skip to main content


Title: Chemistry and Human Exposure Implications of Secondary Organic Aerosol Production from Indoor Terpene Ozonolysis
Surface cleaning using commercial disinfectants, which has recently increased during the coronavirus disease 2019 pandemic, can generate secondary indoor pollutants both in gas and aerosol phases. It can also affect indoor air quality and health, especially for workers repeatedly exposed to disinfectants. Here, we cleaned the floor of a mechanically ventilated office room using a commercial cleaner while concurrently measuring gas-phase precursors, oxidants, radicals, secondary oxidation products, and aerosols in real time; these were detected within minutes after cleaner application. During cleaning, indoor monoterpene concentrations exceeded outdoor concentrations by two orders of magnitude, increasing the rate of ozonolysis under low (<10 ppb) ozone levels. High number concentrations of freshly nucleated sub–10-nm particles (≥105 cm−3) resulted in respiratory tract deposited dose rates comparable to or exceeding that of inhalation of vehicle-associated aerosols.  more » « less
Award ID(s):
1847493
NSF-PAR ID:
10316077
Author(s) / Creator(s):
; ; ; ; ; ; ; ; ; ; ;
Date Published:
Journal Name:
Science advances
Volume:
8
ISSN:
2375-2548
Format(s):
Medium: X
Sponsoring Org:
National Science Foundation
More Like this
  1. Abstract

    This study introduces a new chemistry option in the Weather Research and Forecasting model data assimilation (WRFDA) system, coupled with the WRF‐Chem model (Version 4.4.1), to incorporate aqueous chemistry (AQCHEM) in the assimilation of ground‐level chemical measurements. The new DA capability includes the integration of aqueous‐phase aerosols from the Regional Atmospheric Chemistry Mechanism (RACM) gas chemistry, the Modal Aerosol Dynamics Model for Europe (MADE) aerosol chemistry, and the Volatility Basis Set (VBS) for secondary organic aerosol production. The RACM‐MADE‐VBS‐AQCHEM scheme facilitates aerosol‐cloud‐precipitation interactions by activating aerosol particles in cloud water during the model simulation. With the goal of enhancing air quality forecasting in cloudy conditions, this new implementation is demonstrated in the weakly coupled three‐dimensional variational data assimilation (3D‐Var) system through regional air quality cycling over East Asia. Surface particulate matter (PM) concentrations and four gas species (SO2, NO2, O3, and CO) are assimilated every 6 hr for the month of March 2019. The results show that including aqueous‐phase aerosols in both the analysis and forecast can represent aerosol wet removal processes associated with cloud development and rainfall production. During a pollution event with high cloud cover, simulations without aerosols defined in cloud water exhibit significantly higher values for liquid water path, and surface PM10(PM2.5) concentrations are overestimated by a factor of 10 (3) when wet scavenging processes dominate. On the contrary, AQCHEM proves to be helpful in simulating the wet deposition of aerosols, accurately predicting the evolution of surface PM concentrations without such overestimation.

     
    more » « less
  2. Free chlorine and free bromine ( e.g. , HOCl and HOBr) are employed as disinfectants in a variety of aqueous systems, including drinking water, wastewater, ballast water, recreational waters, and cleaning products. Yet, the most widely used methods for quantifying free halogens, including those employing N , N -diethyl- p -phenylenediamine (DPD), cannot distinguish between HOCl and HOBr. Herein, we report methods for selectively quantifying free halogens in a variety of aqueous systems using 1,3,5-trimethoxybenzene (TMB). At near-neutral pH, TMB reacted on the order of seconds with HOCl, HOBr, and inorganic bromamines to yield halogenated products that were readily quantified by liquid chromatography or, following liquid–liquid extraction, gas chromatography-mass spectrometry (GC-MS). The chlorinated and brominated products of TMB were stable, and their molar concentrations were used to calculate the original concentrations of HOCl (method quantitation limit (MQL) by GC-MS = 15 nmol L −1 = 1.1 μg L −1 as Cl 2 ) and HOBr (MQL by GC-MS = 30 nmol L −1 = 2 μg L −1 as Cl 2 ), respectively. Moreover, TMB derivatization was efficacious for quantifying active halogenating agents in drinking water, pool water, chlorinated surface waters, and simulated spa waters treated with 1-bromo-3-chloro-5,5-dimethylhydantoin. TMB was also used to quantify bromide as a trace impurity in 20 nominally bromide-free reagents (following oxidation of bromide by HOCl to HOBr). Several possible interferents were tested, and iodide was identified as impeding accurate quantitation of HOCl and HOBr. Overall, compared to the DPD method, TMB can provide lower MQLs, larger linear ranges, and selectivity between HOCl and HOBr. 
    more » « less
  3. 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.

     
    more » « less
  4. This paper explores the data cleaning challenges that arise in using WiFi connectivity data to locate users to semantic indoor locations such as buildings, regions, rooms. WiFi connectivity data consists of sporadic connections between devices and nearby WiFi access points (APs), each of which may cover a relatively large area within a building. Our system, entitled semantic LOCATion cleanER (LOCATER), postulates semantic localization as a series of data cleaning tasks - first, it treats the problem of determining the AP to which a device is connected between any two of its connection events as a missing value detection and repair problem. It then associates the device with the semantic subregion (e.g., a conference room in the region) by postulating it as a location disambiguation problem. LOCATER uses a bootstrapping semi-supervised learning method for coarse localization and a probabilistic method to achieve finer localization. The paper shows that LOCATER can achieve significantly high accuracy at both the coarse and fine levels. 
    more » « less
  5. In order to examine the reaction products, kinetics, and implications of ISOPOOH with aqueous sulfite, ammonium bisulfate particles were injected into the UNC 10‐m3 indoor environmental chamber under humid (i.e., 72% RH) and dark conditions. After the inorganic sulfate concentration stabilized, selected concentrations of gas‐phase 1,2‐ISOPOOH were injected into the chamber, and aerosols showed a minimal mass increase. Gaseous SO2 was subsequently injected into the chamber and a significant amount of aerosol mass was produced. The gas‐phase ISOPOOH and particle‐phase species were sampled with online instruments, including a chemical ionization mass spectrometer (CIMS), an aerosol chemical speciation monitor (ACSM), a particle‐into‐liquid sampler (PILS) for analysis by ion chromatography analysis (IC), and filter samples were analyzed by an ultra‐performance liquid chromatography coupled to an electrospray ionization highresolution quadrupole time‐of‐flight mass spectrometry (UPLCESI‐ HR‐QTOFMS) to obtain offline molecular‐level information. Results show that a significant amount of inorganic sulfate and organosulfates were formed rapidly after injecting SO2, altering the chemical and physical properties of the particles including phase state, pH, reactivity, and composition. Multifunctional C5‐organic species that were previously measured in atmospheric fine aerosol samples were also reported here as reaction products, including 2‐methyletrols and 2‐methyltetrol sulfates that were previously thought to be only produced from the reactive uptake of isoprene‐derived epoxydiols (IEPOX). Such results indicate that the multiphase reactions of ISOPOOH could have significant impacts on the atmospheric lifecycle of organic aerosols and sulfur, as well as the physicochemical properties of ambient particles. 
    more » « less