An extensive set of primary and secondary pollutants was measured at a ground site in a remote location in the Yellow River Delta, China during the Ozone Photochemistry and Export from China Experiment (OPECE) from March to April 2018. The measurements include volatile organic compounds (VOCs), peroxyacyl nitrates (PANs), ozone (O3), particulate species, nitrogen oxides (NOx), and SO2. Observed VOC mixing ratios were comparable to those measured in heavily polluted cities in the U.S. and China. The VOC source signatures suggest a strong influence from Oil and Natural Gas (O&NG) emissions with potentially large contributions from Liquified Petroleum Gas (LPG) sources as well. Consistently elevated concentrations of O3, PAN, and its rarely measured homologs peroxybenzoylic nitric anhydride (PBzN) and peroxyacrylic nitric anhydride (APAN) at the OPECE site indicate complex photochemistry in a heterogeneous VOC environment. Diagnostic 0‐D box model simulations are used to investigate the budgets of ROx(OH + HO2 + RO2), and the rate and efficiency of O3production. Model sensitivity calculations indicate that O3production at OPECE site is VOC limited in spring. This suggests that reduction in VOCs should be a priority for reducing O3, where production and fugitive emissions from O&NG provide an attractive target. While initial reductions in NOxmight increase O3production, reduction of NOxalong with VOCs will be a necessary step to achieve long‐term ozone reduction.
Emerging investigator series: primary emissions, ozone reactivity, and byproduct emissions from building insulation materials
Building insulation materials can affect indoor air by (i) releasing primary volatile organic compounds (VOCs) from building enclosure cavities to the interior space, (ii) mitigating exposure to outdoor pollutants through reactive deposition (of oxidants, e.g. , ozone) or filtration (of particles) in infiltration air, and (iii) generating secondary VOCs and other gas-phase byproducts resulting from oxidant reactions. This study reports primary VOC emission fluxes, ozone (O 3 ) reaction probabilities ( γ ), and O 3 reaction byproduct yields for eight common, commercially available insulation materials. Fluxes of primary VOCs from the materials, measured in a continuous flow reactor using proton transfer reaction-time of flight-mass spectrometry, ranged from 3 (polystyrene with thermal backing) to 61 (cellulose) μmol m −2 h −1 (with total VOC mass emission rates estimated to be between ∼0.3 and ∼3.3 mg m −2 h −1 ). Major primary VOC fluxes from cellulose were tentatively identified as compounds likely associated with cellulose chemical and thermal decomposition products. Ozone-material γ ranged from ∼1 × 10 −6 to ∼30 × 10 −6 . Polystyrene with thermal backing and polyisocyanurate had the lowest γ , while cellulose and fiberglass had the highest. In the presence of O 3 , total observed volatile byproduct yields ranged from 0.25 (polystyrene) to 0.85 (recycled denim) moles of VOCs produced per mole of O 3 consumed, or equivalent to secondary fluxes that range from 0.71 (polystyrene) to 10 (recycled denim) μmol m −2 h −1 . Major emitted products in the presence of O 3 were generally different from primary emissions and were characterized by yields of aldehydes and acetone. This work provides new data that can be used to evaluate and eventually model the impact of “hidden” materials ( i.e. , those present inside wall cavities) on indoor air quality. The data may also guide building enclosure material selection, especially for buildings in areas of high outdoor O 3 .
more »
« less
- NSF-PAR ID:
- 10134013
- Date Published:
- Journal Name:
- Environmental Science: Processes & Impacts
- Volume:
- 21
- Issue:
- 8
- ISSN:
- 2050-7887
- Page Range / eLocation ID:
- 1255 to 1267
- Format(s):
- Medium: X
- Sponsoring Org:
- National Science Foundation
More Like this
-
more » « less
Abstract -
Abstract. The impact of biomass burning (BB) on the atmospheric burden of volatile organic compounds (VOCs) is highly uncertain. Here we apply the GEOS-Chemchemical transport model (CTM) to constrain BB emissions in the western USA at ∼ 25 km resolution. Across three BB emission inventorieswidely used in CTMs, the inventory–inventory comparison suggests that the totals of 14 modeled BB VOC emissions in the western USA agree with eachother within 30 %–40 %. However, emissions for individual VOCs can differ by a factor of 1–5, driven by the regionally averaged emissionratios (ERs, reflecting both assigned ERs for specific biome and vegetation classifications) across the three inventories. We further evaluate GEOS-Chemsimulations with aircraft observations made during WE-CAN (Western Wildfire Experiment for Cloud Chemistry, Aerosol Absorption and Nitrogen) andFIREX-AQ (Fire Influence on Regional to Global Environments and Air Quality) field campaigns. Despite being driven by different global BBinventories or applying various injection height assumptions, the model–observation comparison suggests that GEOS-Chem simulations underpredictobserved vertical profiles by a factor of 3–7. The model shows small to no bias for most species in low-/no-smoke conditions. We thus attribute thenegative model biases mostly to underestimated BB emissions in these inventories. Tripling BB emissions in the model reproduces observed verticalprofiles for primary compounds, i.e., CO, propane, benzene, and toluene. However, it shows no to less significant improvements for oxygenatedVOCs, particularly for formaldehyde, formic acid, acetic acid, and lumped ≥ C3 aldehydes, suggesting the model is missing secondarysources of these compounds in BB-impacted environments. The underestimation of primary BB emissions in inventories is likely attributable tounderpredicted amounts of effective dry matter burned, rather than errors in fire detection, injection height, or ERs, as constrained by aircraftand ground measurements. We cannot rule out potential sub-grid uncertainties (i.e., not being able to fully resolve fire plumes) in the nestedGEOS-Chem which could explain the negative model bias partially, though back-of-the-envelope calculation and evaluation using longer-term groundmeasurements help support the argument of the dry matter burned underestimation. The total ERs of the 14 BB VOCs implemented in GEOS-Chem onlyaccount for half of the total 161 measured VOCs (∼ 75 versus 150 ppb ppm−1). This reveals a significant amount of missing reactiveorganic carbon in widely used BB emission inventories. Considering both uncertainties in effective dry matter burned (× 3) and unmodeledVOCs (× 2), we infer that BB contributed to 10 % in 2019 and 45 % in 2018 (240 and 2040 Gg C) of the total VOC primaryemission flux in the western USA during these two fire seasons, compared to only 1 %–10 % in the standard GEOS-Chem.more » « less
-
more » « less
Abstract We use observations from dual high‐resolution mass spectrometers to characterize ecosystem‐atmosphere fluxes of reactive carbon across an extensive range of volatile organic compounds (VOCs) and test how well that exchange is represented in current chemical transport models. Measurements combined proton‐transfer reaction mass spectrometry (PTRMS) and iodide chemical ionization mass spectrometry (ICIMS) over a Colorado pine forest; together, these techniques have been shown to capture the majority of ambient VOC abundance and reactivity. Total VOC mass and associated OH reactivity fluxes were dominated by emissions of 2‐methyl‐3‐buten‐2‐ol, monoterpenes, and small oxygenated VOCs, with a small number of compounds detected by PTRMS driving the majority of both net and upward exchanges. Most of these dominant species are explicitly included in chemical models, and we find here that GEOS‐Chem accurately simulates the net and upward VOC mass and OH reactivity fluxes under clear sky conditions. However, large upward terpene fluxes occurred during sustained rainfall, and these are not captured by the model. Far more species contributed to the downward fluxes than are explicitly modeled, leading to a major underestimation of this key sink of atmospheric reactive carbon. This model bias mainly reflects missing and underestimated concentrations of depositing species, though inaccurate deposition velocities also contribute. The deposition underestimate is particularly large for assumed isoprene oxidation products, organic acids, and nitrates—species that are primarily detected by ICIMS. Net ecosystem‐atmosphere fluxes of ozone reactivity were dominated by sesquiterpenes and monoterpenes, highlighting the importance of these species for predicting near‐surface ozone, oxidants, and aerosols.
-
The continued development of the automotive industry has led to a rapid increase in the amount of waste rubber tires, the problem of “black pollution” has become more serious but is often ignored. In this study, the emission characteristics, health risks, and environmental effects of volatile organic compounds (VOCs) from a typical, recycled rubber plant were studied. A total of 15 samples were collected by summa canisters, and 100 VOC species were detected by the GC/MS-FID system. In this study, the total VOCs (TVOCs) concentration ranged from 1000 ± 99 to 19,700 ± 19,000 µg/m3, aromatics and alkanes were the predominant components, and m/p-xylene (14.63 ± 4.07%–48.87 ± 3.20%) could be possibly regarded as a VOCs emission marker. We also found that specific similarities and differences in VOCs emission characteristics in each process were affected by raw materials, production conditions, and process equipment. The assessment of health risks showed that devulcanizing and cooling had both non-carcinogenic and carcinogenic risks, yarding had carcinogenic risks, and open training and refining had potential carcinogenic risks. Moreover, m/p-xylene and benzene were the main non-carcinogenic species, while benzene, ethylbenzene, and carbon tetrachloride were the dominant risk compounds. In the evaluation results of LOH, m/p-xylene (25.26–67.87%) was identified as the most key individual species and should be prioritized for control. In conclusion, the research results will provide the necessary reference to standardize the measurement method of the VOCs source component spectrum and build a localized source component spectrum.more » « less
-
null (Ed.)Abstract. Mixing ratios of volatile organic compounds (VOCs) were recordedin two field campaigns in central Beijing as part of the Air Pollution andHuman Health in a Chinese Megacity (APHH) project. These data were used tocalculate, for the first time in Beijing, the surface–atmosphere fluxes ofVOCs using eddy covariance, giving a top-down estimation of VOC emissionsfrom a central area of the city. The results were then used to evaluate theaccuracy of the Multi-resolution Emission Inventory for China (MEIC). TheAPHH winter and summer campaigns took place in November and December 2016and May and June 2017, respectively. The largest VOC fluxes observed were ofsmall oxygenated compounds such as methanol, ethanol + formic acid andacetaldehyde, with average emission rates of 8.31 ± 8.5, 3.97 ± 3.9 and 1.83 ± 2.0 nmol m−2 s−1, respectively, in the summer.A large flux of isoprene was observed in the summer, with an average emissionrate of 5.31 ± 7.7 nmol m−2 s−1. While oxygenated VOCs madeup 60 % of the molar VOC flux measured, when fluxes were scaled by ozoneformation potential and peroxyacyl nitrate (PAN) formation potential thehigh reactivity of isoprene and monoterpenes meant that these speciesrepresented 30 % and 28 % of the flux contribution to ozone and PANformation potential, respectively. Comparison of measured fluxes with theemission inventory showed that the inventory failed to capture the magnitudeof VOC emissions at the local scale.more » « less
- Free Publicly Accessible Full Text
-
Accepted Manuscript1.0
- Journal Article:
- https://doi.org/10.1039/c9em00024k
