A comprehensive study of the removal of selected biologically active compounds (pharmaceuticals and pesticides) from different water types was conducted using bare TiO₂ nanoparticles and TiO₂/polyaniline (TP-50, TP-100, and TP-150) nanocomposite powders. In order to investigate how molecular structure of the substrate influences the rate of its removal, we compared degradation efficiency of the initial substrates and degree of mineralization for the active components of pharmaceuticals (propranolol, and amitriptyline) and pesticides (sulcotrione, and clomazone) in double distilled (DDW) and environmental waters. The results indicate that the efficiency of photocatalytic degradation of propranolol and amitriptyline was higher in environmental waters: rivers (Danube, Tisa, and Begej) and lakes (Moharač, and Sot) in comparison with DDW. On the contrary, degradation efficacy of sulcotrione and clomazone was lower in environmental waters. Further, of the all catalysts applied, bare TiO₂ and TP-100 were found to be most effective in the mineralization of propranolol and amitriptyline, respectively, while TP-150 appeared to be the most efficient in terms of sulcotrione and clomazone mineralization. Also, there was no significant toxicity observed after the irradiation of pharmaceuticals or pesticides solutions using appropriate catalysts on rat hepatoma (H-4-II-E), mouse neuroblastoma (Neuro-2a), human colon adenocarcinoma (HT-29), and human fetal lung (MRC-5) cell lines. Subsequently, detection and identification of the formed intermediates in the case of sulcotrione photocatalytic degradation using bare TiO₂ and TP-150 showed slightly different pathways of degradation. Furthermore, tentative pathways of sulcotrione photocatalytic degradation were proposed and discussed.

Metal enrichment of road dust is well characterized but available data on the bioaccessibility of metals in particle size fractions relevant to human respiratory health remain limited. The study goal was to investigate the bioaccessibility of platinum group elements (PGE), which are used as catalysts in automotive exhaust converters, in the inhalable fraction of road dust. Street sweepings were provided by the City of Toronto, Canada, collected as part of its Clean Roads to Clean Air program.The particle size relevance of road dust for inhalation exposures was confirmed using a laser diffraction particle size analyzer (mean Dx(50): 9.42 μm). Total PGE were determined in both bulk and inhalable fractions using nickel sulfide (NiS) fire-assay and instrumental neutron-activation analysis (INAA). PGE lung solubility was examined for the inhalable fraction using Gamble’s extraction. Sample digests were co-precipitated with Te-Sn, to pre-concentrate and isolate PGE, prior to their measurement using inductively coupled plasma mass spectrometry (ICP-MS).Total PGE concentrations were enriched in the inhalable fraction of road sweepings. Geomean concentrations in the inhalable fraction were: palladium (Pd) (152 μg/kg), platinum (Pt) (55 μg/kg), rhodium (Rh) (21 μg/kg) and iridium (Ir) (0.23 μg/kg). Osmium (Os) concentrations were below the limit of detection (LOD). Bioaccessible PGEs (n = 16) using Gamble’s solution were below LOD for Ir and ruthenium (Ru). For the remainder, the geomean % bioaccessibility was highest for platinum (16%), followed by rhodium (14%) and palladium (3.4%). This study provides evidence that PGE in road dust are bioaccessible in the human lung.

Acceleration of Fe³⁺/Fe²⁺ cycle and simultaneous reduction of particle size with enhanced stability is extremely important for iron-based heterogeneous Fenton catalysts. In this work, Fe⁰-Fe₂O₃ composite nanoparticles embedded ordered mesoporous carbon hybrid materials (Fe⁰-Fe₂O₃/OMC) were rationally designed as efficient heterogeneous Fenton catalysts. Because of the confinement and reduction of OMC, highly dispersed Fe⁰-Fe₂O₃ active species with diameter of ∼8 nm were generated by an optimized carbothermic reduction process. In addition, Fe⁰-Fe₂O₃/OMC possesses ordered mesoporous structure with uniform mesopore, high surface area and pore volume. For comparison, two other catalysts, including solely Fe⁰ nanoparticles supported on ordered mesoporous carbon (Fe⁰/OMC) and solely Fe₂O₃ nanoparticles supported on ordered mesoporous carbon (Fe₂O₃/OMC) were also prepared. The Fenton catalytic performance of synthesized catalysts was evaluated by using H₂O₂ as oxidizing agent to degrade Acid Orange II (AOII). The results show that almost 98.1% of 100 mg L⁻¹ AOII was removed by Fe⁰-Fe₂O₃/OMC in condition of neutral pH and nearly room temperature, which is much higher than those of compared catalysts. The enhanced catalytic activity of Fe⁰-Fe₂O₃/OMC for AOII removal is due to the efficient electron transfer between the Fe⁰ and iron oxide and the accelerated Fe³⁺/Fe²⁺ cycle. The stability and reusability of the catalyst was also investigated, which showed a good performance even after five consecutive runs. The as-synthesized catalyst is proved to be an attractive candidate in heterogeneous Fenton chemistry and practical application.

In this work we have investigated in details the process of degradation of the 4-amino-6-chlorobenzene-1,3-disulfonamide (ABSA), stable hydrolysis product of frequently used pharmaceutical hydrochlorothiazide (HCTZ), as one of the most ubiquitous contaminants in the sewage water. The study encompassed investigation of degradation by hydrolysis, photolysis, and photocatalysis employing commercially available TiO₂ Degussa P25 catalyst. The process of direct photolysis and photocatalytic degradation were investigated under different type of lights. Detailed insights into the reactive properties of HCTZ and ABSA have been obtained by density functional theory calculations and molecular dynamics simulations. Specifically, preference of HCTZ towards hydrolysis was confirmed experimentally and explained using computational study. Results obtained in this study indicate very limited efficiency of hydrolytic and photolytic degradation in the case of ABSA, while photocatalytic degradation demonstrated great potential. Namely, after 240 min of photocatalytic degradation, 65% of ABSA was mineralizated in water/TiO₂ suspension under SSI, while the nitrogen was predominantly present as NH4+. Reaction intermediates were studied and a number of them were detected using LC-ESI-MS/MS. This study also involves toxicity assessment of HCTZ, ABSA, and their mixtures formed during the degradation processes towards mammalian cell lines (rat hepatoma, H-4-II-E, human colon adenocarcinoma, HT-29, and human fetal lung, MRC-5). Toxicity assessments showed that intermediates formed during the process of photocatalysis exerted only mild cell growth effects in selected cell lines, while direct photolysis did not affect cell growth.

Mercury (Hg) emissions from point sources to air may disperse over long distance depending on Hg speciation in the plume. A significant fraction of Hg, particularly in its divalent forms, deposits locally and causes pollution to surrounding biomes. The objective of this study was to investigate (1) the historic Hg deposition to the immediate vicinity of an industrial complex that had intentional use of Hg (i.e., chlor-alkali and polyvinyl chloride production) for 5 decades until 2011, and (2) the Hg⁰ re-emission from soil to air soon after the closure of the facility. The spatial distribution of near-ground Hg⁰ vapor in air, soil Hg concentration and stable isotope ratio, air-soil Hg⁰ flux and Hg⁰ concentration in soil pore-gas were measured. It was found that the surrounding soils are severely contaminated with Hg due to the Hg release of the industrial complex, displaying soil Hg content up to 4.8 μg g⁻¹. A spatial trend of Hg mass dependent isotope fractionation signature (δ²⁰²Hg = −2.11‰ to 0.72‰) with respect to the distance from the closed facility was identified, representing a mixing between regional background and industrial Hg sources. Hg release from the industrial operation enhanced surface soil Hg content within a 6.5-km radius from the facility. Inside the facility, residual Hg wastes (i.e., electrolysis sludge and consumed HgCl₂ catalyst) represent a strong localized emission source of atmospheric Hg⁰. Near-ground atmospheric Hg⁰ concentration and soil Hg⁰ efflux progressively elevated toward the facility with an increase by 2–3 orders of magnitude compared to the values observed in the off-site background. These results suggest that the natural soil surfaces surrounding the closed industrial facility act as a large nonpoint source emitting legacy deposited Hg as much as the release from naturally enriched mines.

The aim of this study was to evaluate the mobility of platinum (Pt) and palladium (Pd) emissions from automotive catalysts in soils and to contribute to the risk assessment of platinum group metals (PGMs) discharged from catalysts in the environment. To address this question, for the first time risk assessment code (RAC) was applied to consider the results from sequential extraction of different Pd and Pt species from soils. For this purpose, model soil samples were prepared spiking defined Pd or Pt species, respectively, at known concentrations. In order to mimic emitted species as well as possible transformation products of traffic-related Pd and Pt emissions in soils, coated and uncoated elemental nanoparticles (cPd/cPt NPs, Pd/Pt NPs) and ionic divalent metal species (Pd(II)/Pt(II)) were applied. All model samples were characterized in detail and the developed sequential extraction scheme was validated. RAC values ranged between 24 and 8% revealing medium to low risk. The order of mobility for the studied species was found to be Pt(II) > cPd NPs » Pd(II) > Pd NPs > Pt NPs > cPt NPs. Furthermore, migration of Pd species in gravity columns was studied confirming highest transport of cPd NPs.

The presence of pathogenic microorganisms in water is a great threat to human health, and photocatalysis is promising for disinfection. However, the research on virus inactivation with visible-light photocatalysis is still limited, especially the coexistence of virus and its host bacteria. In this study, bacteriophage f2 and its host E. coil 285 were used as the model microorganisms, and the disinfection performance of prepared Cu-TiO2 nanofibers under visible light was investigated. The result showed that the prepared Cu-TiO2 nanofibers showed a brilliant ability in terms of removing bacteriophage f2 and E. coil 285 under visible light. Series experiments indicated that the initial pH didn't affect the photocatalytic disinfection performance significantly. In the certain range, the removal efficiency of bacteriophage f2 increased with the increase of catalyst dosage, light intensity and temperature, but decreased with the increase of initial virus concentration. In virus/bacteria mixed system, bacteriophage f2 exhibited stronger resistance to photocatalytic oxidation than E. coil 285, and the removal of bacteriophage f2 was obviously affected by being mixed with E. coil 285, while the removal of E. coil 285 almost remained unchanged after being mixed with bacteriophage f2. Further research proved that competitive adsorption in mixed system played a certain role in E. coli 285 inactivation, while the free reactive oxygen species (ROSs) in the bulk phase played a crucial role in phage f2 inactivation.

Mg-Al-Ox supported monometallic (Ni) and bimetallic (Ni-Co) catalysts with different compositions of Mg and Al were investigated for CO₂ reforming of CH₄, using both coal and pure gas feeds, to limit the emission of these environmental pollutant gases into the atmosphere. Results showed that all the catalysts were active for dry reforming reaction using both feeds. Reactants conversion, stoichiometric product selectivity, and resistance to carbon deposition of catalysts remarkably improved when the Mg/Al ratio was greater than 1. Characterization results revealed changes in the bulk structure, textural and surface properties as the Mg/Al ratio and composition of catalysts changed. Improved active metal reduction, metal-support and metal-metal interaction (in the bimetallic) were also noted in the catalysts with Mg/Al ratio greater than 1. With respect to feed composition, less carbon deposition was recorded in the corresponding catalysts using coal gas compared to the pure gas. Ni-Co interaction and their interaction with MgO facilitated better basicity, increased metal dispersion and smaller particle size in Ni-Co-Mg₁.₇-Al₁-Ox, which showed best catalytic performance with no carbon deposition in both feeds. These interactions and properties stabilized the Ni site, which made the Ni-Co-Mg₁.₇-Al₁-Ox, catalyst resistant to sintering and carbon deposition.

Effects of discharge power, O₂ content, reaction temperature, catalyst introduction, and presence of NO and dichloromethane (DCM) on the formation of nitrogen oxides (N₂O, NO, and NO₂) by discharge in N₂-O₂ mixture have been systematically investigated using a dielectric barrier discharge (DBD) reactor. Results show that discharge in N₂-O₂ mixture always produces several to hundreds ppm of nitrogen oxides as byproducts. The production of nitrogen oxides increases with the increase of O₂ content and the introduction of Al₂O₃ or RuO₂/Al₂O₃ catalyst. N₂O production first increases and then decreases/levels off with increasing discharge power at room temperature, but increases monotonously at 300 °C. NO and NO₂ are produced only at relatively high discharge power at room temperature but are produced at all discharge power tested at 300 °C. Increasing the reaction temperature from room temperature to 300 °C significantly reduces the production of N₂O but increases that of NO and NO₂. The presence of hundreds ppm NO in N₂-O₂ mixture significantly reduces the production of N₂O due to the effective quenching of the vital species for N₂O formation (N₂(A³Σᵤ⁺)) by NO. The presence of hundreds ppm DCM, however, hardly affects the production of nitrogen oxides, demonstrating the precedence of nitrogen oxide production over DCM decomposition in N₂-O₂ plasma.

In this study, we prepared a homogeneous dispersion of CaO-SiO₂ sorbent with advanced nanostructures as an efficient solid-reducing agent for the elimination of hazardous chemicals. The hydrophobic properties of SiO₂ ceramic particles are of interest for reducing the limitations and enhancing the chemical properties of highly hygroscopic materials. Nano-sized SiO₂ is introduced and composited with CaO through a facile synthetic route. The structural and microstructural characteristics and elemental compositional analyses confirm the uniform distribution of the CaO-SiO₂ nanocomposite. The as-prepared nanocomposites have particle sizes in the range of ~ 20–100 nm. Optimization of the composition reveals that the 60 wt% CaO-SiO₂ can be considered as an efficient solid-reducing agent for the hydrogen fluoride (HF) removal process. In order to identify the catalytic effect and binder ratio, the specific surface area and HF removal performance was investigated and compared to CaO-SiO₂ nanostructures with individual CaO catalyst. The higher amount of HF concentration was absorbed by CaO-SiO₂ catalyst than the CaO only. In the first 2.5-h reaction, the outlet HF concentration is rapidly increased to 380 ppm by using CaO catalyst as a HF sorbent. However, the outlet HF concentration is sluggishly increased up to 180 ppm, when nanostructured CaO-SiO₂ catalyst used as a sorbent in RE-RCS. It has been found that the addition of hydrophobic properties of SiO₂ has prevented the reaction between water/moisture and CaO in CaO-SiO₂ catalyst system, which is a major reason for enhancement in HF removal process. Furthermore, the CaF₂ byproduct can be effectively used in the ceramic industry and building material applications.