Elemental Characterization of Ambient Particulate Matter for a Globally Distributed Monitoring Network: Methodology and Implications.

Global ground-level measurements of elements in ambient particulate matter (PM) can provide valuable information to understand the distribution of dust and trace elements, assess health impacts, and investigate emission sources. We use X-ray fluorescence spectroscopy to characterize the elemental composition of PM samples collected from 27 globally distributed sites in the Surface PARTiculate mAtter Network (SPARTAN) over 2019-2023. Consistent protocols are applied to collect all samples and analyze them at one central laboratory, which facilitates comparison across different sites. Multiple quality assurance measures are performed, including applying reference materials that resemble typical PM samples, acceptance testing, and routine quality control. Method detection limits and uncertainties are estimated. Concentrations of dust and trace element oxides (TEO) are determined from the elemental dataset. In addition to sites in arid regions, a moderately high mean dust concentration (6 µg/m3) in PM2.5 is also found in Dhaka (Bangladesh) along with a high average TEO level (6 µg/m3). High carcinogenic risk (>1 cancer case per 100000 adults) from airborne arsenic is observed in Dhaka (Bangladesh), Kanpur (India), and Hanoi (Vietnam). Industries of informal lead-acid battery and e-waste recycling as well as coal-fired brick kilns likely contribute to the elevated trace element concentrations found in Dhaka.

Insights into interactions of biodegradable and non-biodegradable microplastics with heavy metals.

Biodegradable microplastics (BMPs) are considered to be environmentally friendly compared to non-biodegradable plastics (NMPs). However, BMPs are likely to become toxic during their transport because of the adsorption of pollutants (e.g., heavy metals) onto them. This study investigated the uptake of six heavy metals (Cd2+, Cu2+, Cr3+, Ni2+, Pb2+, and Zn2+) by a common BMPs (polylactic acid (PLA)) and compared their adsorption characteristics to those of three types of NMPs (polyethylene (PE), polypropylene (PP), and polyvinyl chloride (PVC)) for the first time. The order of heavy metal adsorption capacity among the four MPs was PE > PLA > PVC > PP. The findings suggest that BMPs contained more toxic heavy metals than some NMPs. Among the six heavy metals, Cr3+ showed considerably stronger adsorption than other heavy metals in both BMPS and NMPs. The adsorption of heavy metals on MPs can be well explained using the Langmuir isotherm model, while the adsorption kinetic curves showed the best fit to the pseudo-second-order kinetic equation. Desorption experiments revealed that BMPs released a higher percentage of heavy metals (54.6-62.6%) in the acidic environment in a shorter time (~ 6 h) compared to NMPs. Overall, this study provides insights into interactions of BMPs and NMPs with heavy metals and their removal mechanisms in aquatic environment.

Greenhouse Gas Emission Mitigation Pathways for Urban Passenger Land Transport under Ambitious Climate Targets.

Urban passenger land transport is an important source of greenhouse gas (GHG) emissions globally, but it is challenging to mitigate these emissions as this sector interacts with many other economic sectors. We develop the Climate change constrained Urban passenger Transport Integrated Life cycle assessment (CURTAIL) model to outline mitigation pathways of urban passenger land transport that are consistent with ambitious climate targets. CURTAIL uses the transport activity of exogenously defined modal shares to simulate the associated annual vehicle stocks, sales, and life cycle GHG emissions. It estimates GHG emission budgets that are consistent with global warming below 2 and 1.5 °C above preindustrial levels and seeks mitigation strategies to remain within the budgets. We apply it to a case study of Singapore, a city-state. Meeting a 1.5 °C target requires strong commitments in the transport and electricity sectors, such as reducing the motorized passenger activity, accelerating the deployment of public transit and of electrification, and decarbonizing the power generation system. Focusing on one mitigation technology or one mode of transport alone will not be sufficient to meet the target. Our novel model could be applied to any city to provide insights relevant to the design of urban climate change mitigation targets and policies.

Mitigation of indoor human exposure to airborne particles of outdoor origin in an urban environment during haze and non-haze periods.

During the 2019 smoke haze episode in Singapore, elevated levels of fine particulate matter (PM2.5) were observed, deteriorating both ambient and indoor air quality (IAQ). We investigated the mitigation of indoor human exposure to PM2.5 of outdoor origin under diverse exposure scenarios with and without filtration of PM2.5 during both hazy and non-hazy days. The key objective of our study was to make a comparative evaluation of the effectiveness of portable air cleaners (PACs) and air conditioning (AC) systems equipped with particle filters in improving IAQ and to assess related long-term carcinogenic and non-carcinogenic health risks. We conducted real-time measurements of PM2.5, black carbon mass concentrations and particle number concentrations in both indoor and outdoor areas, quantified the relative concentrations of the water-soluble fraction of toxic trace elements in PM2.5 for health risk assessment, and estimated the levels of thermal comfort. In addition, we calculated the total estimated cost of indoor air pollution control. Our findings suggest that indoor air cleaners are more effective at mitigating human exposure to airborne particles and reducing health risk with less consumption of electricity and better cost-effectiveness compared to AC. This information would be beneficial for public health interventions during major air pollution events.

Insights into characteristics of light absorbing carbonaceous aerosols over an urban location in Southeast Asia.

Light absorbing carbonaceous aerosols (LACA) consisting of black carbon (BC) and brown carbon (BrC) have received considerable attention because of their climate and health implications, but their sources, characteristics and fates remain unclear in Southeast Asia (SEA). In this study, we investigated spatio-temporal characteristics of LACA, their radiative properties and potential sources in Singapore under different weather conditions. Hourly BC concentrations, measured from May 2017 to March 2018, ranged from 0.31 µg/m3 to 14.37 µg/m3 with the mean value being 2.44 ±â€¯1.51 µg/m3. High mass concentrations of BC were observed during the south-west monsoon (SWM, 2.60 ±â€¯1.56 µg/m3) while relatively low mass concentrations were recorded during the north-east monsoon (NEM, 1.68 ±â€¯0.96 µg/m3). There was a shift in the Absorption Ångström exponent (AAE) from 1.1 to 1.4 when the origin of LACA changed from fossil fuel (FF) to biomass burning (BB) combustion. This shift is attributed to the presence of secondary BrC in LACA, derived from transboundary BB emissions during the SWM. Lower AAE values were observed when local traffic emissions were dominant during the NEM. This explanation is supported by measurements of water-soluble organic carbon (WSOC) in LACA and the corresponding AAE values determined at 365 nm using a UV-vis spectrophotometer. The AAE values, indicative of the presence of brown carbon (BrC), showed that photochemically aged LACA contribute to an enhancement in the light absorption of aerosols. In addition, spatio-temporal characteristics of BC in the intra-urban environment of Singapore were investigated across diverse outdoor and indoor microenvironments. High variability of BC was evident across these microenvironments. Several air pollution hotspots with elevated BC concentrations were identified. Overall, the results stress a need to control anthropogenic emissions of BC and BrC in order to mitigate near-term climate change impacts and provide health benefits.

Enzyme-assisted hydrothermal treatment of food waste for co-production of hydrochar and bio-oil.

Food waste was subjected to enzymatic hydrolysis prior to hydrothermal treatment to produce hydrochars and bio-oil. Pre-treatment of food waste with an enzyme ratio of 1:2:1 (carbohydrase:protease:lipase) proved to be effective in converting food waste to the two products with improved yields. The carbon contents and calorific values ranged from 43.7% to 65.4% and 17.4 to 26.9 MJ/kg for the hydrochars obtained with the enzyme-assisted pre-treatment, respectively while they varied from 38.2% to 53.5% and 15.0 to 21.7 MJ/kg, respectively for the hydrochars obtained with no pre-treatment. Moreover, the formation of carbonaceous microspheres with low concentrations of inorganic elements and diverse surface functional groups was observed in the case of enzyme-assisted food waste hydrochars. The enzymatic pre-treatment also facilitated the formation of the bio-oil with a narrow distribution of organic compounds and with the highest yield obtained at 350 °C.

2013 Southeast Asian smoke haze: fractionation of particulate-bound elements and associated health risk.

Recurring biomass burning-induced smoke haze is a serious regional air pollution problem in Southeast Asia (SEA). The June 2013 haze episode was one of the worst air pollution events in SEA. Size segregated particulate samples (2.5-1.0 µm; 1.0-0.5 µm; 0.5- 0.2 µm; and <0.2 µm) were collected during the June 2013 haze episode. PM2.5 concentrations were elevated (up to 329 µg/m(3)) during the haze episode, compared to those during the nonhaze period (11-21 µg/m(3)). Chemical fractionation of particulate-bound trace elements (B, Ca, K, Fe, Al, Ni, Zn, Mg, Se, Cu, Cr, As, Mn, Pb, Co, and Cd) was done using sequential extraction procedures. There was a 10-fold increase in the concentration of K, an inorganic tracer of biomass burning. A major fraction (>60%) of the elements was present in oxidizable and residual fractions while the bioavailable (exchangeable) fraction accounted for up to 20% for most of the elements except K and Mn. Deposition of inhaled potentially toxic trace elements in various regions of the human respiratory system was estimated using a Multiple-Path Particle Dosimetry model. The particle depositions in the respiratory system tend to be more severe during hazy days than those during nonhazy days. A prolonged exposure to finer particles can thus cause adverse health outcomes during hazy days. Health risk estimates revealed that the excessive lifetime carcinogenic risk to individuals exposed to biomass burning-impacted aerosols (18 ± 1 × 10(-6)) increased significantly (P < 0.05) compared to those who exposed to urban air (12 ± 2 × 10(-6)).

Human health risk associated with exposure to toxic elements in mainstream and sidestream cigarette smoke.

Toxic particulate elements present in cigarette smoke pose health threats to the life of smokers due to direct inhalation and at the same time increase health risks to non-smokers present in the vicinity of smokers because of their exposure. This study conducted a series of experiments using a controlled experimental chamber, equipped with simulated smoking conditions for characterization of particulate trace elements in mainstream and sidestream cigarette smoke. Four popular commercial cigarette brands available in Singapore market were used in this study. The target elements for extraction and analysis were Al, As, B, Ba, Be, Bi, Ca, Cd, Co, Cr, Cs, Cu, Fe, Ga, Hg, K, Li, Mg, Mn, Na, Ni, Pb, Rb, Se, Sn, Sr, Te, Tl and Zn of both water-soluble and total constituents. The human health risk assessment results showed that the sidestream smoke had higher concentrations of toxic elements than those in the mainstream smoke. However, risk assessment analysis revealed that the sidestream smoke resulted in less human health risks compared to the mainstream smoke due to the influence of dilution of particulate emissions in sidestream smoke prior to inhalation exposure experienced by non-smokers. The cumulative non-cancer and cancer risks of toxic elements varied from 2.0 to 3.1 and from 398.4×10(-6) to 626.1×10(-6) due to inhalation of cigarette smoke by an active smoker. In the case of non-smokers, the risks were estimated under three possible cases of exposure. The cumulative cancer risks under three different cases were greater than the permissible limits. Therefore, it could be concluded that the toxic particulate elements present in cigarette smoke have significant carcinogenic and non-carcinogenic health effects due to inhalation exposure in the environment.

A comparative toxicity evaluation of Escherichia coli-targeted ssDNA and chlorine in HepG2 cells.

In this study, a comparative assessment of the effectiveness of ssDNA and chlorine as disinfectants for treating water contaminated with Escherichia coli (E. coli) was investigated on the basis of cytotoxicity and genotoxicity. The gene targets addressed for the ssDNA based inhibition method were marA (multiple antibiotic resistance) and groL (essential gene Hsp60) in E. coli. Based on the maximum log reduction in E. coli cell numbers when compared to no ssDNA control, groL-1 was chosen as the optimized ssDNA for gene silencing-based inactivation. For toxicity assessment, HepG2 cells were exposed to extracts corresponding to concentrations of 0.2, 1, 5, 25 and 50 mL water/mL medium of chlorine doped water and 1, 10, 100, 300 nM of ssDNA. Compared with ssDNA, HepG2 cells exposed to extracts of chlorine doped water for 24 h showed higher cytotoxicity, caspase 3/7 levels, DNA damage, micronuclei frequency, and decreased cell viability. Water doped with chlorine was found to be more toxic than that by ssDNA when exposed to HepG2 cells. The results of this study provide a scientific basis for comparative evaluation of new and conventional disinfection methods by taking into consideration the outcome of cytotoxicity and genotoxicity assessments.

Emissions of particulate-bound elements from biodiesel and ultra low sulfur diesel: size distribution and risk assessment.

Use of waste cooking oil derived biodiesel (WCOB) as an alternative fuel in diesel engines has increased significantly in recent years. The impact of WCOB on particulate emissions from diesel engines needs to be investigated thoroughly. This study was conducted to make a comparative evaluation and size-differentiated speciation of the particulate bound elements from ultra low sulfur diesel (ULSD) and WCOB and a blend of both of the fuels (B50). Particle mass and their elemental size distributions ranging from 0.01-5.6 µm were measured. It was observed that more ultrafine particles (UFPs, <100 nm) were emitted when the engine was fueled with WCOB. Fifteen particulate-bound elements such as K, Al, Mg, Co, Cr, Cu, Fe, Mn, Cd, Ni, As, Ba, Pb, Zn and Sr were investigated and reported in this study. Potential health risk associated with these particulate bound elements upon inhalation was also evaluated based on dose-response assessments for both adults and children. The findings indicate that the exposure to PM of the B100 exhaust is relatively more hazardous and may pose adverse health effects compared to that of ULSD. Also, investigations on human health risk due to exposure to UFPs indicate that UFPs contribute a major fraction (>70%) of the total estimated health risk.

Physicochemical and toxicological characteristics of urban aerosols during a recent Indonesian biomass burning episode.

Air particulate matter (PM) samples were collected in Singapore from 21 to 29 October 2010. During this time period, a severe regional smoke haze episode lasted for a few days (21-23 October). Physicochemical and toxicological characteristics of both haze and non-haze aerosols were evaluated. The average mass concentration of PM2.5 (PM with aerodynamic diameter of ≤2.5 µm) increased by a factor of 4 during the smoke haze period (107.2 µg/m(3)) as compared to that during the non-smoke haze period (27.0 µg/m(3)). The PM2.5 samples were analyzed for 16 priority polycyclic aromatic hydrocarbons (PAHs) listed by the United States Environmental Protection Agency and 10 transition metals. Out of the seven PAHs known as potential or suspected carcinogens, five were found in significantly higher levels in smoke haze aerosols as compared to those in the background air. Metal concentrations were also found to be higher in haze aerosols. Additionally, the toxicological profile of the PM2.5 samples was evaluated using a human epithelial lung cell line (A549). Cell viability and death counts were measured after a direct exposure of PM2.5 samples to A459 cells for a period of 48 h. The percentage of metabolically active cells decreased significantly following a direct exposure to PM samples collected during the haze period. To provide further insights into the toxicological characteristics of the aerosol particles, glutathione levels, as an indirect measure of oxidative stress and caspase-3/7 levels as a measure of apoptotic death, were also evaluated.

Particulate emissions from a stationary engine fueled with ultra-low-sulfur diesel and waste-cooking-oil-derived biodiesel.

Stationary diesel engines, especially diesel generators, are increasingly being used in both developing countries and developed countries because of increased power demand. Emissions from such engines can have adverse effects on the environment and public health. In this study, particulate emissions from a domestic stationary diesel generator running on ultra-low-sulfur diesel (ULSD) and biodiesel derived from waste cooking oil were characterized for different load conditions. Results indicated a reduction in particulate matter (PM) mass and number emissions while switching diesel to biodiesel. With increase in engine load, it was observed that particle mass increased, although total particle counts decreased for all the fuels. The reduction in total number concentration at higher loads was, however, dependent on percentage of biodiesel in the diesel-biodiesel blend. For pure biodiesel (B100), the reduction in PM emissions for full load compared to idle mode was around 9%, whereas for ULSD the reduction was 26%. A large fraction of ultrafine particles (UFPs) was found in the emissions from biodiesel compared to ULSD. Nearly 90% of total particle concentration in biodiesel emissions comprised ultrafine particles. Particle peak diameter shifted from a smaller to a lower diameter with increase in biodiesel percentage in the fuel mixture.

Determination of aldehydes in rainwater using micro-solid-phase extraction and high-performance liquid chromatography.

A simple and rapid extraction procedure was developed for determining aldehydes in rainwater samples. This extraction technique involved the use of micro-solid-phase extraction in which the sorbent was held within a polypropylene membrane envelope, followed by high-performance liquid chromatographic analysis. Aldehydes such as formaldehyde, acetaldehyde, propionaldehyde and valeraldehyde were used as model compounds. Extraction conditions were optimized. The method linearity ranged between 0.5 and 50 µgl(-1) with the correlation coefficient of 0.987-0.999. The relative standard deviations (RSDs) of the method ranged from 7 to 12%. Method detection limits were in the range of 0.07-0.15 µgl(-1), which is lower than those previously reported for solid-phase microextraction combined with gas chromatography-mass spectrometric techniques. The proposed extraction technique was used for determination of aldehydes in rainwater samples to demonstrate the applicability of the method.

Ionic liquid supported three-phase liquid-liquid-liquid microextraction as a sample preparation technique for aliphatic and aromatic hydrocarbons prior to gas chromatography-mass spectrometry.

For the first time hollow fiber-protected ionic liquid supported three-phase (liquid-liquid-liquid) microextraction (HFM-LLLME) was developed for the gas chromatography-mass spectrometric (GC-MS) analysis of aromatic and aliphatic hydrocarbons. The hydrocarbons were extracted from 10 ml of aqueous samples though small volumes of ionic liquid and organic solvent in the hollow fiber membrane HFM) wall and channel, respectively. The ionic liquid was immiscible with both the aqueous sample and the organic solvent (toluene). After extraction, the enriched solvent was directly injected into a GC-MS system for analysis without any further pretreatment. Ionic liquid supported HFM-LLLME shows better extraction performance than two-phase HFM-liquid-phase microextraction, in which only organic solvent is involved, and solid-phase microextraction. The ionic liquid and organic solvent combination found most suitable for HFM-LLLME was 1-butyl-3-methylimidazolium hexafluorophosphate, and toluene, respectively. This new technique provided up to 210-fold enrichment of aliphatic and aromatic hydrocarbons in 40 min with good reproducibility (<11%) and limits of detection (1-7 ng l(-1)).

Assessing exposure to diesel exhaust particles: a case study.

The assessment of the vehicular contributions to urban pollution levels is of particular importance given the current interest in the possible adverse health effects. This study focused on human exposure to diesel-engine-derived particulate matter. Diesel vehicles are known to emit fine particulate matter (PM2.5) containing carcinogens such as polycyclic aromatic hydrocarbons (PAHs), and have therefore received considerable attention. In this study, the physical (mass and number concentration, and size distribution) and chemical (PAHs) properties were investigated at a major bus interchange in Singapore, influenced only by diesel exhausts. Number concentration and size distribution of particles were determined in real time, while the mass concentrations of PM2.5, and PAHs were measured during operating and nonoperating hours. The average mass concentrations of PM2.5 and PAHs increased by a factor of 2.34 and 5.18, respectively, during operating hours. The average number concentration was also elevated by a factor of 5.07 during operating hours. This increase in the concentration of PM2.5 particles and their chemical constituents during operating hours was attributable to diesel emissions from in-use buses based on the particle size analysis, correlation among PAHs, and the commonly used PAHs diagnostic ratios. To evaluate the potential health threat due inhalation of air pollutants released from diesel engines, the incremental lifetime cancer risk was also calculated for a maximally exposed individual. The findings indicate that the air quality at the bus interchange poses adverse health effects.

Health risk assessment of occupational exposure to particulate-phase polycyclic aromatic hydrocarbons associated with Chinese, Malay and Indian cooking.

Food cooking using liquefied petroleum gas (LPG) has received considerable attention in recent years since it is an important source of particulate air pollution in indoor environments for non-smokers. Exposure to organic compounds such as polycyclic aromatic hydrocarbons (PAHs) contained in particles is of particular health concern since some of these compounds are suspected carcinogens. It is therefore necessary to chemically characterize the airborne particles emitted from gas cooking to assess their possible health impacts. In this work, the levels of fine particulate matter (PM(2.5)) and 16 priority PAHs were determined in three different ethnic commercial kitchens, specifically Chinese, Malay and Indian food stalls, where distinctive cooking methods were employed. The mass concentrations of PM(2.5) and PAHs, and the fraction of PAHs in PM(2.5) were the highest at the Malay stall (245.3 microg m(-3), 609.0 ng m(-3), and 0.25%, respectively), followed by the Chinese stall (201.6 microg m(-3), 141.0 ng m(-3), and 0.07%), and the Indian stall (186.9 microg m(-3), 37.9 ng m(-3), and 0.02%). This difference in the levels of particulate pollution among the three stalls may be attributed to the different cooking methods employed at the food stalls, the amount of food cooked, and the cooking time, although the most sensitive parameter appears to be the predominant cooking method used. Frying processes, especially deep-frying, produce more air pollutants, possibly due to the high oil temperatures used in such operations. Furthermore, it is found that frying, be it deep-frying at the Malay stall or stir-frying at the Chinese stall, gave rise to an abundance of higher molecular weight PAHs such as benzo[b]fluoranthene, indeno[1,2,3-cd]pyrene and benzo[g,h,i]perylene whereas low-temperature cooking, such as simmering at the Indian stall, has a higher concentration of lower molecular weight PAHs. In addition, the correlation matrices and diagnostic ratios of PAHs were calculated to determine the markers of gas cooking. To evaluate the potential health threat due to inhalation exposure from the indoor particulate pollution, excess lifetime cancer risk (ELCR) was also calculated for an exposed individual. The findings suggest that cooking fumes in the three commercial kitchens pose adverse health effects.

Determination of organic micropollutants in rainwater using hollow fiber membrane/liquid-phase microextraction combined with gas chromatography-mass spectrometry.

A simple and rapid liquid-phase microextraction (LPME) method using a hollow fiber membrane (HFM) in conjunction with gas chromatography-mass spectrometry (GC-MS) is presented for the quantitative determination of 16 polycyclic aromatic hydrocarbons (PAHs) and 12 organochlorine pesticides (OCPs) in rainwater samples. The LPME conditions were optimized for achieving high enrichment of the analytes from aqueous samples, in terms of hollow fiber exposure time, stirring rate, sample pH, and composition. Enrichment factors of more than 100 could be achieved within 35 min of extraction with relative standard deviations (R.S.D.s) 1.3-13.6% for PAHs and 1.7-13.8% for OCPs, respectively, over a wide range of analyte concentrations. Detection limits ranged from 0.002 to 0.047 microg l(-1) for PAHs, and from 0.013 to 0.059 microg l(-1) for OCPs, respectively. The newly developed LPME-GC-MS method has been validated for the analysis of PAHs and OCPs in rainwater samples. Extraction recoveries from spiked synthetic rainwater samples varied from 73 to 115% for PAHs and from 75 to 113% for OCPs, respectively. Real rainwater samples were analyzed using the optimized method. The concentrations of PAHs and OCPs in real rainwater samples were between 0.005-0.162, and 0.063 microg l(-1), respectively.