Exposure and health risk assessment of PM2.5-bound polycyclic aromatic hydrocarbons during winter at residential homes: A case study in four Chinese cities.

Residential indoor PM2.5 were concurrently collected in Hong Kong, Guangzhou, Shanghai, and Xi'an during the winter and early spring seasons of 2016-2017, for updating the current knowledge of the spatial variation of indoor air pollution and the potential health risks in China. PM2.5-bound polycyclic aromatic hydrocarbons (PAHs) were characterized, and the associated inhalation cancer risks were assessed by a probabilistic approach. Higher levels of indoor PAHs were identified in Xi'an residences (averaged at 176.27 ng m-3) with those of other cities ranging from 3.07 to 15.85 ng m-3. Traffic-related fuel combustion was identified as a common contributor to indoor PAHs through outdoor infiltration for all investigated cities. Indoor PAHs profiles showed city-specific differences, while distinctions between profiles based on indoor activities or ambient air quality were limited. Similar with the total PAHs concentrations, the estimated toxic equivalencies (TEQ) with reference to benzo[a]pyrene in Xi'an residences (median at 18.05 ng m-3) were above the recommended value of 1 ng m-3 and were magnitudes higher than the other investigated cities with estimated median TEQ ranging from 0.27 to 1.55 ng m-3. Incremental lifetime cancer risk (ILCR) due to PAHs inhalation exposure was identified with a descending order of adult (median at 8.42 × 10-8) > adolescent (2.77 × 10-8) > children (2.20 × 10-8) > senior (1.72 × 10-8) for different age groups. Considering the lifetime exposure-associated cancer risk (LCR), potential risks were identified for residents in Xi'an as an LCR level over 1 × 10-6 was identified for half of the adolescent group (median at 8.96 × 10-7), and exceedances were identified for about 90 % of the groups of adults (10th percentile at 8.29 × 10-7) and seniors (10th percentile at 1.02 × 10-6). The associated LCR estimated for other cities were relatively insignificant.

Exploring the photocatalytic conversion mechanism of gaseous formaldehyde degradation on TiO2-x-OV surface.

To understand the conversion mechanism of photocatalytic gaseous formaldehyde (HCHO) degradation, strontium (Sr)-doped TiO2-x-OV catalysts was designed and synthesized in this study, with comparable HCHO removal performance. Our results proved that foreign-element doping reduced Ti4+ to the lower oxidation state Ti(4- x)+, and that the internal charge kinetics was largely facilitated by the unbalanced electron distribution. Oxygen vacancies (OVs) were developed spontaneously to realize an electron-localized phenomenon in TiO2-x-OV, thereby boosting O2 adsorption and activation for the enhanced generation of reactive oxygen species (ROS). At the chemisorption stage, in-situ DRIFTS spectra and density functional theory calculation results revealed that surface adsorbed O2 (Oads) and lattice O (Olat) engaged in the isomerisation of HCHO to dioxymethylene (DOM) on TiO2-x-OV and TiO2, respectively. Time-resolved DRIFTS spectra under light irradiation revealed that the DOM was then converted to formate and thoroughly oxidized to CO2 and H2O in TiO2-x-OV. While bicarbonate byproducts were detected from DOM hydroxylation or possible side conversion of CO2 in TiO2, owing to insufficient consumption of surface hydroxyl. Our study enhances the understanding on the photocatalytic oxidation of HCHO, thereby promoting the practical application in indoor air purification.

FeCo alloy encased in nitrogen-doped carbon for efficient formaldehyde removal: Preparation, electronic structure, and d-band center tailoring.

Formaldehyde is a typical indoor air pollutant that has posed severely adverse effects on human health. Herein, a novel FeCo alloy nanoparticle-embedded nitrogen-doped carbon (FeCo@NC) was synthesized with the aim of tailoring the transition-metal d-band structure toward an improved formaldehyde oxidation activity for the first time. A unique core@shell metal-organic frameworks (MOFs) architecture with a Fe-based Prussian blue analogue core and Co-containing zeolite imidazole framework shell was firstly fabricated. Then, Fe and Co ion alloying was readily achieved owing to the inherent MOF porosity and interionic nonequilibrium diffusion occurring during pyrolysis. High-angle annular dark-field scanning transmission electron microscopy and X-ray absorption fine structure spectra confirm that small FeCo alloys in situ form in FeCo@NC, which exhibits a higher formaldehyde removal efficiency (93%) than the monometallic Fe-based catalyst and a remarkable CO2 selectivity (85%) at room temperature. Density functional theory calculations indicate the number of electrons transferred from the metal core to the outer carbon layer is altered by alloying Fe and Co. More importantly, a downshift in the d-band center relative to the Fermi level occurs from - 0.93 to - 1.04 eV after introducing Co, which could alleviate the adsorption of reaction intermediates and greatly improve the catalytic performance.

Effects of indoor activities and outdoor penetration on PM2.5 and associated organic/elemental carbon at residential homes in four Chinese cities during winter.

There is increasing public attention on exposure to PM2.5 and its related health impacts. It is essential to study the pollution levels, sources, and health implications of indoor PM2.5, especially for residential homes, as people tend to spend most of their time indoors. The indoor PM2.5 mass and organic/elemental carbon (OC/EC) during winter and early spring period of 2016-2017 at 68 residential households in four large Chinese cities (i.e. Hong Kong, Guangzhou, Shanghai, and Xi'an) were studied. Average indoor PM2.5 varied by two-fold, lowest in Hong Kong (34.0 ± 14.6 µg m-3) and highest in Xi'an (78.7 ± 49.3 µg m-3), with comparable levels for Guangzhou (47.2 ± 5.4 µg m-3) and Shanghai (50.3 ± 17.9 µg m-3). Lowest air exchange rate (AER, 0.8 ± 0.8 h-1) and PM2.5 indoor/outdoor (I/O) ratio (0.72 ± 0.23) were found for Xi'an households, indicating the limited influence from indoor sources, while importance of indoor PM2.5 sources is signified with the highest PM2.5 I/O ratio (1.32 ± 0.43) identified for Shanghai households. For households in four cities, OC and EC accounted for 29.5%-38.5% and 7.5%-8.9% of the indoor PM2.5 mass, indicating the significance of carbonaceous aerosols. Larger differences between indoor and outdoor OC (2.6-8.4%) than EC (-2.2-1.5%) indicate the presence of indoor OC sources. Decreasing trends of PM2.5 I/O ratio and indoor OC proportion were found as the worsening ambient air quality. On average, 11.8 µg m-3 (23.1%) and 3.02 µg m-3 (18.7%) higher indoor PM2.5 and OC concentrations were identified for households with other indoor combustions (e.g., tobacco smoking, incense burning) compared to those with only cooking activities. For Hong Kong and Shanghai households, increments of 13.2 µg m-3 (54.1%) of PM2.5 and 4.1 µg m-3 (45.4%) of OC were found at households with cooking activities as compared to households with no specific indoor combustion.

Active Complexes on Engineered Crystal Facets of MnOx-CeO2 and Scale-Up Demonstration on an Air Cleaner for Indoor Formaldehyde Removal.

Crystal facet-dominated surfaces determine the formation of surface-active complexes, and engineering specific facets is desirable for improving the catalytic activity of routine transition-metal oxides that often deactivate at low temperatures. Herein, MnOx-CeO2 was synthetically administered to tailor the exposure of three major facets, and their distinct surface-active complexes concerning the formation and quantitative effects of oxygen vacancies, catalytically active zones, and active-site behaviors were unraveled. Compared with two other low-index facets {110} and {001}, MnOx-CeO2 with exposed {111} facet showed higher activity for formaldehyde oxidation and CO2 selectivity. However, the {110} facet did not increase activity despite generating additional oxygen vacancies. Oxygen vacancies were highly stable on the {111} facet, and its bulk lattice oxygen at high migration rates could replenish the consumption of surface lattice oxygen, which was associated with activity and stability. High catalytically active regions were exposed at the {111}-dominated surfaces, wherein the predominated Lewis acid-base properties facilitated oxygen mobility and activation. The mineralization pathways of formaldehyde were examined by a combination of in situ X-ray photoemission spectroscopy and diffuse reflectance infrared Fourier transform spectrometry. The MnOx-CeO2-111 catalysts were subsequently scaled up to work as filter substrates in a household air cleaner. In in-field pilot tests, 8 h of exposure to an average concentration of formaldehyde after start-up of the air cleaner attained the Excellent Class of Indoor Air Quality Objectives in Hong Kong.

In Situ Intermediates Determination and Cytotoxicological Assessment in Catalytic Oxidation of Formaldehyde: Implications for Catalyst Design and Selectivity Enhancement under Ambient Conditions.

Formation and decay of formaldehyde oxides (CH2OO) affect the complete oxidation of formaldehyde. However, the speciation and reactivity of CH2OO are poorly understood because of its extremely fast kinetics and indirect measurements. Herein, three isomers of CH2OO (i.e., main formic acid, small dioxirane, and minor CH2OO Criegee) were in situ determined and confirmed as primary intermediates of the room-temperature catalytic oxidation of formaldehyde with two reference catalysts, that is, TiO2/MnO x-CeO2 and Pt/MnO x-CeO2. CH2OO Criegee is quite reactive, whereas formic acid and dioxirane have longer lifetimes. The production, stabilization, and removal of the three intermediates are preferentially performed at high humidity, matching well with the decay rate of CH2OO at approximately 6.6 × 103 s-1 in humid feed gas faster than 4.0 × 103 s-1 in dry feed. By contrast, given that a thinner water/TiO2 interface was well-defined in TiO2/MnO x-CeO2, fewer reductions in the active sites and catalytic activity were found when humidity was decreased. Furthermore, lethal intermediates mostly captured at the TiO2/MnO x-CeO2 surface suppressed the toxic off-gas emissions. This study provides practical insights into the rational design and selectivity enhancement of a reliable catalytic process for indoor air purification under unfavorable ambient conditions.

Evaluation and characterization of volatile air toxics indoors in a heavy polluted city of northwestern China in wintertime.

Hazardous volatile organic compounds (VOCs) and carbonyls were evaluated in typical dwellings in Xi'an in northwestern China in wintertime. High indoor concentrations were observed for formaldehyde, acetone, naphthalene, methylene chloride and acetaldehyde, associated with characteristic pollution sources. In comparison, many of the target VOCs were higher in Chinese dwellings than those in other countries, suggesting the significances of indoor pollutions in China. Source apportionment with receptor model shows that furniture and building materials (44.5%), paints and adhesives (11.9%), household products (17.3%), smoking (14.5%), and cooking (9.8%) are the major contributors to the indoor VOCs and carbonyls. The health risk assessment shows that the cancer risks for formaldehyde (5.73 × 10-5), 1,3-butadiene (2.07 × 10-5) and 1,2-dichloroethane (1.44 × 10-5) were much higher than the acceptable level of 1 × 10-6 recommended by International Register for Certified Auditors (IRCA). The hazard quotient (HQ) of target VOCs were far less than the threshold (HQ = 1). Moreover, the practical efficiency of household air purifier in removal of the VOCs and carbonyls was examined first time in dwellings in northern China. The results prove that most of the indoor organic pollutants and their cancer risk to humans can be efficiently reduced, particularly for formaldehyde and 1,3-butadiene. The findings of the study offer useful preliminary and updated information on current indoor air toxics levels, dominant pollution sources and their potential health risks to residents in northwest China.

Biocompatible FeOOH-Carbon quantum dots nanocomposites for gaseous NOx removal under visible light: Improved charge separation and High selectivity.

Development of biocompatible photocatalysts with improved charge separation and high selectivity is essential for effective removal of air pollutants. Iron-containing catalysts have attracted extensive attention due to their low-toxicity and high natural abundance. Here, carbon quantum dots (CQDs) modified FeOOH nanocomposites fabricated using a facile hydrothermal route showed enhanced NO removal efficiency (22%) compared to pure FeOOH. Moreover, generation of toxic NO2 intermediates was significantly inhibited using the nanocomposites, demonstrating high selectivity for final nitrate formation. Photo-electrochemical results showed that both charge separation and transfer efficiency were significantly improved by CQDs addition, and the lifetime of photo-generated carriers was increased eventually. Density functional theory calculations further elucidated that the suppressed recombination of photo-induced electron-hole pairs was due to enhanced electron migration from the FeOOH to CQDs. A NO degradation mechanism was proposed based on detection of the reactive oxygen species using electron paramagnetic spectroscopy. In addition, the nanocomposite showed good biocompatibility and low cytotoxity, ensuring minimal environmental impact for potential application in large-scale.

Personal exposure to fine particles (PM2.5) and respiratory inflammation of common residents in Hong Kong.

BACKGROUND: Given the lack of research on the personal exposure to fine particles (PM2.5) in Hong Kong, we examined the association between short-term personal exposure to PM2.5 and their constituents and inflammation in exhaled breath in a sample of healthy adult residents. METHOD: Forty-six participants underwent personal PM2.5 monitoring for averagely 6 days to obtain 276 samples. Fractional exhaled nitric oxide (FeNO), a biomarker of inflammation in exhaled breath, was measured at the end of each 24-h personal monitoring. PM2.5 chemical constituents, including organic carbon, elemental carbon, 16 polycyclic aromatic hydrocarbons (PAHs), and 6 phthalate esters, were speciated from the personal samples collected. A mixed-effects model was used to estimate the association of PM2.5 and their constituents with FeNO. The comparison was also made with parallel analyses using ambient concentrations. RESULTS: Personal exposures to PM2.5 (28.1 ±â€¯23.3 µg/m3) were higher than the ambient levels (13.3 ±â€¯6.4 µg/m3) monitored by stations. The composition profile and personal-to-ambient concentration ratio varied among subjects with different occupations. An interquartile range (IQR) change in personal exposure to PM2.5 was positively associated with 12.8% increase in FeNO (95% confidence interval, CI: 5.5-20.7%), while nil association was found for ambient PM2.5. Among the constituents measured, only the carcinogenic PAHs were significantly associated with 12% increase in FeNO responses (95% CI, 0.0-25.6%). CONCLUSION: In conclusion, our study provides the first understanding about personal exposure to PM2.5 and possible sources in Hong Kong. The results also showed that personal exposure to PM2.5 and c-PAHs were linked to increased FeNO levels among healthy adults.

Human cancer risk estimation for 1,3-butadiene: An assessment of personal exposure and different microenvironments.

This study estimated the lifetime cancer risk (LCR) attributable to 1,3-butadiene (BD) personal exposure and to other microenvironments, including residential home, outdoor, in-office, in-vehicle, and dining. Detailed life expectancy by country (WHO), inhalation rate and body weight by gender reported by USEPA were used for the calculation, focusing on adult population (25≤Age<65). LCR estimation of the adult population due to personal exposure exceeded the USEPA benchmark of 1×10-6 in many cities. For outdoor BD exposure, LCR estimations in 45 out of 175 cities/sites (sharing 26%) exceeded the USEPA benchmark. Out of the top 20 cities having high LCR estimations, developing countries contributed 19 cities, including 14, 3, 1, 1 cities in China, India, Chile, and Pakistan. One city in the United States was in the list due to the nearby industrial facilities. The LCR calculations for BD levels found in residential home, in-vehicle and dining microenvironments also exceeded 1×10-6 in some cities, while LCR caused by in-office BD levels had the smallest risk. Four cities/regions were used for investigating source distributions to total LCR results because of their sufficient BD data. Home exposure contributed significantly to total LCR value (ranging 56% to 86%), followed by in-vehicle (4% to 38%) and dining (4 to 7%). Outdoor microenvironment shared highly in Tianjin with 6%, whereas in-office contributed from 2-3% for all cities. High LCR estimations found in developing countries highlighted the greater cancer risk caused by BD in other cities without available measurement data.

Cancer risk from gaseous carbonyl compounds in indoor environment generated from household coal combustion in Xuanwei, China.

Airborne carbonyls were characterized from emitted indoor coal combustion. Samples were collected in Xuanwei (Yunnan Province), a region in China with a high rate of lung cancer. Eleven of 19 types of samples (58%) demonstrated formaldehyde concentrations higher than the World Health Organization exposure limit (a 30-min average of 100 µg m-3). Different positive significant correlations between glyoxal/methylglyoxal and formaldehyde/acetaldehyde concentrations were observed, suggesting possible different characteristics in emissions between two pairs of carbonyl compounds. A sample in the highest inhalation risk shows 29.2 times higher risk than the lowest sample, suggesting different coal sampling locations could contribute to the variation of inhalation risk. Inhabitants in Xuanwei also tend to spend more time cooking and more days per year indoors than the national average. The calculated cancer risk ranged from 2.2-63 × 10-5, which shows 13 types of samples at high-risk level. Cumulative effect in combination with different carbonyls could have contributed to the additive actual inhalation cancer risk. There is a need to explicitly address the health effects of environmentally relevant doses, considering life-long exposure in indoor dwellings.

Revisiting nitrous acid (HONO) emission from on-road vehicles: A tunnel study with a mixed fleet.

Nitrous acid (HONO) is an important precursor of OH radicals in the atmosphere. In urban areas, emissions from vehicles are the main source of air pollutants, including reactive nitrogen. Previously reported emission ratios of HONO (HONO/NOx) from vehicles were measured in the late 1990s and need to be updated due to the significant changes in emission control technologies. We measured the emission ratio of a fleet of vehicles (38% diesel on average) from March 11 to 21, 2015, in a road tunnel in Hong Kong. The emission ratio of 1.24% (±0.35%) obtained is greater than the commonly adopted 0.8% or 0.3%. The elevated emission ratio is found to be related to the presence of vehicles equipped with diesel particle filters (DPFs). Positive correlation between HONO and black carbon (BC) shows that HONO and BC were emitted together, while the lack of correlation or even anticorrelation between HONO/NOx and BC indicates that the BC-mediated conversion of NO2 to HONO in the dark was insignificant in the immediate vicinity of the emission sources. IMPLICATIONS: Vehicular emission is a key source for HONO in the urban atmosphere. However, the most commonly used emission ratio HONO/NOx in modeling studies was measured more than 15 years ago. Our tunnel study suggests that a mixed fleet nowadays has a higher emission ratio, possibly because of the diesel particle filter (DPF) retrofit program and the growing share of Euro IV or more advanced diesel vehicles. Our study also provides new insight into the role of black carbon in HONO formation from vehicles.

Characteristics and health impacts of VOCs and carbonyls associated with residential cooking activities in Hong Kong.

Cooking emission samples collected in two residential kitchens were compared where towngas (denoted as dwelling A) and liquefied petroleum gas (LPG) (denoted as dwelling B) were used as cooking fuels. A total of 50 different volatile organic compounds (VOCs) were quantified during the 90 min cooking periods. None of any carcinogenic compounds like formaldehyde, acetaldehyde or benzene are detected in the raw fuels, confirming that those are almost entirely derived due to cooking activity alone. Alkenes accounted for approximately 53% of the total measured VOCs collected at dwelling A, while alkanes contributed approximately 95% of the VOCs at dwelling B during the cooking periods. The concentration of aromatic hydrocarbons such as benzene and toluene also increased during the cooking periods. The total amount of carbonyls emitted from the cooking processes at dwelling A (2708 µg) is three times higher than that at dwelling B (793 µg). Acetaldehyde was the most abundant carbonyl at the dwelling A but its emission was insignificant at the dwelling B. Carcinogenic risks on chronic exposure to formaldehyde, acetaldehyde, and benzene for housewives and domestic helpers were evaluated. Formaldehyde accounts for 68% and close to 100% of lifetime cancer risks at dwelling A and B, respectively.