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The molecular composition of humic-like substances (HULIS) in different aerosol samples was analyzed using an ultrahigh-resolution mass spectrometer to investigate the influence of biomass burning on ambient aerosol composition. HULIS in background aerosols were characterized with numerous molecular formulas similar to biogenic secondary organic aerosols. The abundance of nitrogen-containing organic compounds (NOC), including nitrogen-containing bases (N-bases) and nitroaromatics, increased dramatically in ambient aerosols affected by crop residue burning in the farm field. The molecular distribution of N-bases in these samples exhibited similar patterns to those observed in smoke particles freshly emitted from lab-controlled burning of straw residues but were significantly different with those observed from wood burning. Signal intensity of the major N-bases correlated well with the atmospheric concentrations of potassium and levoglucosan. These N-bases can serve as molecular markers distinguishing HULIS from crop residue burning with from wood burning. More nitroaromatics were detected in ambient aerosols affected by straw burning than in fresh smoke aerosols, indicating that many of them are formed in secondary oxidation processes as smoke plumes evolve in the atmosphere. This study highlights the significant contribution of crop residue burning to atmospheric NOC. Further study is warranted to evaluate the roles of NOC on climate and human health. [ABSTRACT FROM AUTHOR]

Heterogeneous surface processes such as adsorption and oxidation with surface-adsorbed reactive oxygen species (ROS ad , e.g., adsorbed oxygen atom (*O ad ) and hydroxyl radicals ( • OH ad )) have been suggested to play an important role in pollutant abatement during heterogeneous catalytic ozonation (HCO). However, to date, there is no reliable method to quantitatively evaluate the contribution of heterogeneous surface processes to pollutant abatement ( f S ) during HCO. In this study, we developed a method by combining probe compound-based experiments with kinetic modeling to distinguish heterogeneous surface processes from homogeneous bulk reactions with aqueous O 3 and ROS ( • OH and superoxide radicals (O 2 •- ) in the abatement of various pollutants (e.g., atrazine, ibuprofen, tetrachloroethylene, and perfluorooctanoic acid) during HCO with reduced graphene oxide. The results show that the pollutants that have a low affinity for the rGO surface (e.g., ibuprofen and tetrachloroethylene) were essentially abated by homogeneous bulk reactions, while the contribution of heterogeneous surface processes was negligible ( f S < 5%). In contrast, heterogeneous surface processes played an important or even dominant role in the abatement of pollutants that have a high surface affinity (e.g., f S = 32-82% for atrazine and perfluorooctanoic acid). This study is a critical first step in quantitatively evaluating the role of heterogeneous surface processes for pollutant abatement during HCO, which is crucial to understanding the mechanism of HCO and designing catalysts for effective pollutant abatement.

Herein, we report a new series of divalent 2-(4-hydroxyphenyl)benzothiazole bifunctional chelators (BFCs) with high affinity for amyloid β aggregates and favorable lipophilicity for blood-brain barrier penetration. The addition of an alkyl carboxylate ester pendant arm offers high binding affinity toward Cu(II). The novel BFCs form stable 64 Cu-radiolabeled complexes and exhibit promising partition coefficient (log D ) values of 1.05-1.85. Among the five compounds tested, the 64 Cu-YW-15 complex exhibits significant staining of amyloid β plaques in ex vivo autoradiography studies. In addition, biodistribution studies show that 64 Cu-YW-15-Me exhibits moderate brain uptake (0.69 ± 0.08 %ID/g) in wild type mice.

Timely diagnostic imaging plays a crucial role in managing cerebral amyloid angiopathy (CAA)-the condition in which amyloid β is deposited on blood vessels. To selectively map these amyloid plaques, we have designed amyloid-targeting ligands that can effectively complex with 68 Ga 3+ while maintaining good affinity for amyloid β. In this study, we introduced novel 1,4,7-triazacyclononane-based bifunctional chelators (BFCs) that incorporate a benzothiazole moiety as the Aβ-binding fragment and form charged and neutral species with 68 Ga 3+ . In vitro autoradiography using 5xFAD and WT mouse brain sections (11-month-old) suggested strong and specific binding of the 68 Ga complexes to amyloid β. Biodistribution studies in CD-1 mice revealed a low brain uptake of 0.10-0.33% ID/g, thus suggesting 68 Ga-labeled novel BFCs as promising candidates for detecting CAA., Competing Interests: The authors declare no competing financial interest., (© 2022 The Authors. Published by American Chemical Society.)

Herein, we report a new series of bifunctional chelators (BFCs) with a high affinity for amyloid aggregates, a strong binding affinity toward Cu(II), and favorable lipophilicity for potential blood-brain barrier penetration. The alkyl carboxylate ester pendant arms offer up to 3 orders of magnitude higher binding affinity toward Cu(II) and enable the BFCs to form stable 64 Cu-radiolabeled complexes. Among the five compounds tested, the 64 Cu-YW-7 and 64 Cu-YW-10 complexes exhibit strong and specific staining of amyloid plaques in ex vivo autoradiography studies. Importantly, these BFCs have promising partition coefficient (log D oct ) values of 0.91-1.26 and show some brain uptake in biodistribution studies using CD-1 mice. Overall, these BFCs could serve as lead compounds for the development of positron emission tomography imaging agents for AD diagnosis.

A critical challenge in environmental remediation is the design of adsorbents with proper pore size for the removal of organic pollutants. Three covalent organic frameworks (COFs) with different pore sizes were successfully prepared by a room-temperature solution-suspension method and used to remove a typical aryl-organophosphorus flame retardant [triphenyl phosphate (TPhP)] from aqueous solution. The prepared COFs showed strong acid resistance and thermal stability. The 1,3,5-triformylphloroglucinol (TFP) reacted with benzidine (BD) (COF2) and exhibited the highest sorption capacity for TPhP, followed by the reaction of TFP and 4,4″-diamino- p-terphenyl (DT) (COF3), and the reaction of TFP and p-phenylenediamine (COF1). Their adsorption equilibriums were achieved within 12 h, and COFs with a larger pore size have higher initial sorption rate but longer time to reach sorption equilibrium. According to the Langmuir fitting, the maximum sorption capacities of three COFs for TPhP were 86.1, 387.2, and 371.2 mg/g, respectively. The density functional theory calculation verified that COF1 with a small pore size prevents TPhP molecules from entering the pores, resulting in extremely low sorption capacity, whereas a relatively too large pore size (COF3) will decrease the sorption energy, which is also not conducive to the adsorption of TPhP. Moreover, the prepared COFs can selectively adsorb TPhP in the presence of coexisting compounds and had high removal of TPhP from actual municipal wastewater, showing a promising application potential for selective removal of micropollutants from water by precisely controlling the COF structure.

A rapid (1.5 h) one-step ball milling (BM) method was developed not only to modify commercial MnO2 via top-down approaches (BM0), but also to bottom-up synthesize MnO(x) by cogrinding of KMnO4 and MnC4H6O4 (BM1) or KMnO4 and MnSO4 (BM2). Catalysts activity on gaseous POPs removal was tested using hexachlorobenzene (HCBz) as surrogate. Catalytic performance decreases in the order of BM2 ≈ BM1 (T90% = 180-200 °C) > BM0 (260 °C) > CMO ≈ cryptomelane MnO2 (>300 °C). Both adsorption and destruction contribute to HCBz removal at 180 °C while destruction prevails at 200-300 °C. Mechanism studies show that destruction activity is lineally correlated with the amount of surface reactive oxygen species (Oads); stability is determined by the removal of surface chloride, which is associated with the mobility of bulk lattice oxygen (Olat); adsorption capacities are linearly correlated with surface area and pore structure. With the aid of extensive characterizations the excellent performance of BM prepared samples can be explained as (1) abundant surface vacancies enhance the generation of Oads; (2) massive bulk vacancies promote the mobility of bulk Olat; (3) large surface area and uniform pore size distribution facilitate the physisorption of HCBz.

Hydrophobic interaction has been considered to be responsible for adsorption of perfluorooctanesulfonate (PFOS) on the surface of hydrophobic adsorbents, but the long C-F chain in PFOS is not only hydrophobic but also oleophobic. In this study, for the first time we propose that air bubbles on the surface of hydrophobic carbonaceous adsorbents play an important role in the adsorption of PFOS. The level of adsorption of PFOS on carbon nanotubes (CNTs), graphite (GI), graphene (GE), and powdered activated carbon (PAC) decreases after vacuum degassing. Vacuum degassing time and pressure significantly affect the removal of PFOS by these adsorbents. After vacuum degassing at 0.01 atm for 36 h, the extent of removal of PFOS by the pristine CNTs and GI decreases 79% and 74%, respectively, indicating the main contribution of air bubbles to PFOS adsorption. When the degassed solution is recontacted with air during the adsorption process, the removal of PFOS recovers to the value obtained without vacuum degassing, further verifying the key role of air bubbles in PFOS adsorption. By theoretical calculation, the distribution of PFOS in air bubbles on the adsorbent surfaces is discussed, and a new schematic sorption model of PFOS on carbonaceous adsorbents in the presence of air bubbles is proposed. The accumulation of PFOS at the interface of air bubbles on the adsorbents is primarily responsible for its adsorption, providing a new mechanistic insight into the transport, fate, and removal of PFOS.

Demonstration-scale metal pouring emission tests and bench-scale Curie-point pyrolysis emission tests were conducted to identify and quantify the hazardous air pollutant (HAP) emissions of five kinds of casting materials, namely, bituminous coal, cellulose, conventional phenolic urethane binder (PUB), naphthalene-depleted PUB, and a collagen-based binder. For a given casting material, the major HAP species generated in Curie-point pyrolysis were essentially the same as those generated in demonstration-scale metal pouring. The 8-10 HAP species identified in the Curie-point pyrolysis tests comprised 65-98% (by weight) of the total HAP emissions quantified in the demonstration-scale pouring emission tests. Furthermore, with these two protocols, we appraised the relative emission changes that would be associated with (a) replacing conventional PUB with collagen-based binder, (b) replacing conventional PUB with naphthalene-depleted PUB, and (c) replacing bituminous coal with cellulose for making sand molds or cores in the casting process. The relative emission changes associated with the use of alternative casting materials exhibited similar trends for most of the major HAP species in the demonstration-scale pouring and Curie-point pyrolysis emission tests. The results indicated that Curie-point pyrolysis emission test could be employed as a convenient and cost-effective screening tool to identify the major HAP species and to compare the relative HAP emission levels for various casting materials.

Analytical pyrolysis was conducted to evaluate the major hazardous air pollutant (HAP) emissions from pyrolysis of bituminous coal and a furan binder, which are the two most commonly used casting materials for making green sand and furan no-bake molds in Chinese foundries. These two materials were flash pyrolyzed in a Curie-point pyrolyzer at 920 °C and slowly pyrolyzed in a thermogravimetric analyzer (TGA) from ambient temperature to 1000 °C with a heating rate of 30 °C/min. The emissions from Curie-point and TGA pyrolysis were analyzed with gas chromatography-mass spectrometer/flame ionization detector. Thirteen HAP species were identified and quantified in the pyrolysis emissions of the two materials. The prominent HAP emissions were cresols, benzene, toluene, phenol, and naphthalene for the bituminous coal, whereas they were m,p,o-xylenes for the furan binder. Xylenesulfonic acid, the acidic catalyst in furan binder, was found to be the major source of xylene emissions. Thermogravimetry-mass spectrometer monitored the evolution of HAP emissions during TGA pyrolysis. For both of the casting materials, most of the emissions were released in the temperature range of 350-700 °C.

Analytical pyrolysis was conducted to identify and quantify the major pyrolysis products of a biodiesel phenolic urethane binder as a function of temperature. This biodiesel binder has been used in U.S. foundries recently to replace conventional phenolic urethane binders for making sand cores. Flash pyrolysis and thermogravimetric analytical (TGA) slow pyrolysis were conducted for the core samples to simulate some key features of the heating conditions that the core binders would experience during metal casting. Pyrolysis products from flash and TGA pyrolysis were analyzed with gas chromatography-mass spectrometry/flame ionization detection/thermal conductivity detection. The evolution profiles of the pyrolysis products during TGA slow pyrolysis were also monitored via thermogravimetry-mass spectrometry (TG-MS). The combination of TG-MS and TGA pyrolysis emission data facilitated a quantification of gaseous pyrolysis products of the biodiesel binder as a function of temperature. The major monitored carbonaceous pyrolysis products of the biodiesel binder included CO, CO2, CH4, and a variety of methyl esters such as dimethyl glutarate, dimethyl adipate, and methyl oleate. These latter species were the components of the biodiesel binder's solvent Pyrolysis of the biodiesel binder also generated a variety of hazardous air pollutants listed by the U.S. EPA, with benzene, toluene, xylene, phenol, and cresols being the prominent species. A considerable fraction of the binder's released mass did not appear as exhausted volatile carbonaceous species, but rather recondensed before they exhausted from the TGA. This represented mass that could likewise recondense within a green sand molding system during full-scale operations, as an environmentally favorable containment of air emissions.

Analytical pyrolysis was conducted to study a relative comparison of the hydrocarbon and greenhouse gas emissions of three foundry sand binders as follows: (a) conventional phenolic urethane resin, (b) biodiesel phenolic urethane resin, and (c) collagen-based binder. These binders are used in the metal casting industry for making cores that are used to create internal cavities within castings. In this study, the core samples were flash pyrolyzed in a Curie-point pyrolyzer at 920 degrees C with a heating rate of about 3000 degrees C/sec. This simulated some key features of the fast heating conditions that the core binders would experience at the metal-core interface when molten metal is poured into green sand molds. The core samples were also pyrolyzed in a thermogravimetric analyzer (TGA) from ambient temperature to 1000 degrees C with a heating rate of 30 degrees C/min, and this simulated key features of the slow heating conditions that the core binders would experience at distances that are further away from the metal-core interface during casting cooling. Hydrocarbon emissions from flash pyrolysis were analyzed with a gas chromatography-flame ionization detector, while hydrocarbon and greenhouse gas (CO and CO2) emissions from TGA pyrolysis were monitored with mass spectrometry. The prominent hazardous air pollutant emissions during pyrolysis of the three binders were phenol, cresols, benzene, and toluene for the conventional phenolic urethane resin and biodiesel resin, and they were benzene and toluene for the collagen-based binder. It was also found that volatile organic compound and polycyclic aromatic hydrocarbon emissions considerably decreased in order from conventional phenolic urethane resin to biodiesel resin to collagen-based binder. These results have shown some similarity with those for stack emission testing conducted at demonstration scale and/or full-scale foundries, and the similar trends in the two sets of results offered promise that bench-scale analytical pyrolysis techniques could be a useful screening tool for the foundries to compare the relative emissions of alternative core binders and to choose proper materials in order to comply with air-emission regulations.

This research studied a relative comparison of the hydrocarbon emissions during pyrolysis of four carbonaceous additives that can be used in green sand foundries. These included a highly volatile bituminous coal, anthracite, lignite, and cellulose. Analytic pyrolysis was conducted to simulate the heating conditions that the carbonaceous additives would experience during metal pouring. Specifically, the samples were flash pyrolyzed in a Curie-point pyrolyzer at 920 degrees C with a heating rate of about 3000 degrees C/sec. This simulated some key features of the fast heating conditions that the carbonaceous additives would experience at the metal-mold interface when molten metal is poured into green sand molds. The samples were also pyrolyzed in a thermogravimetric analyzer (TGA) from ambient temperature to 1000 degrees C with a heating rate of 20 degrees C/min; and this simulated key features of the slow heating conditions that the carbonaceous additives would experience within the bulk of green sand molds that is further away from the metal-mold interface. Hydrocarbon emissions from flash pyrolysis were analyzed with GC-FID, while those from TGA pyrolysis were monitored with mass spectroscopy and GC-FID. The anthracite exhibited very low volatile hydrocarbons during both flash pyrolysis and TGA pyrolysis. The cellulose released less hydrocarbons than bituminous coal or lignite in TGA pyrolysis, but more hydrocarbons than those two during flash pyrolysis. This means that cellulose can release sufficient volatile hydrocarbons at the intensely heated molten metal-mold interface where they are most desired for ensuring casting quality, but much less within the bulk of the mold where they are undesirable. This characteristic of cellulose offers an important opportunity for green sand foundries to diminish their hazardous air pollutant (HAP) emissions.

The effects of advanced oxidation (AO) processing on the properties of green sand were studied via pouring cast iron into green sand molds. Upon cooling, the green sand molds were autopsied at various distances from the metal-sand interface. Autopsy green sand samples collected from a mold that incorporated AO water were characterized and compared to controlled samples collected from a similar autopsied mold made with conventional tap water (TAP). It was found that the AO processing removed a coating of coal pyrolysis products from the clay surface that typically accumulated on the clay surface. As a result, the AO-conditioned green sand retained 10-15% more active clay as measured bythe standard ultrasonic methylene blue titration than did the TAP-conditioned green sand. The AO processing also nearly doubled the generation of activated carbon from the normalized amount of coal composition of the green sand during the casting process. The AO-enhanced activated carbon generation and the AO-incurred clay surface cleaning provided the AO-conditioned green sand with higher normalized pore volume, and thus higher normalized m-xylene adsorption capacity, i.e., relative to before-metal-pouring conditions. Furthermore, mathematical analysis indicated that the AO-conditioned green sand better retained its important properties after pouring than did the TAP-conditioned green sand. Effectively, this meant after metal pouring, the AO-conditioned sample offered about the same net properties as the TAP-conditioned sample, even though the AO-conditioned sample contained less clay and coal before metal pouring. These results conformed to the full-scale foundry empirical finding that when AO is used, foundries need less makeup clay and coal addition through each casting cycle, and they release less air emissions.

Prior full-scale foundry data have shown that when an advanced oxidation (AO) process is employed in a green sand system, the foundry needs 20-35% less makeup bentonite clay than when AO is not employed. We herein sought to explore the mechanism of this enhancement and found that AO water displaced the carbon coating of pyrolyzed carbonaceous condensates that otherwise accumulated on the bentonite surface. This was discerned by surface elemental analysis. This AO treatment restored the clay's capacity to adsorb methylene blue (as a measure of its surface charge) and water vapor (as a reflection of its hydrophilic character). In full-scale foundries, these parameters have been tied to improved green compressive strength and mold performance. When baghouse dust from a full-scale foundry received ultrasonic treatment in the lab, 25-30% of the dust classified into the clay-size fraction, whereas only 7% classified this way without ultrasonics. Also, the ultrasonication caused a size reduction of the bentonite due to the delamination of bentonite particles. The average bentonite particle diameter decreased from 4.6 to 3 microm, while the light-scattering surface area increased over 50% after 20 min ultrasonication. This would greatly improve the bonding efficiency of the bentonite according to the classical clay bonding mechanism. As a combined result of these mechanisms, the reduced bentonite consumption in full-scale foundries could be accounted for.