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The Science of the Total Environment Feb 2022Biochar promotes C sequestration and improvement of soil properties. Nevertheless, the effects of biochar addition on soil condition are poorly understood, especially...
Biochar promotes C sequestration and improvement of soil properties. Nevertheless, the effects of biochar addition on soil condition are poorly understood, especially with respect to greenhouse gas (GHG) emissions. A large proportion of GHG emissions derive from agriculture and, thus, recognition of the effect of biochar addition to soil on GHG emissions from terrestrial ecosystems is an important issue. The purpose of our study was to evaluate the short- and long-term effects of biochar application on soil in aspects of: GHG exchange (CH and CO), basic physicochemical soil properties and structure of microbial communities in Haplic Luvisol. Soil was collected from fallow fields enriched with three doses of wood offcuts biochar (10, 20 and 30 Mg ha) and incubated at two moisture levels (60 and 100% WHC) with the addition of 1% CH. To evaluate the influence of biochar aging in soil, the samples were analysed directly (short-term response) and five years (long-term response) after amendment. Generally, biochar addition increased soil pH, redox potential (Eh), organic carbon (SOC) and dissolved organic carbon (DOC) contents. Under 60% WHC, direct biochar application to the soil resulted in a clear improvement in the CH uptake rate. In contrast to that (at 100% WHC) methane uptake rates were twofold decreased. The positive effect was reduced due to biochar aging in the soil, but five years after application, at 60% WHC and the highest biochar dose (30 Mg ha) still significantly enhanced CH oxidation. From a short-term perspective, biochar application increased CO emissions, but after five years this effect was not observed. Microbial tests confirmed that the improvement in CH oxidation was correlated with methanotroph abundance in the soil. Moreover, an increase of Methylocystis abundance in the soil enriched with biochar along with enhanced CH uptake rates confirm the positive biochar influence on methanotrophic communities.
Topics: Agriculture; Carbon Dioxide; Charcoal; Ecosystem; Methane; Nitrous Oxide; Soil
PubMed: 34715215
DOI: 10.1016/j.scitotenv.2021.151259 -
The Science of the Total Environment Nov 2022Ozonation has been used to effectively remove micropollutants from the secondary effluent in several wastewater treatment plants. It is known that ozonation transforms...
Ozonation has been used to effectively remove micropollutants from the secondary effluent in several wastewater treatment plants. It is known that ozonation transforms tertiary amine compounds into their respective N-oxides, however in an earlier study a mass balance could not be closed at elevated ozone concentrations, leading to the assumption that more ozonation products are possible. This study was conducted to elucidate which (hitherto unknown) ozonation products can be formed from venlafaxine and tramadol when ozonating wastewater. Ozonation experiments were performed with tramadol and venlafaxine N-oxide in two different set-ups. Both tramadol- and venlafaxine N-oxide degraded during ozonation in pure (deionized) water in both semi-continuous and batch mode ozonation set-ups. 13 and 17 new transformation products were detected from tramadol- and venlafaxine N-oxide respectively, using high resolution mass spectrometry with ESI(+) ionization. Empirical chemical formulas were proposed based on the determination of the exact masses and interpretation of the product ion spectra. These transformation products result from the addition of one to three oxygen atoms and removal of C, -CH, CH, CH, etc., from the parent molecule, respectively. Quenching experiments suggested that most of the transformation products originated from the direct reaction with ozone (eight for tramadol N-oxide and ten for venlafaxine N-oxide), whereas fewer products originated from the reaction with OH radicals (three for tramadol N-oxide and three for venlafaxine N-oxide). Reaction mechanisms and chemical structures of products are proposed, based on the available active sites and past literature on ozone reaction mechanisms. The experimental results are compared to theory and literature on ozone reactive sites and ozone reaction mechanisms. All in all this shows that there can be multiple ozonation products, and ozonation pathways can be complex, even if initially only one ozonation product is formed.
Topics: Organic Chemicals; Oxides; Ozone; Tramadol; Venlafaxine Hydrochloride; Waste Disposal, Fluid; Wastewater; Water Pollutants, Chemical; Water Purification
PubMed: 35817117
DOI: 10.1016/j.scitotenv.2022.157259 -
International Journal of Molecular... Aug 2022The pnictogen bond, a somewhat overlooked supramolecular chemical synthon known since the middle of the last century, is one of the promising types of non-covalent... (Review)
Review
The Pnictogen Bond, Together with Other Non-Covalent Interactions, in the Rational Design of One-, Two- and Three-Dimensional Organic-Inorganic Hybrid Metal Halide Perovskite Semiconducting Materials, and Beyond.
The pnictogen bond, a somewhat overlooked supramolecular chemical synthon known since the middle of the last century, is one of the promising types of non-covalent interactions yet to be fully understood by recognizing and exploiting its properties for the rational design of novel functional materials. Its bonding modes, energy profiles, vibrational structures and charge density topologies, among others, have yet to be comprehensively delineated, both theoretically and experimentally. In this overview, attention is largely centered on the nature of nitrogen-centered pnictogen bonds found in organic-inorganic hybrid metal halide perovskites and closely related structures deposited in the Cambridge Structural Database (CSD) and the Inorganic Chemistry Structural Database (ICSD). Focusing on well-characterized structures, it is shown that it is not merely charge-assisted hydrogen bonds that stabilize the inorganic frameworks, as widely assumed and well-documented, but simultaneously nitrogen-centered pnictogen bonding, and, depending on the atomic constituents of the organic cation, other non-covalent interactions such as halogen bonding and/or tetrel bonding, are also contributors to the stabilizing of a variety of materials in the solid state. We have shown that competition between pnictogen bonding and other interactions plays an important role in determining the tilting of the MX (X = a halogen) octahedra of metal halide perovskites in one, two and three-dimensions. The pnictogen interactions are identified to be directional even in zero-dimensional crystals, a structural feature in many engineered ordered materials; hence an interplay between them and other non-covalent interactions drives the structure and the functional properties of perovskite materials and enabling their application in, for example, photovoltaics and optoelectronics. We have demonstrated that nitrogen in ammonium and its derivatives in many chemical systems acts as a pnictogen bond donor and contributes to conferring stability, and hence functionality, to crystalline perovskite systems. The significance of these non-covalent interactions should not be overlooked, especially when the focus is centered on the rationale design and discovery of such highly-valued materials.
Topics: Calcium Compounds; Halogens; Nitrogen; Oxides; Titanium
PubMed: 35955945
DOI: 10.3390/ijms23158816 -
The Science of the Total Environment Nov 2022Observations of key gaseous trace pollutants, namely NO, NO, CO, SO and O performed at several curb, residential, industrial, background and free-troposphere sites were...
Observations of key gaseous trace pollutants, namely NO, NO, CO, SO and O performed at several curb, residential, industrial, background and free-troposphere sites were analyzed to assess the temporal and spatial variability of pollution in Cyprus. Notably, the analysis utilized one of the longest datasets of 17 years of measurements (2003-2019) in the East Mediterranean and the Middle East (EMME). This region is considered a regional hotspot of ozone and aerosol pollution. A trend analysis revealed that at several stations, a statistically significant decrease in primary pollutant concentration is recorded, most likely due to pollution control strategies. In contrast, at four stations, a statistically significant increase in ozone levels, ranging between 0.36 ppb y and 0.82 ppb y has been observed, attributed to the above strategies targeting the reduction of nitrogen oxides (NO) but not that of Volatile Organic Compounds (VOCs). The NO and NO, and CO levels at the Agia Marina regional background station were two orders of magnitude and four times lower, respectively, than the ones of the urban centers. The latter denotes that local emissions are not negligible and control a large fraction of the observed interannual and diurnal variability. Speciation analysis showed that traffic and other local emissions are the sources of urban NO and NO. At the same time, 46 % of SO and 40 % of CO, on average, originate from long-range regional transport. Lastly, a one-year analysis of tropospheric NO vertical columns from the TROPOMI satellite instrument revealed a west-east low-to-high gradient over the island, with all major hotspots, including cities and powerplants, being visible from space. With the help of an unsupervised machine learning approach, it was found that these specific hotspots contribute overall around 10 % to the total NO tropospheric columns.
Topics: Air Pollutants; Air Pollution; Cyprus; Environmental Monitoring; Nitrogen Dioxide; Ozone
PubMed: 35839895
DOI: 10.1016/j.scitotenv.2022.157315 -
NanoImpact Jan 2022Increased use and production of engineered nanoparticles (NPs) lead to an elevated risk of their diffuse dispersion into the aquatic environment and increased concern on...
Increased use and production of engineered nanoparticles (NPs) lead to an elevated risk of their diffuse dispersion into the aquatic environment and increased concern on unknown effects induced by their release into the aquatic ecosystem. An improved understanding of the environmental transformation processes of NPs of various surface characteristics is hence imperative for risk assessment and management. This study presents results on effects of natural organic matter (NOM) on the environmental transformation and dissolution of metal and metal oxide NPs of different surface and solubility properties in synthetic freshwater (FW) with and without NOM. Adsorption of NOM was evident on most of the studied NPs, except Sb and SbO, which resulted in the formation of negatively charged colloids of higher stability and smaller size distribution compared with the same NPs in FW only. The dissolution rate of the NPs in the presence of NOM correlated with the strength of interactions between the carboxylate group of NOM and the particle surface, and resulted in either no (Mn, Sb, ZnO NPs), increased (Co, Sn NPs) and decreased (Ni, NiO, SbO, YO NPs) levels of dissolution. One type of metal NP from each group (Mn, Ni, Sn) were investigated to assess whether observed differences in adsorption of NOM and dissolution would influence their ecotoxic potency. The results showed Mn, Ni, and Sn NPs to generate intracellular reactive oxygen species (ROS) in a time and dose-dependent manner. The extent of ROS generation in FW was similar for both Mn and Ni NPs but higher for Sn NPs. These findings are possibly related to interactions and infiltration of the NPs with the cells, which lead to redox imbalances which could induce oxidative stress and cell damage. At the same time, the presence of NOM generally reduced the intracellular ROS generation by 20-40% for the investigated NPs and also reduced cytotoxicity of Sn NPs, which can be attributed to the stronger interaction of carboxylate groups of NOM with the surface of the NPs.
Topics: Ecosystem; Metal Nanoparticles; Metals; Oxides; Reactive Oxygen Species; Zinc Oxide
PubMed: 35559892
DOI: 10.1016/j.impact.2022.100386 -
Molecules (Basel, Switzerland) Oct 2022Direct conversion of methane to methanol is an effective and practical process to improve the efficiency of natural gas utilization. Copper (Cu)-based catalysts have... (Review)
Review
Direct conversion of methane to methanol is an effective and practical process to improve the efficiency of natural gas utilization. Copper (Cu)-based catalysts have attracted great research attention, due to their unique ability to selectively catalyze the partial oxidation of methane to methanol at relatively low temperatures. In recent decades, many different catalysts have been studied to achieve a high conversion of methane to methanol, including the Cu-based enzymes, Cu-zeolites, Cu-MOFs (metal-organic frameworks) and Cu-oxides. In this mini review, we will detail the obtained evidence on the exact state of the active Cu sites on these various catalysts, which have arisen from the most recently developed techniques and the results of DFT calculations. We aim to establish the structure-performance relationship in terms of the properties of these materials and their catalytic functionalities, and also discuss the unresolved questions in the direct conversion of methane to methanol reactions. Finally, we hope to offer some suggestions and strategies for guiding the practical applications regarding the catalyst design and engineering for a high methanol yield in the methane oxidation reaction.
Topics: Methanol; Methane; Catalytic Domain; Catalysis; Zeolites
PubMed: 36363972
DOI: 10.3390/molecules27217146 -
International Journal of Environmental... Nov 2022Volatile organic compounds (VOCs) are an important source of air pollution, harmful to human health and the environment, and important precursors of secondary organic...
Volatile organic compounds (VOCs) are an important source of air pollution, harmful to human health and the environment, and important precursors of secondary organic aerosols, O and photochemical smog. This study focused on the low-temperature catalytic oxidation and degradation of benzene, dichloroethane, methanethiol, methanol and methylamine by ozone. Benzene was used as a model compound, and a molecular sieve was selected as a catalyst carrier to prepare a series of supported active metal catalysts by impregnation. The effects of ozone on the catalytic oxidation of VOCs and catalysts' activity were studied. Taking benzene as a model compound, low-temperature ozone catalytic oxidation was conducted to explore the influence of the catalyst carrier, the active metal and the precious metal Pt on the catalytic degradation of benzene. The optimal catalyst appeared to be 0.75%Pt-10%Fe/HZSM(200). The catalytic activity and formation of the by-products methylamine, methanethiol, methanol, dichloroethane and benzene over 0.75%Pt-10%Fe/HZSM(200) were investigated. The structure, oxygen vacancy, surface properties and surface acidity of the catalysts were investigated. XRD, TEM, XPS, H-TPR, EPR, CO-TPD, BET, CH-TPD and Py-IR were combined to establish the correlation between the surface properties of the catalysts and the degradation activity.
Topics: Humans; Zeolites; Volatile Organic Compounds; Benzene; Temperature; Methanol; Ethylene Dichlorides; Catalysis; Ozone; Oxidation-Reduction; Methylamines
PubMed: 36361395
DOI: 10.3390/ijerph192114515 -
Molecules (Basel, Switzerland) Nov 2022Organophosphorus compounds are the core structure of many active natural products. The synthesis of these compounds is generally achieved by metal catalysis requiring...
Organophosphorus compounds are the core structure of many active natural products. The synthesis of these compounds is generally achieved by metal catalysis requiring specifically functionalized substrates or harsh conditions. Herein, we disclose the phospha-Michael addition reaction of biphenyphosphine oxide with various substituted β-nitrostyrenes or benzylidene malononitriles. This biocatalytic strategy provides a direct route for the synthesis of C-P bonds with good functional group compatibility and simple and practical operation. Under the optimal conditions (styrene (0.5 mmol), biphenyphosphine oxide (0.5 mmol), Novozym 435 (300 U), and EtOH (1 mL)), lipase leads to the formation of organophosphorus compounds in yields up to 94% at room temperature. Furthermore, we confirm the role of the catalytic triad of lipase in this phospha-Michael addition reaction. This new biocatalytic system will have broad applications in organic synthesis.
Topics: Lipase; Stereoisomerism; Catalysis; Organophosphorus Compounds; Oxides
PubMed: 36431898
DOI: 10.3390/molecules27227798 -
International Journal of Molecular... Oct 2023Graphitic carbon nitride (g-CN), a metal-free polymer semiconductor, has been recognized as an attractive photocatalytic material for environmental remediation because... (Review)
Review
Graphitic carbon nitride (g-CN), a metal-free polymer semiconductor, has been recognized as an attractive photocatalytic material for environmental remediation because of its low band gap, high thermal and photostability, chemical inertness, non-toxicity, low cost, biocompatibility, and optical and electrical efficiency. However, g-CN has been reported to suffer from many difficulties in photocatalytic applications, such as a low specific surface area, inadequate visible-light utilization, and a high charge recombination rate. To overcome these difficulties, the formation of g-CN heterojunctions by coupling with metal oxides has triggered tremendous interest in recent years. In this regard, zinc oxide (ZnO) is being largely explored as a self-driven semiconductor photocatalyst to form heterojunctions with g-CN, as ZnO possesses unique and fascinating properties, including high quantum efficiency, high electron mobility, cost-effectiveness, environmental friendliness, and a simple synthetic procedure. The synergistic effect of its properties, such as adsorption and photogenerated charge separation, was found to enhance the photocatalytic activity of heterojunctions. Hence, this review aims to compile the strategies for fabricating g-CN/ZnO-based Z-scheme and S-scheme heterojunction photocatalytic systems with enhanced performance and overall stability for the photodegradation of organic pollutants. Furthermore, with reference to the reported system, the photocatalytic mechanism of g-CN/ZnO-based heterojunction photocatalysts and their charge-transfer pathways on the interface surface are highlighted.
Topics: Zinc Oxide; Photolysis; Oxides; Environmental Pollutants
PubMed: 37834469
DOI: 10.3390/ijms241915021 -
Biochimica Et Biophysica Acta.... Oct 2021Lipid hydroperoxides are the primary reaction products of lipid oxidation, a natural outcome of life under oxygen. While playing a major role in cell metabolism, the...
Lipid hydroperoxides are the primary reaction products of lipid oxidation, a natural outcome of life under oxygen. While playing a major role in cell metabolism, the microscopic origins of the effects of lipid hydroperoxidation on biomembranes remain elusive. Here we probe the polar structure of partially to fully hydroperoxidized bilayers of 1-palmitoyl-2-oleoyl-sn-glycero-3-phosphocholine (POPC) by a combination of environment-sensitive fluorescent probes and coarse-grained Martini numerical simulations. We find that the inserted organic hydroperoxide group -OOH migrates preferentially to the surface for bilayers with small fractions of hydroperoxidized lipids, but populates also significantly the bilayer interior for larger fractions. Our findings suggest that by modifying the intimate polarity of biomembranes, lipid peroxidation will have a significant impact on the activity of transmembrane proteins and on the bio-medical efficiency of membrane active molecules such as cell-penetrating and antimicrobial peptides.
Topics: Hydrogen Peroxide; Hydrophobic and Hydrophilic Interactions; Lipid Bilayers; Oxidation-Reduction; Phosphatidylcholines; Spectrometry, Fluorescence
PubMed: 34052197
DOI: 10.1016/j.bbamem.2021.183659