with an average daytime maximum equivalentOH concentration of approximately 5×106 cm−3. Subtraction of theinterference resulted in measured OH concentrations of approximately4×106 cm−3 (average daytime maximum) that were in better agreement with modelpredictions although the models underestimated the measurements in the evening. The addition ofversions of the LIM1 mechanism increased the base RACM2 and MCM 3.2 modeled OH concentrationsby approximately 20 % and 13 %, respectively, with the RACM2-LIM1 mechanism providing thebest agreement with the measured concentrations, predicting maximum daily OH concentrationsto within 30 % of the measured concentrations. Measurements of HO2 concentrationsduring the campaign (approximately a 1×109 cm−3 average daytime maximum)included a fraction of isoprene-based peroxy radicals(HO2*=HO2+αRO2) and were found to agree with modelpredictions to within 10 %–30 %. On average, the measured reactivity was consistent with thatcalculated from measured OH sinks to within 20 %, with modeled oxidation productsaccounting for the missing reactivity, however significant missing reactivity (approximately40 % of the total measured reactivity) was observed on some days.