Insight study of rare earth elements in PM2.5 during five years in a Chinese inland city: Composition variations, sources, and exposure assessment.

The booming development of rare earth industry and the extensive utilization of its products accompanied by urban development have led to the accelerated accumulation of rare earth elements (REEs) as emerging pollutants in atmospheric environment. In this study, the variation of REEs in PM2.5 with urban (a non-mining city) transformation was investigated through five consecutive years of sample collection. The compositional variability and provenance contribution of REEs in PM2.5 were characterized, and the REEs exposure risks of children and adults via inhalation, ingestion and dermal absorption were also evaluated. The results showed an increase in the total REEs concentration from 46.46 ± 35.16 mg/kg (2017) to 81.22 ± 38.98 mg/kg (2021) over the five-year period, with Ce and La making the largest contribution. The actual increment of industrial and traffic emission source among the three pollution sources was 1.34 ng/m3. Coal combustion source displayed a downward trend. Ingestion was the main exposure pathway for REEs in PM2.5 for both children and adults. Ce contributed the most to the total intake of REEs in PM2.5 among the population, followed by La and Nd. The exposure risks of REEs in PM2.5 in the region were relatively low, but the trend of change was of great concern. It was strongly recommended to strengthen the concern about traffic-related non-exhaust emissions of particulate matter.

Efficient immobilization and detoxification of gaseous elemental mercury by nanoflower/rod WSe2/halloysite composite: Performance and mechanisms.

Gaseous mercury pollution control technologies with low stability and high releasing risks always face with great challenges. Herein, we developed one halloysite nanotubes (HNTs)-supported tungsten diselenide (WSe2) composite (WSe2/HNTs) by one-pot solvothermal approach, curing Hg0 from complicated flue gas (CFG) and reducing second environment risks. WSe2 as a monolayer with nano-flower structure and HNTs with rod shapes in the as-prepared sorbent exhibited outstanding synergy efficiency, resulting in exceptional performance for Hg0 removal with high capture capacity of 30.6 mg·g-1 and rate of 9.09 µg·g-1·min-1, which benefited from the high affinity of selenium and mercury (1 ×1045) and the adequate exposure of Se-terminated. The adsorbent showed beneficial tolerance to high amount of NOx and SOx. An online lab-built thermal decomposition system (TPD-AFS) was employed to explore Hg species on the used-sorbent, finding that the adsorbed-mercury species were principally mercury selenide (HgSe). Density functional theory calculations indicated that the hollow-sites were the major adsorption sites and exhibited excellent selectivity for Hg0, as well as HgSe generation needed to overcome the 0.32 eV energy barrier. The adsorbed mercury displayed high environmental stability after the leaching toxicity test, which significantly decreased its secondary environmental risks. With these advantages, WSe2/HNTs possess enormous potential to achieve the effective and permanent immobilization of gaseous mercury from CFG in the future.

Decryption analysis of antimony pollution sources in PM2.5 through a multi-source isotope mixing model based on lead isotopes.

Antimony (Sb) in PM2.5 has attracted close attention as a new air pollutant due to its extensive use in daily life. The identification of antimony sources in PM2.5 by scientific methods is important to control its pollution. In this study, the Sb and other elements concentrations and Pb isotopic compositions in PM2.5 and possible pollution sources (soil, road dust, traffic emission, coal-fired fly ash, local factory emission dust and cement dust) were analyzed. The results showed that the Sb in the PM2.5 samples had seasonal change. The enrichment factors of Sb in PM2.5 samples were all above 100 in four seasons, which indicated anthropogenic pollution. The average value of potential ecological risk index was at extremely high-risk level greater than 320. Based on Pearson correlation coefficient and hierarchical cluster analysis results, the pollution sources of antimony and lead in PM2.5 samples were highly consistent which means that Pb isotopes might be a new and feasible tracer for Sb pollution in air. The sources analysis results based on Pb isotopes indicated that the proportion of Pb and Sb from coal-fired fly ash was the highest in winter (47.7%) and inclined to road dust in spring (34.5%), but it was mainly from traffic emissions in summer and autumn (34.2% and 32.8%). This study showed that Pb isotope tracing can be applied to predict the potential pollution sources, and it was also a feasible substitute for tracing Sb pollution in PM2.5.

Facile fabrication of Fe/Zr binary MOFs for arsenic removal in water: High capacity, fast kinetics and good reusability.

A water-stable bimetallic Fe/Zr metal-organic framework [UiO-66(Fe/Zr)] for exceptional decontamination of arsenic in water was fabricated through a facile one-step strategy. The batch adsorption experiments revealed the excellent performances with ultrafast adsorption kinetics due to the synergistic effects of two functional centers and large surface area (498.33 m2/g). The absorption capacity of UiO-66(Fe/Zr) for arsenate [As(V)] and arsenite [As(III)] reached as high as 204.1 mg/g and 101.7 mg/g, respectively. Langmuir model was suitable to describe the adsorption behaviors of arsenic on UiO-66(Fe/Zr). The fast kinetics (adsorption equilibrium in 30 min, 10 mg/L As) and pseudo-second-order model implied the strong chemisorption between arsenic ions and UiO-66(Fe/Zr), which was further confirmed by DFT theoretical calculations. The results of FT-IR, XPS analysis and TCLP test demonstrated that arsenic was immobilized on the surface of UiO-66(Fe/Zr) through Fe/Zr-O-As bonds, and the leaching rates of the adsorbed As(III) and As(V) from the spent adsorbent were only 5.6% and 1.4%, respectively. UiO-66(Fe/Zr) can be regenerated for five cycles without obvious removal efficiency decrease. The original arsenic (1.0 mg/L) in lake and tap water was effectively removed in 2.0 hr [99.0% of As(III) and 99.8% of As(V)]. The bimetallic UiO-66(Fe/Zr) has great potentials in water deep purification of arsenic with fast kinetics and high capacity.

Identification of mercury species in coal combustion by-products from power plants using thermal desorption-atomic fluorescence spectrometry on-line coupling system.

Along with the environmental protection policies becoming strict in China, the air pollution control devices (especially selective catalytic reduction (SCR)) are widely equipped in coal-fired power plants. The installation and run of these devices will inevitably affect mercury (Hg) species distribution in coal fired by-products such like fly ash (FA) and gypsum. In this work, a new on-line coupling system based on atomic fluorescence spectrometry (AFS) with a home-made chromatographic workstation was successfully developed to identify Hg species through thermal programmed desorption (TPD). The influences of matrix, furnace temperature, and carrier gas flow on analytical performance were investigated and the parameters were optimized. The FA and gypsum samples from coal-fired power plants equipped with SCR were collected and the mercury species were analyzed by the developed coupling system. HgCl2 and HgO were the main species in FA, while Hg2Cl2 and HgO were the main species in gypsum. All of Hg species in the studied FA and gypsum samples were released below 400 °C. A sequential extraction procedure was applied to further verify the operational Hg species including mobile and non-mobile fractions in FA and gypsum samples. This study demonstrated that AFS coupled with TPD procedure was an effective method to analyze Hg species in coal combustion by-products from power plants.

Exceptional removal and immobilization of selenium species by bimetal-organic frameworks.

Binary metallic organic frameworks can always play excellent functions for pollutants removal. One binary MOFs, UiO-66(Fe/Zr)), was newly synthesized and applied to remove aquatic selenite (SeIV) and selenate (SeVI). The adsorption behaviors and mechanisms were investigated using batch experiments, spectroscopic analyses, and theoretical calculations (DFT). The characterization results showed that the material inherited the topological structure of UiO-66 and excellent thermal stability. The large specific surface area (467.52 m2/g) and uniform mesoporous structures of the synthesized MOFs resulted in fast adsorption efficiency and high adsorption capacity for selenium species. The adsorbent kept high adsorption efficiency in a wide pH range from 2 to 11 with good anti-interference ability. The maximum adsorption capacity for Se(IV) and Se(VI) reached as high as 196 mg/g at pH 3 and 258 mg/g at pH 5, respectively. The process was conformed to fit pseudo-second-order kinetics and Langmuir isotherm, and could be explained by the formation of Fe/Zr-O-Se bond on the material surface, which was interpreted by the results of XPS, FTIR and DFT calculation. The regeneration and TCLP experiments demonstrated that UiO-66(Fe/Zr) could be regenerated for five cycles without obvious decrease of efficiencies, and the leaching rate of the adsorbed Se(IV) and Se(VI) in the spent adsorbent were only 4.8% and 2.3%. More than 99% of original Se(IV) and Se(VI) in the lake and tap water samples (1.0 mg/L of Se) could be removed in 2.0 h.

Simultaneous removal of arsenate and arsenite in water using a novel functional halloysite nanotube composite.

This work aims at exploring a novel environment-friendly nanomaterial based on natural clay minerals for arsenic removal in aqueous samples. Halloysite nanotubes (HNTs) were selected as the substrate with Mn oxides loaded on the surface to enhance its arsenic adsorption ability and then grafted onto the SiO2-coated Fe3O4 microsphere to get a just enough magnetic performance facilitating the material's post-treatment. The prepared composite (Fe3O4@SiO2@Mn-HNTs) was extensively characterized by various instruments including Fourier transform infrared spectroscope (FTIR), scanning electron microscope (SEM), transmission electron microscope (TEM), thermogravimetric analysis (TG), vibrating sample magnetometer (VSM), X-ray photoelectron spectroscope (XPS), and X-ray diffraction (XRD). Batch experiments were carried out to get the optimum test conditions for arsenic adsorption by the composite, including pH, loading amount of Mn oxides, adsorbent dosage, and the co-existing ions. The adsorption of AsIII and AsV on Fe3O4@SiO2@Mn-HNTs were both well fitted with the pseudo-second-order kinetic model as well as the Langmuir adsorption isotherm model revealing the chemisorption between arsenic and Fe3O4@SiO2@Mn-HNTs. The adsorption process of AsIII and AsV were both endothermic and spontaneous displayed by the thermodynamic study. The capacities of the prepared composite are 3.28 mg g-1 for AsIII and 3.52 mg g-1 for AsV, respectively, which are comparable or better than those of many reported materials in the references. Toxicity characteristic leaching procedure (TCLP) and synthetic precipitation leaching procedure (SPLP) tests were carried out to access the secondary environmental risk of the composite and showed that it was quite environmentally stable and can be safely disposed. The composite was successfully applied in environmental water samples indicating its great potential applicability in future.

Gaseous Arsenic Capture in Flue Gas by CuCl2-Modified Halloysite Nanotube Composites with High-Temperature NOx and SOx Resistance.

Gaseous arsenic emitted from coal combustion flue gas (CCFG) causes not only severe contamination of the environment but also the failure of selective catalytic reduction (SCR) catalysts in power plants. Development of inexpensive and effective adsorbents or techniques for the removal of arsenic from high-temperature CCFG is crucial. In this study, halloysite nanotubes (HNTs) at low price were modified with CuCl2 (CuCl2-HNTs) through ultrasound assistance and applied for capturing As2O3(g) in simulated flue gas (SFG). Experiments on arsenic adsorption performance, adsorption mechanism, and adsorption energy based on density functional theory were performed. Modification with CuCl2 clearly enhanced the arsenic uptake capacity (approximately 12.3 mg/g) at 600 °C for SFG. The adsorbent exhibited favorable tolerance to high concentrations of NOx and SOx. The As2O3(III) was oxidized and transformed into As2O5(V) on the CuCl2-HNTs. The Al-O bridge had the highest adsorption energy for the O end of the As-O group (-2.986 eV), and the combination formed between arsenic-containing groups and aluminum was stable. In addition, the captured arsenic could be stabilized in the sorbent at high temperature, making it possible to use the sorbent before the SCR system. This demonstrates that CuCl2-HNTs is a promising sorbent for arsenic oxidation and removal from CCFG.

Microwave-assisted continuous flow phytosynthesis of silver nanoparticle/reduced graphene oxide composites and related visible light catalytic performance.

The creation of an environmentally friendly synthesis method for silver nanomaterials (AgNPs) is an urgent concern for sustainable nanotechnology development. In the present study, a novel straightforward and green method for the preparation of silver nanoparticle/reduced graphene oxide (AgNP/rGO) composites was successfully developed through the combination of phytosynthesis, continuous flow synthesis and microwave-assistance. Oriental persimmon (Diospyros kaki Thunb.) extracts were used as both plant reducing and capping agents for fast online synthesis of AgNP/rGO composites. The experimental parameters were optimized and the morphologies of the prepared materials were investigated. The characterization results reveal that spherical AgNPs were quickly synthesized and uniformly dispersed on rGO sheets using the proposed online system. Fourier transform infrared spectroscopy analysis confirmed that phenols, flavonoids, and other substances in the plant extracts played a decisive role in the synthesis of AgNP/rGO composites. Using sodium borohydride (NaBH4) degradation of p-nitrophenol (4-NP) as a model, the catalytic activity of the prepared AgNP/rGO materials was evaluated. The complete degradation of 4-NP was achieved within 12 min through the use of AgNP/rGO materials, and the composite had a much better catalytic activity than the bare AgNPs and rGO had. Compared with the conventional chemical method, our online method is facile, fast, cost-efficient, and environmentally friendly.

Electrospun metal-organic frameworks hybrid nanofiber membrane for efficient removal of As(III) and As(V) from water.

Metal-organic frameworks (MOFs) have been widely applied for pollutants removal in water. However, the powdered MOFs are always suffered from aggregation during use and difficult collection after use. These problems discount their efficiency and inhibit their reusability. In this work, Zr-based MOF (UiO-66) was successfully imprisoned into a water-stable polyacrylonitrile (PAN) substrate by electrospinning. The containing UiO-66 hybrid membrane was confirmed by instrumental characterizations and its stability was also investigated by ICP-OES analysis. The obtained composite membrane can efficiently remove both arsenite (AsIII) and arsenate (AsV) from water under natural pH conditions. The adsorption kinetic fitted well with pseudo-second-order model and was dominated by chemisorption. Its adsorption isotherm can be described by Langmuir model. The maximal adsorption capacities of the hybrid membrane for As(V) and As(III) were 42.17 mg/g and 32.90 mg/g, respectively. Our results demonstrated that the MOFs-dispersed electrospun nanofiber membrane can greatly inherit the MOFs' original adsorption properties and exhibits good regenerability without loss of MOFs. Electrospinning is an effective and practical method for the preparation of MOFs hybrid membrane, which makes the composite very easy to be collected after use.

Distribution and chemical speciation of arsenic in different sized atmospheric particulate matters.

The distribution and chemical speciation of arsenic (As) in different sized atmospheric particulate matters (PMs), including total suspended particles (TSP), PM10, and PM2.5, collected from Baoding, China were analyzed. The average total mass concentrations of As in TSP, PM10, and PM2.5 were 31.5, 35.3, and 54.1 µg/g, respectively, with an order of PM2.5 >PM 10 > TSP, revealing that As is prone to accumulate on fine particles. Due to the divergent toxicities of different As species, speciation analysis of As in PMs is further conducted. Most of previous studies mainly focused on inorganic arsenite (iAsIII), inorganic arsenate (iAsV), monomethylarsonate (MMA), and dimethylarsinate (DMA) in PMs, while the identification and sensitive quantification of trimethylarsine oxide (TMAO) were rarely reported. In this study, a high-performance liquid chromatography coupled to inductively coupled plasma mass spectrometry system was optimized for As speciation including TMAO in PMs. An anion exchange column was used to separate MMA, DMA and iAsV, while a cation exchange column to separate TMAO and iAsIII. Results showed that iAsV was the dominate component in all the samples, corresponding to a portion of 79.2% ± 9.3% of the total extractable species, while iAsIII, TMAO and DMA made up the remaining 21%. Our study demonstrated that iAsIII accounted for about 14.4% ± 11.4% of the total extracted species, with an average concentration of 1.7 ± 1.6 ng/m3. It is worth noting that TMAO was widely present in the samples (84 out of 97 samples), which supported the assumption that TMAO was ubiquitous in atmospheric particles.

Synergistic effects of Fe-Mn binary oxide for gaseous arsenic removal in flue gas.

High-efficient and economic sorbents are highly desired for arsenic (As) emission control in flue gas from coal-fired power plant. A series of Fe-Mn binary oxides were prepared by a facile method, and their behaviors for gaseous arsenic removal in flue gas were investigated. The binary oxide exhibited a remarkable synergistic effect for arsenic removal compared with Mn or Fe monometallic oxide. The possible effects of CO2, NO, SO2, and O2 on the removal performance were also studied. The adsorption ability was excellent and stable in simulated flue gas conditions. X-ray photoelectron spectroscopy (XPS) and high-performance liquid chromatography atomic fluorescence spectroscopy (HPLC-AFS) coupling system were applied to analyze the species of surface-adsorbed arsenicals and soluble arsenicals. It was confirmed that the good sorption performance resulted from oxidation of As2O3 (As(III)) to As2O5 (As(V)) by Mn oxide and followed by efficient adsorption of As(V) on Fe oxide. Considering the toxicity of pentavalent arsenicals is lower than trivalent arsenicals, the oxidation of arsenic compounds can not only enhance its removal capacity but also decrease the toxicity of arsenicals after capture.

Preparation of halloysite nanotubes-encapsulated magnetic microspheres for elemental mercury removal from coal-fired flue gas.

Halloysite nanotubes (HNTs) as a natural and inexpensive clay mineral with hollow nanotubular structures, good biocompatibility and active surfaces have been ubiquitously applied in many fields. In this work, a novel multifunctional core-shell sorbent based on HNTs, CuCl2-HNTs encapsulated magnetic microspheres (SiO2@Fe3O4), was successfully fabricated and applied for Hg0 removal from flue gas with good performance for the first time. The core-shell structure prevented the composites from aggregating but kept their magnetism, which enabled the adsorbents being easily separated for reuse by an external magnetic field. In addition, the special structure also significantly enhanced the adsorption capacity of the composites by dispersing the CuCl2 modified HNTs on the prepared magnetic microspheres. The adsorption performance was comprehensively investigated and fitted by dynamic models. The adsorption followed surface adsorption, particle diffusion and chemisorption with very good SO2 tolerance. The Cu+, Cl- and lattice oxygen were the crucial components for Hg0 removal. In order to further understand the possible mechanism, an online home-made coupling system of temperature-programmed decomposition (TPD) was used to investigate the mercury species on the spent adsorbent in addition to X-ray photoelectron spectroscopy analysis. The results confirmed the mercury species adsorbed were primarily Hg0, HgO and HgCl2.

Elimination of elemental mercury in flue gas by Arachis hypogaea Linn. shell generated activated carbon.

It is very necessary to produce bio-activated carbon for special use with easy procedure and low cost. One kind of huge surface area microporous bio-material was successfully prepared from agricultural residues (peanut shell, Arachis hypogaea Linn.) and beneficially applied to control elemental mercury (Hg0) in simulated coal-fired flue gas in this study. The possible effects of experimental factors including activator, reaction temperature, and flue components were investigated. The physicochemical properties of the prepared adsorbents were characterized by Brunauer-Emmett-Teller (BET), scanning electron microscopy with energy-dispersive X-ray spectrometry (SEM-EDX), and X-ray photoelectron spectroscopy (XPS). The results indicated that the peanut shell activated carbon presented excellent Hg0 removal efficiency near 90% at 150 °C. The characterization analysis indicated that the removal characteristics were governed by both physical adsorption and chemical adsorption. The chemisorbed mercury on the activated carbon was mainly distinguished into mercuric chloride (HgCl2) and mercuric oxide (HgO). The presence of C-Cl and O* promoted Hg0 into HgCl2 and HgO. Zinc chloride could not only improve the micropore quantity of activated carbon but also have remarkably positive effects on the elemental mercury removal. This study provided a practical and easy preparation method of bio-activated carbon for Hg0 removal with low cost. Graphical Abstract.

PM2.5-bound potentially toxic elements (PTEs) fractions, bioavailability and health risks before and after coal limiting.

Fractions, bioavailability, health risks of fine particulate maters (PM2.5)-bound potentially toxic elements (PTEs) (Pb, Cd, Cr, Cu and Zn) were investigated before and after coal limiting in Baoding city. The winter PM2.5 samples were collected at different functional areas such as residential area (RA), industrial area (IA), suburb (SB), street (ST) and Botanical Garden Park (BG) in 2016 (coal dominated year) and 2017 (gas dominated year). The fractions and bioavailability of PTEs were determined and evaluated based on BCR sequential extraction. Health risks through inhalation exposure were evaluated by US EPA health risk assessment model. The results from different years and functional areas were compared and discussed. The fractions and bioavailability of PM2.5-bound PTEs varied with functional areas. The percentages of cadmium (Cd) and zinc (Zn) in acid-soluble fraction (F1-Cd and F1-Zn) to the total amount of Cd and Zn were low in BG samples (p < 0.05). Bioavailability of Cd were high in SB samples (p < 0.05). Total contents of PM-bound PTEs in 2017 generally decreased compared with 2016. The differences of fraction and bioavailability between 2016 and 2017 depended on the elements and areas. Higher proportions of copper (Cu) in acid-soluble fraction (F1-Cu) and bioavailability of Cu (p < 0.05) were found in 2017 samples. Significant differences were found just at IA and RA for Pb, Cd and Zn. Our results indicated that the health risks from inhalation exposure for PTEs in PM2.5 declined about 11%-52% after the coal limiting in this city.

Comparison of arsenic fractions and health risks in PM2.5 before and after coal-gas replacement.

Coal-Gas replacement project has been implemented to decrease haze pollution in China in recent years. Airborne arsenic (As) mostly originates from coal burning processes. It is noteworthy to compare the distribution of arsenic fraction in PM2.5 before and after coal-gas replacement. Eighty PM2.5 samples were collected in Baoding in December 2016 (coal dominated year) and December 2017 (gas dominated year) at different functional areas including residential area (RA), industrial area (IA), suburb (SB), roadside (ST) and Botanical Garden Park (BG). The fraction, bioavailability and health risk of As in the PM2.5 samples were investigated and compared between these two years. Arsenic was mainly distributed in the non-specifically sorbed fraction (F1) and the residual fraction (F5). However, the proportion of F1 to the total As in 2017 was higher than that in 2016, while the proportion of As in the amorphous and poorly-crystalline hydrous oxides of Fe and Al fraction (F3) in 2017 was lower. The distributions of fraction and bioavailability showed temporal and spatial characteristics. The total concentration and bioavailability of As in SB and IA were significantly higher than those in RA, ST and BG. The BF (Bioavailability Factor) values of As ranged from 0.30 to 0.61. Health risk assessment indicated that the hazard quotient (HQ) and carcinogenic risk (CR) of As in PM2.5 significantly decreased after coal-gas replacement.

Fractions of arsenic and selenium in fly ash by ultrasound-assisted sequential extraction.

Sequential extraction has been validated as an effective method to assess the fractions of elements in fly ash. However, the time consumption and high labor costs limit the application of the conventional sequential extraction (CSE) for fast screening of elemental fractions in fly ash. In this study, two ultrasound-assisted sequential extraction (UASE) methods were developed for fast analysis of arsenic (As) and selenium (Se) fractions in fly ash (FA). The parameters of UASE were optimized by comparing the results of As and Se obtained from UASE with those values observed via CSE. The operation time of sequential extraction procedures for As and Se were shortened from 24.5 h to less than 90 min. A certified reference material (CRM, GBW08401) and real fly ash samples were applied to validate the developed UASE. The recoveries of As and Se were found in the range of 82.3% to 114%. For all fractions, the performance of UASE was faster than CSE with the acceptable uncertainties. The analytical results demonstrated that the concentration of As in F3 was found to be higher than other fractions, while the main forms of Se were found to be in F1 and F3 in the fly ash samples. Based on the advantages of high efficiency and easy operation, the developed UASE procedures can be applied for fast screening of the mobility and bioavailability of As and Se in FA from coal fired power plants.

Accelerated screening of arsenic and selenium fractions and bioavailability in fly ash by microwave assistance.

Huge amounts of fly ash (FA) can be annually produced in power plants. Fly ash always contains high levels of arsenic (As) and selenium (Se) due to the preconcentration of these two elements during coal combustion process. It would be much concerned to screen their fractions and potential environmental behaviors in fly ash for beneficial use and treatment. Fast and practical methods for this purpose are urgently needed. Two fast and effective microwave-assisted sequential extraction schemes (MASE) were developed for fast screening As and Se fractions in fly ash for the first time. The extraction parameters including microwave irradiation time, temperature and power energy were optimized by comparing the results from MASE and the conventional scheme (Wenzel method). The results indicate that the extraction efficiency of As and Se in various fractions can be significantly accelerated by microwave irradiation. The whole procedure operation time can be significantly reduced from 24.5 h to 44 min by microwave assistance compared with the conventional shaking schemes. The recoveries of As and Se in the various extracted fractions were all above 80% with relative standard deviations (RSDs) below 8%. The developed methods were further confirmed by the validation of the certified reference material GBW08401 and fly ash samples from six power plants. The developed MASE methods are practical and effective for fast screening arsenic and selenium fractions in fly ash samples.

Fraction distribution of arsenic in different-sized atmospheric particulate matters.

The sequential extraction method was used to determine the fraction of arsenic (As) in different-sized particulate matters (PMs) (i.e., PM2.5, PM10, and total suspended particles (TSP)). Samples were collected from Baoding, a typical medium-sized city with the serious haze pollution in China. The bioavailabilities of As in the samples were estimated based on the fraction results. A large percentage of fine particles were detected in TSP, with the average PM2.5/PM10 and PM10/TSP ratios all above 0.69. The total concentrations of As in PM2.5, PM10, and TSP samples were in the range of 4.5-296.4, 14.1-708.0, and 32.8-798.0 ng m-3, respectively. The mass percentages of As in PM2.5, PM2.5-10, and PM10-100 were calculated; the results indicated that As tended to concentrate in fine particles. PM-bound As mainly presented in the nonspecifically sorbed fraction (F1) during all of the sampling periods. The percentages of F1-As and bioavailability of As were higher in PM2.5, followed by PM10 and TSP. By contrast, the residual fraction (F5-As) contents declined in the order of TSP > PM10 > PM2.5. Significant differences in the speciation and bioavailability of As in different-sized PMs were found, and the influence of particle size on the speciation and bioavailability of As in PMs was verified. Fine particles adsorbed more As with higher bioavailability, and potentially led to more serious adverse effects on human health than the larger ones.

A comparative study on arsenic fractions in indoor/outdoor particulate matters: a case in Baoding, China.

The distribution and bioavailability of arsenic (As) in indoor/outdoor total suspended particulates (TSP), inhalable particulate matters (PM10), and fine particulate matters (PM2.5) in Baoding, China were investigated. The average I/O ratios for TSP, PM10, and PM2.5 were 0.52, 0.66, and 0.96, respectively. There was no significant correlation between indoor/outdoor TSP, PM10, and PM2.5. The indoor/outdoor concentrations of As surpassed the limited value of As. I/O ratios of arsenic in TSP, PM10, and PM2.5 were 0.52, 0.58, and 0.55, respectively. The contents of arsenic in different fractions were mainly affected by the total concentrations of arsenic in particulate matters (PM) rather than the particle sizes for TSP and PM10. Arsenic was mainly in non-specifically sorbed fraction (F1) in both indoor and outdoor PM2.5. The evaluated carcinogenic risk (CR) was within the safe level. The bioavailability of As increased with particle size decreasing for both indoor and outdoor PM. The potential bioavailability of As in outdoor particles was higher than that of indoor particles with the same size, especially PM2.5.