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.

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.

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.

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.

Establishment and characterization of arsenic trioxide resistant KB/ATO cells.

Arsenic trioxide (ATO) is used as a chemotherapeutic agent for the treatment of acute promyelocytic leukemia. However, increasing drug resistance is reducing its efficacy. Therefore, a better understanding of ATO resistance mechanism is required. In this study, we established an ATO-resistant human epidermoid carcinoma cell line, KB/ATO, from its parental KB-3-1 cells. In addition to ATO, KB/ATO cells also exhibited cross-resistance to other anticancer drugs such as cisplatin, antimony potassium tartrate, and 6-mercaptopurine. The arsenic accumulation in KB/ATO cells was significantly lower than that in KB-3-1 cells. Further analysis indicated that neither application of P-glycoprotein inhibitor, breast cancer resistant protein (BCRP) inhibitor, or multidrug resistance protein 1 (MRP1) inhibitor could eliminate ATO resistance. We found that the expression level of ABCB6 was increased in KB/ATO cells. In conclusion, ABCB6 could be an important factor for ATO resistance in KB/ATO cells. The ABCB6 level may serve as a predictive biomarker for the effectiveness of ATO therapy.

Occurrence and distribution of organochlorine pesticides (HCH and DDT) in sediments collected from East China Sea.

Sediments used in this study were collected from different depths of eight sites in East China Sea in November 2002. The levels and distribution patterns of the selected organochlorine pesticides (OCPs=p,p'-DDT, o,p'-DDT, p,p'-DDE, p,p'-DDD, alpha-, beta-, gamma- and delta-HCH) in samples were investigated by the technique of sonication extraction followed by the analysis of gas chromatography (GC) coupled with a micro-electron capture detector (muECD). The concentrations of SigmaHCH and SigmaDDT in the surface sediments were in the range of <0.05-1.45 ng/g (mean 0.76 ng/g), <0.06-6.04 ng/g (mean 3.05 ng/g) based on dry weight (dw), respectively. In the vertical distributions, the SigmaHCH and SigmaDDT were in the range of <0.05-2.52 ng/g, <0.06-10.94 ng/g dw, respectively. Residues of OCPs varied significantly with different sampling sites. SigmaDDT in the surface sediments was correlated well with total organic carbon (TOC) content (r2=0.71), while SigmaHCH showed no obvious correlation. The distribution showed that the sediments from the vicinity estuary or near shore had higher TOC contents, and higher OCPs concentrations. The contamination record indicated an extensive use of OCPs in the catchments from Yangtze River in the past might greatly affect the OCP residues.

Simultaneous determination of trace cadmium and arsenic in biological samples by hydride generation-double channel atomic fluorescence spectrometry.

Hydride generation atomic fluorescence spectrometry (HG-AFS) has been used for determination of hydride-forming elements because of its high sensitivity, simplicity, and low costs, but most of such work has been concentrated on single element analysis, and reports dealing with multielement determination by HG-nondispersive (ND)AFS are rare. In this work, a sensitive HG-NDAFS method was developed for simultaneous determination of trace cadmium and arsenic in biological materials. The conditions for the generation of volatile cadmium and arsenic species from the reaction with KBH4 in aqueous solution were investigated using a double-channel AFS integrated with an intermittent flow reactor. Like thiourea and Co(II), ascorbic acid was found to significantly enhance the generation efficiency of volatile Cd and As species. The interferences of coexisting ions were evaluated. Under optimal conditions, the detection limits for Cd and As were determined to be 10 and 150 ng L(-1), respectively. The precision for 11 replicate determinations at the 1 microg L(-1) Cd level and the 10 microg L(-1) As level were 3.5 and 2.7% (RSD), respectively. The recoveries of spike analytes in the biological samples studied ranged from 94 to 109%. The proposed method was successfully applied to the simultaneous determination of Cd and As in a variety of biological samples.

[Determination of cadmium in Chinese herbs by atomic absorption spectrometry using atom trapping technique].

A method has been proposed for the determination of cadmium by flame atomic absorption spectrometry (FAAS) using atom trapping technique. The experimental conditions including the flame condition, the trap position, the coolant water flow rate and the collection time, which affected on the absorbance of cadmium, were studied, and the optimum experimental conditions were the acetylene flow rate of 90 L.h-1, the distance of tube from the burner of 5 mm, the distance of tube from the light path of 2 mm and the coolant water flow rate of 1.5 L.min-1. The results showed that the absorbance was linearly dependent on the collection time in the range of 0-6 min for cadmium solution of 50 ng.mL-1. For 2 min collection time, the characteristic concentration and the detection limit for cadmium were 1.8 ng.mL-1 and 0.42 ng.mL-1, which were 16 and 5 times better than those of conventional flame atomic absorption spectrometry, respectively. The relative standard deviation(RSD) was 1.8% and the proposed method was successfully applied to the determination of cadmium in Chinese herbs with a recovery range of 89.5%-104%.