Anna L Hodshire1, Ellison Carter2, James M Mattila1, Vito Ilacqua3, Jordan Zambrana3, Jonathan P D Abbatt4, Andrew Abeleira1, Caleb Arata5, Peter F DeCarlo6, Allen H Goldstein5, Lea Hildebrandt Ruiz7, Marina E Vance8, Chen Wang4, Delphine K Farmer1. 1. Department of Chemistry, Colorado State University, Fort Collins, Colorado 80524, United States. 2. Department of Civil and Environmental Engineering, Colorado State University, Fort Collins, Colorado 80521, United States. 3. U.S. Environmental Protection Agency, Office of Radiation and Indoor Air, Washington District of Columbia 20460, United States. 4. Department of Chemistry, University of Toronto, Toronto, ON M5S 3H6, Canada. 5. Department of Environmental Science, Policy, and Management, University of California at Berkeley, Berkeley, California 94720, United States. 6. Department of Environmental Health and Engineering, Johns Hopkins University, Baltimore, Maryland 21212, United States. 7. McKetta Department of Chemical Engineering, The University of Texas at Austin, Austin, Texas 78712, United States. 8. Department of Mechanical Engineering, University of Colorado Boulder, 1111 Engineering Drive, 427 UCB, Boulder, Colorado 80309, United States.
Abstract
Analytical capabilities in atmospheric chemistry provide new opportunities to investigate indoor air. HOMEChem was a chemically comprehensive indoor field campaign designed to investigate how common activities, such as cooking and cleaning, impacted indoor air in a test home. We combined gas-phase chemical data of all compounds, excluding those with concentrations <1 ppt, with established databases of health effect thresholds to evaluate potential risks associated with gas-phase air contaminants and indoor activities. The chemical composition of indoor air is distinct from outdoor air, with gaseous compounds present at higher levels and greater diversity─and thus greater predicted hazard quotients─indoors than outdoors. Common household activities like cooking and cleaning induce rapid changes in indoor air composition, raising levels of multiple compounds with high risk quotients. The HOMEChem data highlight how strongly human activities influence the air we breathe in the built environment, increasing the health risk associated with exposure to air contaminants.
Analytical capabilities in atmospheric chemistry provide new opportunities to investigate indoor air. HOMEChem was a chemically comprehensive indoor field campaign designed to investigate how common activities, such as cooking and cleaning, impacted indoor air in a test home. We combined gas-phase chemical data of all compounds, excluding those with concentrations <1 ppt, with established databases of health effect thresholds to evaluate potential risks associated with gas-phase air contaminants and indoor activities. The chemical composition of indoor air is distinct from outdoor air, with gaseous compounds present at higher levels and greater diversity─and thus greater predicted hazard quotients─indoors than outdoors. Common household activities like cooking and cleaning induce rapid changes in indoor air composition, raising levels of multiple compounds with high risk quotients. The HOMEChem data highlight how strongly human activities influence the air we breathe in the built environment, increasing the health risk associated with exposure to air contaminants.
Entities:
Keywords:
air pollution; atmospheric chemistry; health risk assessment; household activities; indoor air
People in the United States
spend ∼90% of their time indoors
and ∼63% in their own homes.[1] Built
environments are sources of chemical air contaminants, some of which
are hazardous or linked with negative health outcomes.[2] Inhalation of gaseous compounds is an important exposure
source for volatile and semivolatile pollutants.[3,4] Gas-phase
components of indoor air have diverse sources including release from
building materials,[5−7] use of personal care products and other volatile
chemical products,[8,9] occupant activities like cooking
and cleaning,[10,11] and secondary chemistry occurring
on building surfaces or via gas-phase oxidation reactions.[12−16] Building materials and furnishings of residences emit known air
toxics such as phthalate esters, formaldehyde, and acrolein,[17−20] while cleaning with bleach releases chlorine gas, particles and
additional air toxics.[11,13] However, the health impacts of
these individual compounds, let alone the complex mixtures present
in indoor environments, on both short (minutes to days) and long (months
to years) timescales are poorly understood.[21]Indoor environmental stressors like noise and air quality
influence
patterns of illness, wellbeing, and adverse health endpoints among
diverse populations.[22] Air quality stressors
include particle- and gas-phase pollutants. While particle number
and mass are often measured indoors, particle composition and gas-phase
species are more challenging to comprehensively measure due to their
diverse functionality.[23] High time-resolution
measurements of particle composition and volatile organic compounds
(VOCs) are thus relatively rare.[24]Risk assessments consider composition, frequency, intensity, and
duration of identified compounds. Such indoor data for most compounds
are lacking beyond simple gases (e.g., CO, CO2) and a few
well-established air toxics (e.g., formaldehyde, benzene). Indoor
sources operate on multiple timescales, presenting another barrier
to quantifying potential exposure and associated health risks. Some
sources, such as household materials, emit continuously and thus vary
on long (weeks to months) timescales.[25] Other sources, such as cooking or cleaning, can be intense but short
(minutes to hours).[26,27] Human activity patterns further
complicate exposure calculations as activities may be either sporadic
(e.g., cleaning) or repeated on weekly, daily, or sub-daily timescales
(e.g., cooking). These varying timescales, coupled with multiple sources
for individual contaminants, challenge traditional approaches to classifying
health risks by acute, short-term, or chronic exposure to individual
compounds.[3]Indoor airborne contaminants
are numerous and diverse in residences.[28−31] Current data is insufficient
to prioritize and allocate resources
to hazard and risk reduction efforts. Atmospheric chemists can now
quantify a vast number of compounds and at high time resolution,[32] but these advances are rarely applied to indoor
air health assessments for occupational settings.[33] Here, we directly apply advanced instrumentation with both
high chemical and time resolution for a health assessment in a residential
setting.Few indoor studies are chemically comprehensive. Large-scale
projects
like OFFICAIR and RIOPA measured compounds in multiple buildings or
homes, but only for 12 and 18 VOCs, respectively.[34,35] Test house, classroom, and building measurements with more comprehensive
chemical measurements[25,36−50] have, for example, shown how chemical transformations of cigarette
smoke on fabric and building surfaces induce particle/gas/surface
repartitioning through ‘third hand cigarette smoke.[51−53] Price et al.[50] noted higher levels of
VOCs and total reactivity inside an art gallery than outdoor air.
Despite these advances, chemically comprehensive indoor datasets have
not yet been applied to quantifying human exposure or identifying
indoor air hazards. Such an assessment is essential because indoor
air is so chemically different from outdoor air that exposure is likely
dominated by different air toxics.[25,50,54] Identifying which compounds are the greatest hazards
is the first step in assessing risks associated with indoor air and
identifying targets for reduction efforts.We use data from
the House Observations of Microbial and Environmental
Chemistry (HOMEChem) study to investigate how different gas-phase
compounds contribute to potential exposure risk during different indoor
activities. First, we use the gas-phase data to quantify total levels
and chemical diversity of air contaminants. Second, we develop a hybrid
approach to classify gas-phase compounds with respect to hazard indices
using databases of known air toxics and predicted human health effects.
Third, we apply this hybrid approach to HOMEChem data to identify
and contrast key air contaminants of concern in indoor versus outdoor
air and during different indoor activities. While HOMEChem investigated
only one house, it provides an unprecedented dataset (Table S1) to study chemical diversity and concentrations
in indoor residential air, allowing us to probe how indoor air and
different household activities may impact human inhalation exposure.
Methods
HOMEChem
HOMEChem investigated how
everyday residential activities impact indoor air.[26] HOMEChem included comprehensive chemical measurements of
gases, particles, and building metrics in the UTest House at the University
of Texas, Austin in June 2018. Cooking activities followed scripted
recipes and included repeated vegetarian stir-fries; beef chili; and
hot breakfast of eggs, toast, and sausage. Cleaning activities included
mopping with bleach, pine-scented, or ‘natural’ products,
mixed to manufacturer specifications. Unoccupied house conditions
provide a proxy for exposure in the absence of indoor activities.
However, humans are emission sources through both biochemistry[55] and personal care product usage[56] and the unoccupied baseline neglects these human emissions.
We periodically ran an ozone generator in the house air supply closet,
which increased indoor ozone to 30 ppb from the 5–15 ppb observed
when windows and doors were closed.[26] These
ozone additions allow us to examine potential effects of infiltration
of pollution or use of products that generate ozone either deliberately
or accidentally.Gas-phase measurements included >300 unique
compounds in both outdoor and indoor air using on-line mass spectrometry,
spectroscopy, and chromatography instruments (Table S2). All inlets were in the kitchen. All systems report
mixing ratios by volume. We refer to actual HOMEChem observations
as mixing ratios or levels but use the term concentration for more
general discussions (e.g., concentrations of compounds during activities).
We further only consider compounds with levels >1 ppt (part per
trillion),
as all of the published threshold concentrations we compare the data
to are at least 100 ppt (Section ).We limit this analysis to on-line, real-time
measurements. We exclude
CO, CO2, and CH4 as the toxicity of these compounds
in indoor environments has been extensively characterized[57−59] but include their concentrations in Table S1. Data from each instrument was rigorously evaluated for quality
and calibrated following instrument-specific procedures (Table S3, SI S2, other publications[11−13,26,54]).
Hybrid Classification Approach
To
classify known, suspected, or unknown air toxics, we developed a hybrid
classification approach to separate molecules into three categories:
(i) known air toxics, as identified on the Hazardous Air Pollutants
(HAPs) list maintained by the U.S. Environmental Protection Agency
(EPA) and the air toxics database maintained by California’s
EPA Office of Environmental Health Hazard Assessment (OEHHA), (ii)
molecules anticipated to be toxic based on the EPA Toxicity Estimation
Software Tool (T.E.S.T.) quantitative structure activity relationship
model,[60] using the developmental toxicity
and Ames mutagenicity toxicity endpoints (SI details HAPs/OEHHA lists,
T.E.S.T. model, and toxicity endpoints), and (iii) chemical air contaminants
not identified in the HAPs/OEHHA lists or T.E.S.T. predictions (Table S1). This third category includes unlisted
compounds. Some unlisted compounds, including dibromomethane, propanethiol,
and methanethiol, are identified as air toxics by the National Institute
for Occupational Safety and Health or other databases. In contrast
to previous indoor and outdoor contaminant exposure studies that identified
hazardous or potentially hazardous species,[2] we combine targeted and untargeted analyses to provide a more comprehensive
and activity-resolved approach.To relate measured concentrations
of a diverse range of gas-phase compounds to potential exposure risk,
we considered three aspects: (1) the number of compounds present (chemical
diversity) by classifying compounds in two ways: their potential health
hazard using the hybrid classification approach (e.g., known, potential,
and unlisted air toxics), and by elemental composition (e.g., compounds
containing C, H, and O atoms versus C, H, O, and Cl); (2) the mixing
ratio (level) of each compound; and (3) the anticipated time period
of exposure.Sorting compounds by mixing ratio provides a metric
for the number
of molecules an individual is potentially exposed to in each chemical
air contaminant category (i.e., “exposure potential”).
We consider mixing ratios present during activities, outside, and
during house background conditions, as well as enhancement ratios
in levels above the initial house background air conditions. We calculate
enhancements as the ratio of the mean levels observed for the 60 min
period after the start of the activity, encompassing the activity
(typically 15–30 min) and time afterward during which levels
remain elevated, to the mean levels observed 60 min before the start
of the activity. For compounds uniquely emitted during the activity,
we calculate enhancements relative to the initial concentration of
the compound, and present data for enhancement ratios of1.1, 3, and
10.To investigate which individual compounds are most likely
to influence
health for anticipated time periods of exposure, we use the databases
of known air toxics to calculate acute, chronic, and chronic-weighted
hazard quotients. Hazard quotients are the ratio of the observed concentration
of a species divided by its threshold concentration,[61] or concentration below which adverse (non-cancer) effects
are unlikely to occur. Adverse (non-cancer) effects are unlikely to
occur for air toxics with hazard quotients ≤1. We consider
acute hazard quotients as exposure over 1 h, chronic hazard quotients
as exposure over a lifetime, and chronic-weighted hazard quotients
as exposure over a lifetime weighted by the time anticipated spent
upon that activity or location (SI S7). Finally, we compare HOMEChem
data to cancer threshold concentrations or concentrations of a carcinogenic
compound that result in 1 excess lifetime tumor per 1 million people.
Any exposure to a carcinogen can result in an increased chance of
getting cancer, and cancer risks here are not considered against acute
versus chronic exposures.This hybrid classification system
is a straightforward method to
sort through a comprehensive and quantitative dataset to identify
potential air contaminants. The use of calibrated, quantitative concentration
measurements contrasts with the qualitative non-targeted analysis
frequently used in pollutant screening.[62] This framework could be applied to other air toxics databases or
predictive models and may be useful for other indoor or outdoor studies.
While the exact mixtures, concentrations, and time periods of exposure
to chemical air contaminants vary by day and home, our approach considers
how different activities or mitigation strategies can impact indoor
air.This analysis assumes that input data are reasonably complete
and
that instrument uncertainties are smaller than experimental variance.
We calculated the relative standard deviation of replicate experiments
(e.g., repeated mopping) for a given compound and find variations
of up to hundreds of percent, while instrument uncertainties were
≪100% (Table 1).Health effects
can be non-linear with exposure, meaning that hazard
quotients >1 do not necessarily indicate correspondingly greater
probabilities
of adverse effects.[61] Additional challenges
with hazard quotients include the choice of database (OEHHA versus
HAPs), consideration of only single pollutants in toxicity rather
than complex mixtures, assumption that short events (e.g., cooking)
should be treated acute exposures even if commonly repeated, and lack
of established thresholds in T.E.S.T. and thus exclusion of predicted
(but not known) toxics from analyses.
Results and Discussion
Chemical Diversity, Levels, and Indoor Activities
Three consistent patterns emerge when simultaneously considering
chemical air contaminant diversity (i.e., total number of compounds; Figure ) and total (summed)
chemical air contaminant levels (Figure and Figure S1) at HOMEChem: (1) outdoor air at the HOMEChem site is less chemically
diverse and has lower concentrations of measured compounds than indoor
air, (2) all indoor activities increase chemical diversity of indoor
air, and (3) cooking elevates indoor concentrations of trace gas compounds
more than any other activity. Known air toxics are only a small fraction
of the compounds observed during HOMEChem, but a substantial fraction
of the total level of compounds predicted to have toxicity.
Figure 1
Chemical diversity
(number of compounds) measured during HOMEChem,
sorted by elemental composition. We only show compounds observed at
mixing ratios >1 ppt. Each pie label indicates the activity or
condition.
The number (#) above each pie label indicates the total number of
species quantified under the stated condition. Numerical percentage
breakdowns of each category by compound number are in Table S4. The pie radii are relative to bleach,
the activity with the greatest number of quantified compounds. The
chemical classes are Cl = compounds containing 1 or more chlorine
atoms, N = compounds containing 1 or more nitrogen atoms, S = compounds
containing 1 or more sulfur atoms, Si = compounds containing 1 or
more silicon atoms, CH = compounds composed of only carbon and hydrogen
atoms (hydrocarbons), CHO = compounds composed of only carbon, hydrogen,
and oxygen atoms (oxygenated organics), and Ox/Rad = O3, OH, HO2. Each compound is assigned to only one class
in this figure.
Figure 2
(a) Scatter plot of the total concentrations in ppb present
of
all measured compounds versus the total number of compounds present
during each activity or condition. (b) Contributions to pollutant
concentrations by chemical air contaminant category. We only include
compounds present at mixing ratios >1 ppt. Numerical percentage
breakdowns
of each category by mixing ratio is listed in Table S4. Pie radii are relative to the highest total levels
(breakfast). The chemical air contaminant categories are OEHHA/HAPs
= identified as an air toxic within the OEHHA and/or HAPs databases,
MUT & DEV TOX = compounds identified in the T.E.S.T. model to
be both potentially mutagenic (MUT) and to potentially cause developmental
toxicity (DEV TOX), MUT = compounds identified in the T.E.S.T. model
to be only potentially mutagenic, DEV TOX = compounds identified in
the T.E.S.T. model to only potentially cause developmental toxicity,
and Not listed = compounds not listed in the OEHHA, HAPs, or T.E.S.T.
model to be a known or potential air toxic. Panel (b) is replotted
in Figure S3 with equal pie radii for ease
of visual comparison between pie sections. Each compound is assigned
to only one class in this figure. Concentrations have been calculated
using the centroid of each data point; while the true concentrations
may vary, the trends shown are not anticipated to change.
Chemical diversity
(number of compounds) measured during HOMEChem,
sorted by elemental composition. We only show compounds observed at
mixing ratios >1 ppt. Each pie label indicates the activity or
condition.
The number (#) above each pie label indicates the total number of
species quantified under the stated condition. Numerical percentage
breakdowns of each category by compound number are in Table S4. The pie radii are relative to bleach,
the activity with the greatest number of quantified compounds. The
chemical classes are Cl = compounds containing 1 or more chlorine
atoms, N = compounds containing 1 or more nitrogen atoms, S = compounds
containing 1 or more sulfur atoms, Si = compounds containing 1 or
more silicon atoms, CH = compounds composed of only carbon and hydrogen
atoms (hydrocarbons), CHO = compounds composed of only carbon, hydrogen,
and oxygen atoms (oxygenated organics), and Ox/Rad = O3, OH, HO2. Each compound is assigned to only one class
in this figure.(a) Scatter plot of the total concentrations in ppb present
of
all measured compounds versus the total number of compounds present
during each activity or condition. (b) Contributions to pollutant
concentrations by chemical air contaminant category. We only include
compounds present at mixing ratios >1 ppt. Numerical percentage
breakdowns
of each category by mixing ratio is listed in Table S4. Pie radii are relative to the highest total levels
(breakfast). The chemical air contaminant categories are OEHHA/HAPs
= identified as an air toxic within the OEHHA and/or HAPs databases,
MUT & DEV TOX = compounds identified in the T.E.S.T. model to
be both potentially mutagenic (MUT) and to potentially cause developmental
toxicity (DEV TOX), MUT = compounds identified in the T.E.S.T. model
to be only potentially mutagenic, DEV TOX = compounds identified in
the T.E.S.T. model to only potentially cause developmental toxicity,
and Not listed = compounds not listed in the OEHHA, HAPs, or T.E.S.T.
model to be a known or potential air toxic. Panel (b) is replotted
in Figure S3 with equal pie radii for ease
of visual comparison between pie sections. Each compound is assigned
to only one class in this figure. Concentrations have been calculated
using the centroid of each data point; while the true concentrations
may vary, the trends shown are not anticipated to change.We observe more compounds and at higher levels
in indoor air than
outdoor air during HOMEChem (Figures and 2). HOMEChem took place
in a major U.S. city and near multiple highways. The relative distributions
of compounds by class were similar, regardless of activity type (Figure and Table S4) – likely because instruments
were so sensitive and house emissions so strong that detectable compounds
were typically above detection limits indoors, even during unoccupied
periods. Unlike chemical diversity, levels of individual compounds
were impacted by location (indoors versus outdoors) and activities
(Figure S1 and Table S4). Levels of chemical
air contaminants are consistently higher indoors than outdoors, and
indoor activities increase total indoor levels by up to 4-fold. Distributions
of each chemical air contaminant category by number are also remarkably
similar between indoor and outdoor air, regardless of activity (Figure S2), while the distributions are dissimilar
by mixing ratio space (Figure and Figure S3). Outdoor air has
substantially lower levels of chemical air contaminants and less chemical
diversity than even the house background air (Figure a,b). Cleaning and cooking are strong sources
of chemical air contaminants to indoor environments.Outdoor
air has the lowest total mixing ratio of measured trace
gases but also the highest percentage of levels that are identified
in the OEHHA/HAPs databases (61%) of all locations and activities
examined. This greater proportion of compounds with established health
effects may be, in part, influenced by the fact that inclusion in
these databases prioritizes compounds measured in ambient air at Superfund
sites. Another 20% of the total mixing ratio of compounds measured
outdoors is predicted by T.E.S.T. to have developmental toxicity.
The house background air contains substantially higher total trace
gas levels (326 vs 67 ppb) than outdoor air, along with a smaller
fraction (35%) of established OEHHA/HAPs and a larger fraction (45%)
of total trace gas levels predicted to have developmental toxicity.
This large fraction of trace gas levels predicted to have developmental
toxicity highlights the need for investigating the extent to which
compounds predicted to have toxicity by T.E.S.T. poses health risks
at real-world exposure levels.Residential activities not only
increased the total number and
level of chemical air contaminants but also the total number and levels
of compounds with potential toxicity. For cooking and cleaning, 30–65%
of compounds by level are known or potential air toxics. Bleach mopping
has the highest fraction of the total level of compounds in the ‘not
listed’ category (65%), while the HOMEChem breakfast (eggs,
sausage, toast, tomato, coffee) has the highest level of compounds
predicted to have mutagenicity, developmental toxicity, or both (53%).
However, we emphasize uncertainties of predictive abilities (false
negatives) and the limited health endpoints in the T.E.S.T. model:
molecules that are ‘not listed’ by this model or the
OEHHA/HAPs databases may still have negative health consequences,
including those beyond developmental toxicity and mutagenicity. For
example, isocyanic acid (HNCO) can undergo carbamoylation reactions,
which are linked with cardiovascular disease, rheumatoid arthritis,
and cataracts.[63] However, HNCO is not listed
in either database nor identified within the endpoints of the T.E.S.T.
model (mutagenicity, developmental toxicity). Bleach mopping releases
many oxygenated and chlorinated organic compounds that are not in
the T.E.S.T. model but warrant further study regarding negative health
effects outside of the T.E.S.T. endpoints.
Hazard Quotients
Few molecules measured
indoors during HOMEChem exceed acute, chronic, or chronic-weighted
limits, and no molecules measured outdoors exceed any limits (Figure , Figure S4, and Table S1). Long-term
exposure to house background air is generally considered a chronic
exposure, but short-term increases represent acute or short-term exposures.
Acute and chronic exposure to the same compound can have different
health outcomes. Acrolein and formaldehyde have both a chronic contribution
from the house background air and an acute contribution from specific
short-term indoor activities. One approach to parsing exposure time
is weighting exposure by time spent in each activity/location. Figure presents ‘chronic-weighted’
hazard quotients based on HOMEChem layered days, which included cooking
three meals and cleaning. No compound’s level exceeded a chronic-weighted
hazard quotient of one, emphasizing that while cooking and cleaning
can release known air toxics, it is indoor air in the absence of activities
that dominates chronic exposure risk due to the amount of time we
spend indoors.
Figure 3
Median hazard quotients (ratio of observed concentration
of a given
species to a guideline threshold concentration for that species) for
background and outdoor (first and third columns; light yellow figure
backgrounds) and cooking (second and fourth columns; light red figure
backgrounds) activities at HOMEChem. We show acute (1 h exposure;
top row), chronic-weighted (lifetime exposure multiplied by the fraction
of time spent upon that activity or location (e.g., indoors with no
activities, the “House background”; middle row; see
Methods & Materials for calculations) and chronic (lifetime exposure;
bottom row) hazard quotients. We compare hazard quotients obtained
from the OEHHA (left side) versus HAPs guidelines (right side). We
only show hazard quotients >0.1 here. Table S1 lists hazard quotients for other compounds identified within
the
OEHHA and/or HAPs guidelines and observed during HOMEChem.
Median hazard quotients (ratio of observed concentration
of a given
species to a guideline threshold concentration for that species) for
background and outdoor (first and third columns; light yellow figure
backgrounds) and cooking (second and fourth columns; light red figure
backgrounds) activities at HOMEChem. We show acute (1 h exposure;
top row), chronic-weighted (lifetime exposure multiplied by the fraction
of time spent upon that activity or location (e.g., indoors with no
activities, the “House background”; middle row; see
Methods & Materials for calculations) and chronic (lifetime exposure;
bottom row) hazard quotients. We compare hazard quotients obtained
from the OEHHA (left side) versus HAPs guidelines (right side). We
only show hazard quotients >0.1 here. Table S1 lists hazard quotients for other compounds identified within
the
OEHHA and/or HAPs guidelines and observed during HOMEChem.Our hazard quotient analysis identifies seven known
air toxics
of concern during HOMEChem: acrolein, acrylic acid, formaldehyde,
acetaldehyde, acetamide, acrylonitrile, and benzene (Figures and 4). Acrolein, a pulmonary toxicant emitted by lumber and heating of
fats,[5,20] has the highest chronic, chronic-weighted,
and acute hazard quotients in both house background and cooking, often
>1. No compounds are near an acute hazard quotient of one during
mopping
with bleach, pine, or natural products, although emissions of molecular
chlorine (Cl2) from bleach mopping are substantial and
would result in hazard quotients ≫1 if considered against chronic
thresholds (Figure S4). Other compounds
with hazard quotients over or near one for house background air and
cooking included acetaldehyde, formaldehyde, and acrylic acid. Potential
instrument interferences cause formaldehyde hazard quotients to represent
lower bounds during HOMEChem (SI S2).
Figure 4
Predicted number of tumors per 1 million
people exposed for (a)
background and outdoor and (b) cooking activities at HOMEChem for
the OEHHA threshold concentrations, assuming a chronic exposure. The
inset figure in (a) shows chronic-weighted tumor calculations for
the background and outside. The HAPs guideline predictions are shown
in Figure S5. We only show species predicted
to cause one or more tumors per 1 million people exposed here, with
the full list of possible carcinogens and number of tumors predicted
for other compounds identified within the OEHHA and/or HAPs guidelines
and observed during HOMEChem listed in Table S1. No compound exceeds a chronic-weighted tumor risk of 1 for the
outside or any cooking activity.
Predicted number of tumors per 1 million
people exposed for (a)
background and outdoor and (b) cooking activities at HOMEChem for
the OEHHA threshold concentrations, assuming a chronic exposure. The
inset figure in (a) shows chronic-weighted tumor calculations for
the background and outside. The HAPs guideline predictions are shown
in Figure S5. We only show species predicted
to cause one or more tumors per 1 million people exposed here, with
the full list of possible carcinogens and number of tumors predicted
for other compounds identified within the OEHHA and/or HAPs guidelines
and observed during HOMEChem listed in Table S1. No compound exceeds a chronic-weighted tumor risk of 1 for the
outside or any cooking activity.Using the OEHHA/HAPs databases, we find elevated
tumor risks for
formaldehyde, acetaldehyde, acetamide, acrylonitrile, and benzene
(Figure a,b and Figure S5; Table S1). Understanding risk from intermittent exposures such as cooking
remains limited and may be mediated by subclinical effects.[64−66] To compare different cooking activities, we calculate cancer risk
based on the same fixed exposure timeframe (continuous lifetime).
Time-weighted (chronic-weighted) risk estimates show the relative
contribution to cancer risk from continuous background exposures vs
intermittent activities (Figure a and Figure S5a). No compounds
exceed a chronic-weighted risk of 1 tumor per 1 million exposed for
the outdoor or cooking activities. For comparison, risks from indoor
exposure to radon at the 4 pCi/L remediation action level are 7300
per million;[67] risks from secondhand and
thirdhand smoke exposure indoors range 1–4100 per million[68−70] and indoor risks from benzene exposure for nonsmoking adults in
Hong Kong were > 18 per million.[71] We
do
not include uncertainty in our hazard quotient and tumor risk calculations,
but such analyses are unlikely to change which compounds have elevated
risks.We compare HOMEChem results with Logue et al.[2] who provide the most comprehensive review to
date of air
toxics for residences in the U.S. and countries that lead similar
lifestyles. Logue et al.[2] identified nine
priority hazards including five gas-phase pollutants that we also
measured at HOMEChem: acetaldehyde, acrolein, benzene, formaldehyde,
and NO2.[2] We observed these
five priority pollutants at HOMEChem at similar background concentrations
(SI S8).[2] During
HOMEChem, NO2 did not exceed a hazard quotient of 1 but
may be higher in other homes due to gas stoves or other combustion
sources. Our findings of additional compounds of interest beyond Logue
(acrylic acid, acetamide, acrylonitrile) highlight the utility of
comprehensive measurements – and the potential diversity in
indoor environments across the U.S.. Finally, particulate matter (PM)
is another key indoor air pollutant[72] and
should be also considered in exposure analyses.[73,74]
Activity-Driven Contaminant Enhancements
The enhancement in chemical air contaminant levels observed during
a given activity above initial house background air conditions highlights
specific categories for further toxicology study (Figure and Figures S6–S8; Table S3). All cooking
and cleaning activities during HOMEChem perturb indoor air composition,
increase chemical diversity, and increase the number of compounds
classified as known or potential air pollutants. However, some activities
cause greater enhancements in air concentration than others. Cleaning
with natural or pine-based products only slightly enhances chemical
diversity and levels of potentially toxic compounds, while cooking
stir-fry substantially enhances both metrics (Figure and Figures S6–S8). Bleach cleaning strongly (>1000%) enhances halogenated and
nitrogen-containing
compounds, although the majority (75–80%) of enhanced compounds
during bleach cleaning are unlisted in terms of potential toxicity.
Bleach cleaning involves secondary chemistry,[11] highlighting the potential for indoor reactions to impact exposure.
Figure 5
Chemical
diversity of compounds for which concentrations increased
by 300% (3×) or more during a given HOMEChem activity, categorized
by chemical air contaminant (top) and elemental composition (bottom).
Each pie radius is normalized by the maximum number of compounds observed
per activity to be enhanced by at least 3 times. We calculate enhancements
as the ratio to the mean levels observed for the 60 min period that
encompasses the activity (which typically took 15–30 min) and
time afterward during which levels remain elevated to the mean levels
observed 60 min before the start of the activity. Table S4 includes numerical percentage breakdowns of each
category by compound number. Figure S7 shows
the same data with the pies not normalized for ease of visual comparison.
Chemical
diversity of compounds for which concentrations increased
by 300% (3×) or more during a given HOMEChem activity, categorized
by chemical air contaminant (top) and elemental composition (bottom).
Each pie radius is normalized by the maximum number of compounds observed
per activity to be enhanced by at least 3 times. We calculate enhancements
as the ratio to the mean levels observed for the 60 min period that
encompasses the activity (which typically took 15–30 min) and
time afterward during which levels remain elevated to the mean levels
observed 60 min before the start of the activity. Table S4 includes numerical percentage breakdowns of each
category by compound number. Figure S7 shows
the same data with the pies not normalized for ease of visual comparison.Infiltration of outdoor urban smog can also introduce
ozone to
homes,[75] as does the use of chemical air
cleaners, such as ozone and hydroxyl radical generators.[76,77] We investigated the potential for human activities (e.g., use of
ozone-generating “air purifier”, window opening during
a smog event) that introduce primary oxidants to induce secondary
chemistry with the addition of ozone to the house through the air
handling system via the return vent. Ozone increases from ∼7
ppb before the generator is turned on to around 30 ppb near the end
of the experiment (Figure S9). Figure and Figure S9 summarize enhancements of air contaminants
during ozone addition and show that (1) changes in chemical composition
are rapid and occur on timescales of seconds to minutes and (2) levels
of not only ozone but also numerous other gas-phase compounds increase
substantially (30 + %). Ozone is a well-known air pollutant that causes
inflammation in lungs and impacts the respiratory system, while the
other compounds, including formaldehyde, are likely products of surface,
particle, and gas-phase ozone reactions. Ten trace gases increased
by >30% during the ozone generator experiment, seven of which are
known (OEHHA/HAPs) or suspected (T.E.S.T.) air toxics. Nitric oxide
(NO) decreased by at least 30% and is in the unlisted category. Ozone
additions is well-established to induce indoor secondary chemistry.[78] Many compounds that increased upon ozone addition
are water-soluble and semivolatile and can thus be influenced by temperature
(Figure ) and relative
humidity.
Figure 6
Enhancement ratios (ratio of observed levels as a function of time
to the mean level observed 1 h before the ozone generator was turned
on) during an ozone generator experiment. Solid lines indicate compounds
identified in the HAPs and/or OEHHA databases. Dot-dashed lines are
compounds identified to have developmental toxicity and/or mutagenicity
by the T.E.S.T. model (Table S1). Dashed
lines are compounds that are not in the HAPs, OEHHA, or TEST databases
as a known or predicted air toxic. This figure only shows compounds
that increase or decrease by at least 30% during the ozone generator
experiment. Air conditioning was turned off during this experiment;
the right axis indicates the house temperature (C) increased by 3.4
°C.
Enhancement ratios (ratio of observed levels as a function of time
to the mean level observed 1 h before the ozone generator was turned
on) during an ozone generator experiment. Solid lines indicate compounds
identified in the HAPs and/or OEHHA databases. Dot-dashed lines are
compounds identified to have developmental toxicity and/or mutagenicity
by the T.E.S.T. model (Table S1). Dashed
lines are compounds that are not in the HAPs, OEHHA, or TEST databases
as a known or predicted air toxic. This figure only shows compounds
that increase or decrease by at least 30% during the ozone generator
experiment. Air conditioning was turned off during this experiment;
the right axis indicates the house temperature (C) increased by 3.4
°C.Chemical air contaminants can undergo transformations
in the indoor
environment both on surfaces and in air, producing an array of secondary
products that may be more or less toxic than the parent compound.[51,79] The vast diversity and total mass present indoors during HOMEChem
highlights the potential for health effects from indoor chemistry
and warrants further study. Bleach mopping provides a compelling example
(Figure S8), as multiphase chemistry substantially
enhanced levels of suspected air toxics such as chloramines, methyl
isocyanate, and cyanogen chloride.[11,13]
Implications
Indoor air has significantly
higher levels of air contaminants
than outdoor air. Chemical air contaminants present in homes can be
more chemically diverse and have higher concentrations than outdoors,
and different activities in the home can change chemical diversity
of indoor air and indoor concentrations of known and possible air
toxics. Traditional approaches to indoor environmental exposure assessment
that time-average and time-integrate indoor concentrations are not
designed to characterize exposures arising from indoor activities
that dramatically and frequently, albeit briefly, elevate levels of
specific compounds.The stark chemical difference between indoor
and outdoor air challenges
the application of outdoor air quality metrics that prioritize ambient
compounds found at National Priority Lists, such as EPA’s Air
Quality Index, to indoor environments. While the Air Quality Index
focuses on air pollutants such as ozone and NOx, our work
suggests that organic compounds like acrolein may be more relevant
and that complex halogenated or nitrogenated organic species warrant
consideration. While HOMEChem focused on one home, the underlying
concept that activities influence indoor air chemistry and thus exposure
is broadly applicable to other environments, even as the composition
and concentrations of indoor air contaminants change through emerging
products, materials, and building technologies.
Disclaimer
The views expressed in this document are
solely those of the authors
and do not necessarily reflect those of the United States Environmental
Protection Agency. The US EPA does not endorse any products or commercial
services mentioned in this publication.
Authors: D K Farmer; M E Vance; J P D Abbatt; A Abeleira; M R Alves; C Arata; E Boedicker; S Bourne; F Cardoso-Saldaña; R Corsi; P F DeCarlo; A H Goldstein; V H Grassian; L Hildebrandt Ruiz; J L Jimenez; T F Kahan; E F Katz; J M Mattila; W W Nazaroff; A Novoselac; R E O'Brien; V W Or; S Patel; S Sankhyan; P S Stevens; Y Tian; M Wade; C Wang; S Zhou; Y Zhou Journal: Environ Sci Process Impacts Date: 2019-08-14 Impact factor: 4.238
Authors: Yingjun Liu; Pawel K Misztal; Jianyin Xiong; Yilin Tian; Caleb Arata; Robert J Weber; William W Nazaroff; Allen H Goldstein Journal: Indoor Air Date: 2019-05-17 Impact factor: 5.770
Authors: Roger Sheu; Christof Stönner; Jenna C Ditto; Thomas Klüpfel; Jonathan Williams; Drew R Gentner Journal: Sci Adv Date: 2020-03-04 Impact factor: 14.136