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The Science of the Total Environment Feb 2020Epidemiology studies over the past five decades have provided convincing evidence that exposure to air pollution is associated with multiple adverse health outcomes,... (Review)
Review
Epidemiology studies over the past five decades have provided convincing evidence that exposure to air pollution is associated with multiple adverse health outcomes, including increased mortality. Air pollution is a complex mixture of particles, vapors and gases emitted from natural and anthropogenic sources as well as formed through photochemical transformation processes. In metropolitan areas, air pollutants from combustion emissions feature a blend of emitted particles, oxides of carbon, sulfur and nitrogen, volatile organic compounds, and secondary reaction products, such as ozone, nitrogen dioxide, and secondary organic aerosols. Because many of the primary and transformed pollutants track together, their relative contributions to health outcomes are difficult to disentangle. Aside from the criteria pollutants ozone and nitrogen dioxide and some of the simpler aldehydes (e.g. formaldehyde and acrolein), other products from photochemical processes are a particularly vexing class of chemicals to investigate since they comprise a dynamic ill-defined complex mixture in both particulate and gas phases. The purpose of this review was to describe and compare health effects of freshly emitted versus oxidatively or photochemically aged air pollutants. In some cases, (e.g. single volatile organic compounds) photochemical transformation resulted in marked enhancements in toxicity through formation of both known and unidentified reaction products, while in other examples (e.g. aging of automobile emissions) the potentiation of effect was variable. The variation in experimental design, aging system employed, concentration and type of starting agent, and toxicity endpoints make comparisons between different studies exceedingly difficult. A more systematic approach with a greater emphasis on higher throughput screening and computational toxicology is needed to fully answer under what conditions oxidatively- or photochemically-transformed pollutants elicit greater health effects than primary emissions.
Topics: Air Pollutants; Air Pollution; Aldehydes; Environmental Exposure; Humans; Nitrogen Dioxide; Ozone; Particulate Matter; Volatile Organic Compounds
PubMed: 31838301
DOI: 10.1016/j.scitotenv.2019.135772 -
Ecotoxicology and Environmental Safety Nov 2023The use of Advance Oxidation Process (AOPs) has been extensively examined in order to eradicate organic pollutants. This review assesses the efficacy of photolysis, O... (Review)
Review
The use of Advance Oxidation Process (AOPs) has been extensively examined in order to eradicate organic pollutants. This review assesses the efficacy of photolysis, O based (O/UV, O/HO, O/HO/UV, HO/UV, Fenton, Fenton-like, hetero-system) and sonochemical and electro-oxidative AOPs in this regard. The main purpose of this review and some suggestions for the advancement of AOPs is to facilitate the elimination of toxic organic pollutants. Initially proposed for the purification of drinking water in 1980, AOPs have since been employed for various wastewater treatments. AOPs technologies are essentially a process intensification through the use of hybrid methods for wastewater treatment, which generate large amounts of hydroxyl (•OH) and sulfate (SO4·-) radicals, the ultimate oxidants for the remediation of organic pollutants. This review covers the use of AOPs and ozone or UV treatment in combination to create a powerful method of wastewater treatment. This novel approach has been demonstrated to be highly effective, with the acceleration of the oxidation process through Fenton reaction and photocatalytic oxidation technologies. It is clear that Advance Oxidation Process are a helpful for the degradation of organic toxic compounds. Additionally, other processes such as •OH and SO4·- radical-based oxidation may also arise during AOPs treatment and contribute to the reduction of target organic pollutants. This review summarizes the current development of AOPs treatment of wastewater organic pollutants.
Topics: Hydroxyl Radical; Hydrogen Peroxide; Wastewater; Oxidation-Reduction; Environmental Pollutants
PubMed: 37890248
DOI: 10.1016/j.ecoenv.2023.115564 -
Journal of Animal Science Apr 2022Sperm are susceptible to excessive reactive oxygen species (ROS). Spermine and spermidine are secreted in large amounts by the prostate and potent natural free radical...
Sperm are susceptible to excessive reactive oxygen species (ROS). Spermine and spermidine are secreted in large amounts by the prostate and potent natural free radical scavengers and protect cells against redox disorder. Thus, we used boar sperm as a model to study the polyamines uptake and elucidate whether polyamines protected sperm from ROS stress. Seven mature and fertile Duroc boars (aged 15 to 30 mo) were used in this study. In experiment 1, spermine and spermidine (3.6 ± 0.3 and 3.3 ± 0.2 mmol/L, respectively) were abundant in seminal plasma, and the content of polyamine decreased (P < 0.05) after preservation at 17 °C for 7 d or incubation at 37 °C for 6 h. In experiment 2, using labeling of spermine or spermidine by conjugation with fluorescein isothiocyanate and ultra-high-performance liquid chromatography, we found that the accumulation of spermine or spermidine in sperm was inhibited by quinidine and dl-tetrahydropalmatine (THP, organic cation transporters [OCT] inhibitors, P < 0.05), but not mildronate and l-carnitine (organic cation/carnitine transporter [OCTN] inhibitors, P > 0.05). In experiment 3, the addition of spermine or spermidine (0.5 mmol/L) in the extender resulted in higher motility, plasma membrane and acrosome integrity, and lower ROS level after preservation in vitro at 17 °C for 7 d (P < 0.05). In experiment 4, in the condition of oxidative stress (treatment with H2O2 at 37 °C for 2 h), the addition of spermine (1 mmol/L) or spermidine (0.5 mmol/L) in extender increased activities of glutathione peroxidase, glutathione reductase, and glutathione S-transferase; reduced glutathione and oxidized glutathione ratio (P < 0.05); and alleviate oxidative stress-induced lipid peroxidation, DNA damage, mitochondrial membrane potential (ΔΨm) decline, adenosine triphosphate depletion, and intracellular calcium concentration ([Ca2+]i) overload (P < 0.05), thereby improving boar sperm motility, the integrity of plasma membrane and acrosome (P < 0.05) in vitro. These data suggest that spermine and spermidine alleviate oxidative stress via the antioxidant capacity, thereby improving the efficacy of boar semen preservation.
Topics: Animals; Hydrogen Peroxide; Male; Oxidative Stress; Polyamines; Semen Preservation; Sperm Motility; Spermatozoa; Swine
PubMed: 35247050
DOI: 10.1093/jas/skac069 -
Journal of Hazardous Materials May 2022The kinetics of monopersulfate based systems in the elimination of potential harmful contaminants has been assessed from a theoretical point of view. A detailed reaction... (Review)
Review
The kinetics of monopersulfate based systems in the elimination of potential harmful contaminants has been assessed from a theoretical point of view. A detailed reaction mechanism sustained in the generation of radicals (mainly hydroxyl and sulfate), propagation and termination stages has been proposed. The system of first order differential equations derived has numerically been solved. The effect of main influencing parameters such as contaminant and peroxymonosulfate initial concentrations, intermediate generation, presence of organic matter, role played by anions, has been theoretically obtained. Discussion of simulated results has been accomplished by comparison with experimental data found in the literature. At the sight of the theoretical and empirical data, use of simplistic pseudo first order kinetics is discouraged. Despite considering a significant number of elemental reactions, modelling of the system reveals that a high fraction of them can be neglected due to their insignificant role played in the mechanism. The entire mechanism has been tested when peroxymonosulfate has been activated by UV radiation, although results can be fairly extrapolated to other activation strategies. Finally, a generic model capable of accounting for the effect of a diversity of parameters is proposed. No theoretical background is behind the model, however the generic model clearly improves the results obtained by simple first order kinetics.
Topics: Hydroxyl Radical; Kinetics; Oxidation-Reduction; Peroxides; Sulfates; Water; Water Pollutants, Chemical; Water Purification
PubMed: 35176700
DOI: 10.1016/j.jhazmat.2022.128383 -
Accounts of Chemical Research Sep 2019In addition to nitric oxide and carbon monoxide, hydrogen sulfide (HS) has been recently recognized as an important biological signaling molecule with implications in a... (Review)
Review
In addition to nitric oxide and carbon monoxide, hydrogen sulfide (HS) has been recently recognized as an important biological signaling molecule with implications in a wide variety of processes, including vasodilation, cytoprotection, and neuromodulation. In parallel to the growing number of reports highlighting the biological impact of HS, interest in developing HS donors as both research tools and potential therapeutics has led to the growth of different HS-releasing strategies. Many HS investigations in model systems use direct inhalation of HS gas or aqueous solutions of NaSH or NaS; however, such systems do not mimic endogenous HS production. This stark contrast drives the need to develop better sources of caged HS. To address these limitations, different small organosulfur donor compounds have been prepared that release HS in the presence of specific activators or triggers. Such compounds, however, often lack suitable control compounds, which limits the use of these compounds in probing the effects of HS directly. To address these needs, our group has pioneered the development of carbonyl sulfide (COS) releasing compounds as a new class of HS donor motifs. Inspired by a commonly used carbamate prodrug scaffold, our approach utilizes self-immolative thiocarbamates to access controlled release of COS, which is rapidly converted to HS by the ubiquitous enzyme carbonic anhydrase (CA). In addition, this design enables access to key control compounds that release CO/HO rather than COS/HS, which enables delineation of the effects of COS/HS from the organic donor byproducts. In this Account, we highlight a library of first-generation COS/HS donors based on self-immolative thiocarbamates developed in our lab and also highlight challenges related to HS donor development. We showcase the release of COS in the presence of specific triggers and activators, including biological thiols and bio-orthogonal reactants for targeted applications. We also demonstrate the design and development of a series of HO/reactive oxygen species (ROS)-triggered donors and show that such compounds can be activated by endogenous levels of ROS production. Utilizing approaches in bio-orthogonal activation, we establish that donors functionalized with an -nitrobenzyl photocage can enable access to light-activated donors. Similar to endogenous production by cysteine catabolism, we also prepared a cysteine-selective COS donor activated by a Strongin ligation mechanism. In efforts to help delineate potential differences in the chemical biology of COS and HS, we also report a simple esterase-activated donor, which demonstrated fast COS-releasing kinetics and inhibition of mitochondrial respiration in BEAS-2B cells. Additional investigations revealed that COS release rates and cytotoxicity correlated directly within this series of compounds with different ester motifs. In more recent and applied applications of this HS donation strategy, we also highlight the development of donors that generate either a colorimetric or fluorescent optical response upon COS release. Overall, the work described in this Account outlines the development and initial application of a new class of HS donors, which we anticipate will help to advance our understanding of the rapidly emerging chemical biology of HS and COS.
Topics: Animals; Carbonic Anhydrases; Cell Survival; HeLa Cells; Humans; Hydrogen Peroxide; Hydrogen Sulfide; Mice; Molecular Structure; RAW 264.7 Cells; Sulfur Oxides; Thiocarbamates
PubMed: 31390174
DOI: 10.1021/acs.accounts.9b00315 -
International Journal of Molecular... Dec 2022This review examines the role of chlorine dioxide (ClO) on inorganic compounds and cell biomolecules. As a disinfectant also present in drinking water, ClO helps to... (Review)
Review
This review examines the role of chlorine dioxide (ClO) on inorganic compounds and cell biomolecules. As a disinfectant also present in drinking water, ClO helps to destroy bacteria, viruses, and some parasites. The Environmental Protection Agency EPA regulates the maximum concentration of chlorine dioxide in drinking water to be no more than 0.8 ppm. In any case, human consumption must be strictly regulated since, given its highly reactive nature, it can react with and oxidize many of the inorganic compounds found in natural waters. Simultaneously, chlorine dioxide reacts with natural organic matter in water, including humic and fulvic acids, forming oxidized organic compounds such as aldehydes and carboxylic acids, and rapidly oxidizes phenolic compounds, amines, amino acids, peptides, and proteins, as well as the nicotinamide adenine dinucleotide NADH, responsible for electron and proton exchange and energy production in all cells. The influence of ClO on biomolecules is derived from its interference with redox processes, modifying the electrochemical balances in mitochondrial and cell membranes. This discourages its use on an individual basis and without specialized monitoring by health professionals.
Topics: Humans; Drinking Water; Chlorine Compounds; Oxides; Oxidation-Reduction; Disinfectants; Water Purification; Chlorine; Disinfection
PubMed: 36555303
DOI: 10.3390/ijms232415660 -
Molecules (Basel, Switzerland) Feb 2022Benzo[a]pyrene (BaP) is a polycyclic aromatic hydrocarbon (PAH) primarily formed by burning of fossil fuels, wood and other organic materials. BaP as group I carcinogen... (Review)
Review
Benzo[a]pyrene (BaP) is a polycyclic aromatic hydrocarbon (PAH) primarily formed by burning of fossil fuels, wood and other organic materials. BaP as group I carcinogen shows mutagenic and carcinogenic effects. One of the important mechanisms of action of (BaP) is its free radical activity, the effect of which is the induction of oxidative stress in cells. BaP induces oxidative stress through the production of reactive oxygen species (ROS), disturbances of the activity of antioxidant enzymes, and the reduction of the level of non-enzymatic antioxidants as well as of cytokine production. Chemical compounds, such as vitamin E, curcumin, quercetin, catechin, cyanidin, kuromanin, berberine, resveratrol, baicalein, myricetin, catechin hydrate, hesperetin, rhaponticin, as well as taurine, atorvastatin, diallyl sulfide, and those contained in green and white tea, lower the oxidative stress induced by BaP. They regulate the expression of genes involved in oxidative stress and inflammation, and therefore can reduce the level of ROS. These substances remove ROS and reduce the level of lipid and protein peroxidation, reduce formation of adducts with DNA, increase the level of enzymatic and non-enzymatic antioxidants and reduce the level of pro-inflammatory cytokines. BaP can undergo chemical modification in the living cells, which results in more reactive metabolites formation. Some of protective substances have the ability to reduce BaP metabolism, and in particular reduce the induction of cytochrome (CYP P450), which reduces the formation of oxidative metabolites, and therefore decreases ROS production. The aim of this review is to discuss the oxidative properties of BaP, and describe protective activities of selected chemicals against BaP activity based on of the latest publications.
Topics: Animals; Antioxidants; Benzo(a)pyrene; Biomarkers; Disease Susceptibility; Energy Metabolism; Gene Expression Regulation; Humans; Lipid Peroxidation; Molecular Structure; Oxidants; Oxidation-Reduction; Oxidative Stress; Reactive Oxygen Species
PubMed: 35209168
DOI: 10.3390/molecules27041379 -
Chemosphere Jun 2023Recalcitrant and toxic organic pollutants from wastewaters are scarcely removed in conventional wastewater treatment plants. To preserve the water quality, organics need... (Review)
Review
Solar photoelectro-Fenton: A very effective and cost-efficient electrochemical advanced oxidation process for the removal of organic pollutants from synthetic and real wastewaters.
Recalcitrant and toxic organic pollutants from wastewaters are scarcely removed in conventional wastewater treatment plants. To preserve the water quality, organics need to be removed by developing powerful oxidation technologies. Our laboratory proposed in 2007 a potent electrochemical advanced oxidation process (EAOP) for wastewater remediation, so-called solar photoelectro-Fenton (SPEF). This review summarizes the advances of this emerging technology up to 2022, making evident its effectiveness and cost-efficiency for the destruction of usual organic pollutants. The simultaneous action of generated hydroxyl radicals and the photolysis by sunlight explains the high oxidation power of SPEF respect to other EAOPs. The review is initiated by describing the fundamentals of the process to remark the role of the produced oxidants and the benefits of using solar irradiation in its performance. The photoelectrochemical systems used (bench tank reactor and solar pre-pilot flow plant) and the assessment of the operating variables are discussed. The characteristics of the most common homogeneous SPEF for the degradation and mineralization of several synthetic solutions of industrial chemicals, herbicides, pharmaceuticals, and synthetic organic dyes, as well as of some real wastewaters, are further described. The influence of the photoelectrochemical cell, electrodes, solution pH, electrolyte composition, Fe and pollutant concentration, and current density is analyzed. The performance of a homogeneous SPEF-like process with active chlorine and heterogeneous SPEF processes with solid catalysts such as FeO and sodium vermiculite is also discussed. Finally, the advances of homogeneous SPEF combined with other techniques like solar photocatalysis, solar photoelectrocatalysis, anaerobic digestion, and nanofiltration are reported.
Topics: Wastewater; Sunlight; Environmental Pollutants; Electrochemical Techniques; Herbicides; Oxidation-Reduction; Hydrogen Peroxide; Water Pollutants, Chemical; Electrodes
PubMed: 37003440
DOI: 10.1016/j.chemosphere.2023.138532 -
Chemosphere Aug 2023In this work, comparative study of paddy and upland soils were carried out to unravel mechanisms of enhanced soil organic carbon (SOC) sequestration in paddy soils using...
In this work, comparative study of paddy and upland soils were carried out to unravel mechanisms of enhanced soil organic carbon (SOC) sequestration in paddy soils using fractionation methods, C NMR and Nano-SIMS analysis, as well as organic layer thickness calculations (Core-Shell model). The results showed that although there is a strong increase in particulate SOC in paddy soils compared to that in the upland soils, the increase in mineral-associated SOC is more important, explaining 60-75% of SOC increase in the paddy soils. In the wet and dry alternate cycles of paddy soil, iron (hydr)oxides adsorb relatively small and soluble organic molecules (fulvic acid-like), promote catalytic oxidation and polymerization, thus accelerating formation of larger organic molecules. Upon reductive iron dissolution, these molecules are released and incorporated into existing less soluble organic compounds (humic acid or humin-like), which are coagulated and associated with clay minerals, becoming part of the mineral-associated SOC. The functioning of this "iron wheel" process stimulates accumulation of relatively young SOC into mineral-associated organic carbon pool, and reduces the difference in chemical structure between oxides-bound and clay-bound SOC. Further, the faster turnover of oxides and soil aggregates in paddy soil also facilities interaction between SOC and minerals. The formation of mineral-associated SOC may delay degradation of organic matter during both wet and dry period in the paddy field, therefore enhancing carbon sequestration in paddy soils.
Topics: Soil; Carbon; Clay; Carbon Sequestration; Oryza; Minerals; Iron; Oxides
PubMed: 37187382
DOI: 10.1016/j.chemosphere.2023.138927 -
Accounts of Chemical Research Dec 2022surface is covered by oceans, a large number of liquid aerosol particles fill the air, and clouds hold a tiny but critical fraction of Earth's water in the air to...
surface is covered by oceans, a large number of liquid aerosol particles fill the air, and clouds hold a tiny but critical fraction of Earth's water in the air to influence our climate and hydrology, enabling the lives of humans and ecosystems. The surfaces of these liquids provide the interface for the transfer of gases, for nucleation processes, and for catalyzing important chemical reactions. Coupling a range of spectroscopic tools to liquid microjets has become an important approach to better understanding dynamics, structure, and chemistry at liquid interfaces. Liquid microjets offer stability in vacuum and ambient pressure environments, thus also allowing X-ray photoelectron spectroscopy (XPS) with manageable efforts in terms of differential pumping. Liquid microjets are operated at speeds sufficient to allow for a locally equilibrated surface in terms of water dynamics and solute surface partitioning. XPS is based on the emission of core-level electrons, the binding energy of which is selective for the element and its chemical environment. Inelastic scattering of electrons establishes the probing depth of XPS in the nanometer range and thus its surface sensitivity.In this Account, we focus on aqueous solutions relevant to the surface of oceans, aqueous aerosols, or cloudwater. We are interested in understanding solvation and acid dissociation at the interface, interfacial aspects of reactions with gas-phase reactants, and the interplay of ions with organic molecules at the interface. The strategy is to obtain a link between the molecular-level picture and macroscopic properties and reactivity in the atmospheric context.We show consistency between surface tension and XPS for a range of surface-active organic species as an important proof for interrogating an equilibrated liquid surface. Measurements with organic acids and amines offer important insight into the question of apparent acidity or basicity at the interface. Liquid microjet XPS has settled the debate of the surface enhancement of halide ions, shown using the example of bromide and its oxidation products. Despite the absence of a strong enhancement for the bromide ion, its rate of oxidation by ozone is surface catalyzed through the stabilization of the bromide ozonide intermediate at the interface. In another reaction system, the one between Fe and HO, a similar intermediate in the form of highly valent iron species could not be detected by XPS under the experimental conditions employed, shedding light on the abundance of this intermediate in the environment but also on the constraints within which surface species can be detected. Emphasizing the importance of electrostatic effects, we show how a cationic surfactant attracts charged bromide anions to the interface, accompanied by enhanced oxidation rates by ozone, overriding the role of surfactants as a barrier for the access of gas-phase reactants. The reactivity and structure at interfaces thus result from a subtle balance between hygroscopic and hydrophobic interactions, electrostatic effects, and the structural properties of both liquids and solutes.
Topics: Humans; Bromides; Ecosystem; Hydrogen Peroxide; Ozone; Water
PubMed: 36472357
DOI: 10.1021/acs.accounts.2c00604