Unintended Consequences of Air Cleaning Chemistry

Amplified interest in maintaining clean indoor air associated with the airborne transmission risks of SARS-CoV-2 have led to an expansion in the market for commercially available air cleaning systems. While the optimal way to mitigate indoor air pollutants or contaminants is to control (remove) the source, air cleaners are a tool for use when absolute source control is not possible. Interventions for indoor air quality management include physical removal of pollutants through ventilation or collection on filters and sorbent materials, along with chemically reactive processes that transform pollutants or seek to deactivate biological entities. This perspective intends to highlight the perhaps unintended consequences of various air cleaning approaches via indoor air chemistry. Introduction of new chemical agents or reactive processes can initiate complex chemistry that results in the release of reactive intermediates and/or byproducts into the indoor environment. Since air cleaning systems are often continuously running to maximize their effectiveness and most people spend a vast majority of their time indoors, human exposure to both primary and secondary products from air cleaners may represent significant exposure risk. This Perspective highlights the need for further study of chemically reactive air cleaning and disinfection methods before broader adoption

Indoor Particulate Matter during HOMEChem: Concentrations, Size Distributions, and Exposures.

It is important to improve our understanding of exposure to particulate matter (PM) in residences because of associated health risks. The HOMEChem campaign was conducted to investigate indoor chemistry in a manufactured test house during prescribed everyday activities, such as cooking, cleaning, and opening doors and windows. This paper focuses on measured size distributions of PM (0.001-20 μm), along with estimated exposures and respiratory-tract deposition. Number concentrations were highest for sub-10 nm particles during cooking using a propane-fueled stovetop. During some cooking activities, calculated PM2.5 mass concentrations (assuming a density of 1 g cm-3) exceeded 250 μg m-3, and exposure during the postcooking decay phase exceeded that of the cooking period itself. The modeled PM respiratory deposition for an adult residing in the test house kitchen for 12 h varied from 7 μg on a day with no indoor activities to 68 μg during a simulated day (including breakfast, lunch, and dinner preparation interspersed by cleaning activities) and rose to 149 μg during a simulated Thanksgiving day

Quantifying proximity, confinement, and interventions in disease outbreaks: a decision support framework for air-transported pathogens

Includes bibliographical references (pages H-I).The inability to communicate how infectious diseases are transmitted in human environments has triggered avoidance of interactions during the COVID-19 pandemic. We define a metric, Effective ReBreathed Volume (ERBV), that encapsulates how infectious pathogens, including SARS-CoV-2, transport in air. ERBV separates environmental transport from other factors in the chain of infection, allowing quantitative comparisons among situations. Particle size affects transport, removal onto surfaces, and elimination by mitigation measures, so ERBV is presented for a range of exhaled particle diameters: 1, 10, and 100 μm. Pathogen transport depends on both proximity and confinement. If interpersonal distancing of 2 m is maintained, then confinement, not proximity, dominates rebreathing after 10–15 min in enclosed spaces for all but 100 μm particles. We analyze strategies to reduce this confinement effect. Ventilation and filtration reduce person-to-person transport of 1 μm particles (ERBV1) by 13–85% in residential and office situations. Deposition to surfaces competes with intentional removal for 10 and 100 μm particles, so the same interventions reduce ERBV10 by only 3–50%, and ERBV100 is unaffected. Prior knowledge of size-dependent ERBV would help identify transmission modes and effective interventions. This framework supports mitigation decisions in emerging situations, even before other infectious parameters are known

Surface reservoirs dominate dynamic gas-surface partitioning of many indoor air constituents

Human health is affected by indoor air quality. One distinctive aspect of the indoor environment is its very large surface area that acts as a poorly characterized sink and source of gas-phase chemicals. In this work, air-surface interactions of 19 common indoor air contaminants with diverse properties and sources were monitored in a house using fast-response, on-line mass spectrometric and spectroscopic methods. Enhanced-ventilation experiments demonstrate that most of the contaminants reside in the surface reservoirs and not, as expected, in the gas phase. They participate in rapid air-surface partitioning that is much faster than air exchange. Phase distribution calculations are consistent with the observations when assuming simultaneous equilibria between air and large weakly polar and polar absorptive surface reservoirs, with acid-base dissociation in the polar reservoir. Chemical exposure assessments must account for the finding that contaminants that are fully volatile under outdoor air conditions instead behave as semivolatile compounds indoors

Indoor black carbon and brown carbon concentrations from cooking and outdoor penetration: Insights from the HOMEChem study

Particle emissions from cooking are a major contributor to residential indoor air pollution and could also contribute to ambient concentrations. An important constituent of these emissions is light-absorbing carbon, including black carbon (BC) and brown carbon (BrC). This work characterizes the contributions of indoor and outdoor sources of BC and BrC to the indoor environment by concurrently measuring real-time concentrations of these air pollutants indoors and outdoors during the month-long HOMEChem study. The median indoor-to-outdoor ratios of BC and BrC during the periods of no activity inside the test house were 0.6 and 0.7, respectively. The absorption &Aring;ngstr&ouml;m exponent was used to characterize light-absorbing particle emissions during different activities and ranged from 1.1 to 2.7 throughout the campaign, with the highest value (indicative of BrC-dominated emissions) observed during the preparation of a simulated Thanksgiving Day holiday style meal. An indoor BC exposure assessment shows that exposure for an occupant present in the kitchen area was ~4 times higher during Thanksgiving Day experiments (primarily due to candle burning) when compared to the background conditions.</p

An overview of the Amazonian Aerosol Characterization Experiment 2008 (AMAZE-08)

The Amazon Basin provides an excellent environment for studying the sources, transformations, and properties of natural aerosol particles and the resulting links between biological processes and climate. With this framework in mind, the Amazonian Aerosol Characterization Experiment (AMAZE-08), carried out from 7 February to 14 March 2008 during the wet season in the central Amazon Basin, sought to understand the formation, transformations, and cloud-forming properties of fine- and coarse-mode biogenic aerosol particles, especially as related to their effects on cloud activation and regional climate. Special foci included (1) the production mechanisms of secondary organic components at a pristine continental site, including the factors regulating their temporal variability, and (2) predicting and understanding the cloud-forming properties of biogenic particles at such a site. In this overview paper, the field site and the instrumentation employed during the campaign are introduced. Observations and findings are reported, including the large-scale context for the campaign, especially as provided by satellite observations. New findings presented include: (i) a particle number-diameter distribution from 10 nm to 10 Î1/4m that is representative of the pristine tropical rain forest and recommended for model use; (ii) the absence of substantial quantities of primary biological particles in the submicron mode as evidenced by mass spectral characterization; (iii) the large-scale production of secondary organic material; (iv) insights into the chemical and physical properties of the particles as revealed by thermodenuder-induced changes in the particle number-diameter distributions and mass spectra; and (v) comparisons of ground-based predictions and satellite-based observations of hydrometeor phase in clouds. A main finding of AMAZE-08 is the dominance of secondary organic material as particle components. The results presented here provide mechanistic insight and quantitative parameters that can serve to increase the accuracy of models of the formation, transformations, and cloud-forming properties of biogenic natural aerosol particles, especially as related to their effects on cloud activation and regional climate. © 2010 Author(s)

Real-Time Measurement of Herbicides in the Atmosphere: A Case Study of MCPA and 2,4-D during Field Application

Atmospheric sources of herbicides enable short- and long-range transport of these compounds to off-target areas but the concentrations and mechanisms are poorly understood due, in part, to the challenge of detecting these compounds in the atmosphere. We present chemical ionization time-of-flight mass spectrometry as a sensitive, real-time technique to detect chlorinated phenoxy acid herbicides in the atmosphere, using measurements during and after application over a field at Colorado State University as a case study. Gas-phase 2,4-dichlorophenoxyacetic acid (2,4-D) mixing ratios were greatest during application (up to 20 pptv), consistent with rapid volatilization from spray droplets. In contrast, atmospheric concentrations of 2-methyl-4-chlorophenoxyacetic acid (MCPA) increased for several hours after the initial application, indicative of a slower source than 2,4-D. The maximum observed gas-phase MCPA was 60 pptv, consistent with a post-application volatilization source to the atmosphere. Exposure to applied pesticides in the gas-phase can thus occur both during and at least several hours after application. Spray droplet volatilization and direct volatilization from surfaces may both contribute pesticides to the atmosphere, enabling pesticide transport to off-target and remote regions

Atmospheric OH Oxidation of Three Chlorinated Aromatic Herbicides

Chlorinated phenoxy acids are a widely used class of herbicides and have been found in remote regions far from sources. However, the atmospheric chemistry of these compounds is poorly understood. We use an oxidative flow reactor coupled to chemical ionization mass spectrometry to investigate OH oxidation of two chlorinated phenoxyacid herbicides (2-methyl-4-chlorophenoxyacetic acid (MCPA) and mecoprop-p) and one chlorinated pyridine herbicide (triclopyr). OH radicals add to the aromatic rings of the three herbicides, produce peroxides via hydrogen abstraction, or fragment at the ether bond. OH oxidation of MCPA produced two potentially toxic compounds: chlorosalicylaldehyde and chlorosalicylic acid. We use standards to validate the detection of these oxidation products by acetate CIMS and quantify the reaction rate. Oxidation of triclopyr produced a known endocrine disruptor, 3,5,6-trichloro-2-pyridinol. Thus, while some OH oxidation products are less toxic than the parent molecules (e.g., C₁-₅ carboxylic acids), others may be as or more toxic than the parent herbicide. We determine effective rate coefficients for OH addition to the aromatic ring (<i>k</i>_OH) for mecoprop-p of 1.5 (±0.7) × 10^–12 cm³ molecules^–1 s^–1 and for MCPA of 2.6 (±0.3) × 10^–12 cm³ molecules^–1 s^–1. The atmospheric lifetimes with respect to OH are thus long enough that photochemistry may be relevant to the environmental fate of these pesticides