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1.
Article in English | MEDLINE | ID: mdl-31924135

ABSTRACT

The influence of the pH and the contaminant desorption/emulsification on ozone (O3), ozone-hydrogen peroxide (O3/H2O2) and ozone-photolysis (O3/UV) oxidation reactions were performed to treat crude petroleum (CP) contaminated soil and water samples. Oxidation efficiency is also related to both free radicals formation in reaction medium (which is dependent of the pH), and contaminant availability (which is dependent of the compounds solubilization or desorption processes). Thus, batch basic processes of O3/H2O2 or O3/UV were improved with sonication system and surfactant addition. In the case of O3/H2O2 process, the reactions were performed at adjusted (pH = 11) and natural pH (free pH= 4-5). The effectiveness of the improved advanced oxidation processes were evaluated through the time-course analysis of the chemical oxygen demand (COD), biochemical oxygen demand (BOD5), and total organic carbon (TOC) values. For both improved treatment processes, CP-contaminated water samples displayed higher values for TOC removal and BOD5/COD ratios than CP-contaminated soil samples. The O3/H2O2 process provided better results than the O3/UV process regarding degradation efficiency, but the former is associated with higher treatment costs due to H2O2 consumption. Overall, oxidation treatment processes increase their efficiencies when reactions are carried out associated with solubilization and desorption systems promoted by sonication/surfactant action.


Subject(s)
Hydrogen Peroxide/chemistry , Ozone/chemistry , Petroleum/analysis , Soil Pollutants/analysis , Ultraviolet Rays , Water Pollutants, Chemical/analysis , Biological Oxygen Demand Analysis , Hydrogen-Ion Concentration , Models, Theoretical , Oxidation-Reduction , Petroleum/radiation effects , Photolysis , Soil/chemistry , Soil Pollutants/radiation effects , Water Pollutants, Chemical/radiation effects , Water Purification/methods
2.
Chemosphere ; 238: 124657, 2020 Jan.
Article in English | MEDLINE | ID: mdl-31473526

ABSTRACT

This study investigates the degradation of petroleum hydrocarbon in contaminated soil using activated persulfate (PS) with ultrasound (US) and US/Fe. Various controlling factors including different PS dosage, ultrasonic power, pH, soil water ratio and soil particle size were considered. It was found that petroleum hydrocarbon degradation efficiency achieved up to 56.41% and 82.23% in US/PS and US/Fe/PS system, respectively. Based on the experimental results, the reaction rate of US/Fe/PS system was faster than US/PS system and the degradation efficiency enhanced significantly with the increasing ultrasonic power. Changing initial solution pH influenced the petroleum hydrocarbon reaction rate and the best performance would be achieved at pH of 5. The present work identified the main components of petroleum hydrocarbon pollutants in shale gas sites. The mechanism of petroleum hydrocarbon degradation on US/Fe/PS system were analyzed.


Subject(s)
Environmental Restoration and Remediation/methods , Hydrocarbons/chemistry , Petroleum Pollution , Soil Pollutants/chemistry , Environmental Pollution/analysis , Hydrocarbons/radiation effects , Natural Gas , Soil , Soil Pollutants/analysis , Soil Pollutants/radiation effects , Sulfates/chemistry , Ultrasonic Waves , Water Pollutants, Chemical
3.
Environ Sci Pollut Res Int ; 25(31): 31318-31325, 2018 Nov.
Article in English | MEDLINE | ID: mdl-30194578

ABSTRACT

Presented in this paper is a study on the photodegradation of two widely used neonicotinoid insecticides clothianidin and thiamethoxam in three soils and in solid phase. The effects of light with differing wavelengths were examined using the natural sunlight and single ultraviolet A (UVA) and ultraviolet B (UVB) light sources. The results indicated that UVB played a key role in the photodegradation of clothianidin and thiamethoxam while the effects of visible and UVA lights were negligible. The degradations of clothianidin and thiamethoxam under all the light sources followed the first-order kinetics, and the half-lives of clothianidin and thiamethoxam in the three soils under the sunlight ranged from 97 to 112 h and 88 to 103 h, respectively. When clothianidin and thiamethoxam were directly exposed to the sunlight without soil, the degradation rates were remarkably higher with half-lives being 13 and 10 h, respectively. Therefore, the insecticides fallen on the surface of soils would be degraded under sunlight much faster than those that enter the soils. The examination of the degradation products revealed four compounds from the photodegradation of clothianidin and three from thiamethoxam, and clothianidin was one of the photodegradation products of thiamethoxam.


Subject(s)
Environmental Restoration and Remediation , Guanidines/chemistry , Insecticides/chemistry , Neonicotinoids/chemistry , Soil Pollutants/chemistry , Thiamethoxam/chemistry , Thiazoles/chemistry , Agriculture , Guanidines/radiation effects , Neonicotinoids/radiation effects , Photolysis , Soil , Soil Pollutants/radiation effects , Sunlight , Thiamethoxam/radiation effects , Thiazoles/radiation effects , Ultraviolet Rays
4.
Environ Sci Pollut Res Int ; 25(3): 2972-2980, 2018 Jan.
Article in English | MEDLINE | ID: mdl-29147986

ABSTRACT

The leachability, potential ecotoxicity, and photolysis of trifluralin-impregnated mulch, a popular retail consumer gardening product, were investigated under environmentally realistic conditions. Leachability of trifluralin from impregnated mulch was low (< 1% of total extractable compound) and in the range of reported values for agricultural soils. No trifluralin transformation products were detected in mulch leachate. Yeast-based estrogenicity and androgenicity screens indicated that aqueous trifluralin is not estrogenic but is moderately androgenic at concentrations ~ 1e - 5 M. Impregnated mulch leachate was not hormonally active, even at undiluted concentrations, but it did exert nonspecific toxicity at dilutions of ~ 1:10. Photolysis of trifluralin was investigated in acetonitrile and water and on mulch surfaces. Degradation on mulch surfaces was diffusion-limited; it was ~ 17 times slower than in aqueous solution, but faster than has been reported on kaolinite. An array of trifluralin transformation products was identified, but in no case did they exceed 10% of the parent compound. Using industry-recommended application guidelines, it is estimated that as much as 1400 µg/m2 of trifluralin may leach from impregnated mulch upon the first rainfall. However, provided that consumers are aware that such mulch products contain trifluralin and are properly educated about its use, the potential for direct ecotoxic impact is likely to be small.


Subject(s)
Agriculture , Soil Pollutants/analysis , Trifluralin/analysis , Ecotoxicology , Photolysis , Rain , Soil Pollutants/radiation effects , Surface Properties , Trifluralin/radiation effects
5.
Bull Environ Contam Toxicol ; 99(4): 475-480, 2017 Oct.
Article in English | MEDLINE | ID: mdl-28840262

ABSTRACT

The role of soil moisture, light and pH on imidacloprid dissipation was investigated. A high performance liquid chromatography (HPLC) based method was developed to quantify imidacloprid present in soil with a recovery of more than 82%. Rate of dissipation of imidacloprid from soil was faster in submerged condition compared to field capacity and air dried condition. Imidacloprid dissipated non-significantly between sterile and non-sterile soils, but at field capacity, the dissipation was faster in non-sterile soil compared to sterile soil after 60 days of incubation. Similarly, under submergence, the dissipation of imidacloprid was 66.2% and 79.8% of the initial in sterile and non-sterile soils, respectively. Imidacloprid was rather stable in acidic and neutral water but was prone to photo-degradation. Therefore, imidacloprid degradation will be faster under direct sunlight and at higher soil moisture.


Subject(s)
Neonicotinoids/analysis , Nitro Compounds/analysis , Soil Pollutants/analysis , Soil/chemistry , Sunlight , Water/analysis , Chromatography, High Pressure Liquid , Environmental Restoration and Remediation , Hydrogen-Ion Concentration , Models, Theoretical , Neonicotinoids/radiation effects , Nitro Compounds/radiation effects , Photolysis , Soil Pollutants/radiation effects
6.
Ecotoxicol Environ Saf ; 143: 275-282, 2017 Sep.
Article in English | MEDLINE | ID: mdl-28551585

ABSTRACT

The Indigo carmine (IC) dye has been widely used in textile industries, even though it has been considered toxic for rats, pigs and humans. Owing to its toxicity, wastes containing this compound should be treated to minimize or eliminate their toxic effects on the biota. As an alternative to wastewater treatment, advanced oxidative processes (AOPs) have been highlighted due to their high capacity to destruct organic molecules. In this context, this study aimed to evaluate Indigo Carmine toxicity to soil organisms using the earthworm Eisenia andrei as a model-organism and also verify the efficiency of AOP in reducing its toxicity to these organisms. To this end, lethal (mortality) and sub-lethal (loss or gain of biomass, reproduction, behavior, morphological changes and immune system cells) effects caused by this substance and its degradation products in these annelids were evaluated. Morphological changes were observed even in organisms exposed to low concentrations, while mortality was the major effect observed in individuals exposed to high levels of indigo carmine dye. The organisms exposed to the IC during the contact test showed mortality after 72h of exposure (LC50 = 75.79mgcm-2), while those exposed to photoproducts showed mortality after 48h (LC50 = 243min). In the chronic study, the organisms displayed a mortality rate of 14%, while those exposed to the photoproduct reached up to 32.7%. A negative influence of the dye on the reproduction rate was observed, while by-products affected juvenile survival. A loss of viability and alterations in the cellular proportion was verified during the chronic test. However, the compounds did not alter the behavior of the annelids in the leak test (RL ranged from 20% to 30%). Although photocatalysis has been presented as an alternative technology for the treatment of waste containing the indigo carmine dye, this process produced byproducts even more toxic than the original compounds to E. andrei.


Subject(s)
Indigo Carmine/toxicity , Oligochaeta/drug effects , Oligochaeta/immunology , Soil Pollutants/toxicity , Titanium/chemistry , Animals , Avoidance Learning/drug effects , Behavior, Animal/drug effects , Biomass , Catalysis , Indigo Carmine/radiation effects , Lethal Dose 50 , Oxidation-Reduction , Reproduction/drug effects , Soil/chemistry , Soil Pollutants/radiation effects , Time Factors , Toxicity Tests
7.
Article in English | MEDLINE | ID: mdl-28287500

ABSTRACT

Yixing, known as the "City of Ceramics", is facing a new dilemma: a raw material crisis. Cadmium (Cd) exists in extremely high concentrations in soil due to the considerable input of industrial wastewater into the soil ecosystem. The in situ technique of diffusive gradients in thin film (DGT), the ex situ static equilibrium approach (HAc, EDTA and CaCl2), and the dissolved concentration in soil solution, as well as microwave digestion, were applied to predict the Cd bioavailability of soil, aiming to provide a robust and accurate method for Cd bioavailability evaluation in Yixing. Moreover, the typical local cash crops-paddy and zizania aquatica-were selected for Cd accumulation, aiming to select the ideal plants with tolerance to the soil Cd contamination. The results indicated that the biomasses of the two applied plants were sufficiently sensitive to reflect the stark regional differences of different sampling sites. The zizania aquatica could effectively reduce the total Cd concentration, as indicated by the high accumulation coefficients. However, the fact that the zizania aquatica has extremely high transfer coefficients, and its stem, as the edible part, might accumulate large amounts of Cd, led to the conclusion that zizania aquatica was not an ideal cash crop in Yixing. Furthermore, the labile Cd concentrations which were obtained by the DGT technique and dissolved in the soil solution showed a significant correlation with the Cd concentrations of the biota accumulation. However, the ex situ methods and the microwave digestion-obtained Cd concentrations showed a poor correlation with the accumulated Cd concentration in plant tissue. Correspondingly, the multiple linear regression models were built for fundamental analysis of the performance of different methods available for Cd bioavailability evaluation. The correlation coefficients of DGT obtained by the improved multiple linear regression model have not significantly improved compared to the coefficients obtained by the simple linear regression model. The results revealed that DGT was a robust measurement, which could obtain the labile Cd concentrations independent of the physicochemical features' variation in the soil ecosystem. Consequently, these findings provide stronger evidence that DGT is an effective and ideal tool for labile Cd evaluation in Yixing.


Subject(s)
Cadmium/analysis , Environmental Monitoring/methods , Soil Pollutants/analysis , Acetates/chemistry , Biological Availability , Cadmium/chemistry , Cadmium/metabolism , Cadmium/radiation effects , Calcium Chloride/chemistry , Crops, Agricultural/metabolism , Ecosystem , Edetic Acid/chemistry , Linear Models , Microwaves , Soil/chemistry , Soil Pollutants/chemistry , Soil Pollutants/metabolism , Soil Pollutants/radiation effects
8.
Chemosphere ; 175: 1-7, 2017 May.
Article in English | MEDLINE | ID: mdl-28211322

ABSTRACT

Carbon-based nanomaterials, such as C60 fullerenes, are expected to accumulate in soil due to direct release and deposition from the atmosphere. However, little is known about the environmental fate of these nanoparticles which may be susceptible to photochemical and microbial degradation. In the present work, C60 was incubated for a period of 28 days and irradiated with UVA light. Three experiments were carried out where the fullerenes were either spiked onto a glass surface or added to quartz sand or sandy soil samples. At specific time intervals the samples were extracted and analysed by liquid chromatography coupled to UV or high resolution mass spectrometric (HRMS) detection. The fullerenes were degraded in all the treatments and the decay followed a pseudo-first-order rate law. In absence of a solid matrix, the half-life (t1/2) of the C60 was 13.1 days, with an overall degradation of 45.1% that was accompanied by the formation of functionalized C60-like structures. Furthermore, mass spectrometric analysis highlighted the presence of a large number of transformation products that were not directly related to the irradiation and presented opened cage and oxidized structures. When C60 was spiked into solid matrices the degradation occurred at a faster rate (t1/2 of 4.5 and 0.8 days for quartz sand and sandy soil, respectively). Minor but consistent losses were found in the non-irradiated samples, presumably due to biotic or chemical processes occurring in these samples. The results of this study suggest that light-mediated transformation of the fullerenes will occur in the environment.


Subject(s)
Environmental Restoration and Remediation/methods , Fullerenes/chemistry , Fullerenes/radiation effects , Soil Pollutants/radiation effects , Soil , Ultraviolet Rays , Chromatography, Liquid , Half-Life , Mass Spectrometry , Models, Chemical , Nanostructures/chemistry , Photochemistry , Soil/chemistry
9.
Chemosphere ; 148: 495-503, 2016 Apr.
Article in English | MEDLINE | ID: mdl-26841292

ABSTRACT

The photodegradation of polycyclic aromatic hydrocarbons (PAHs) in two typical Mediterranean soils, either coarse- or fine-textured, was here investigated. Soil samples, spiked with the 16 US EPA priority PAHs, were incubated in a climate chamber at stable conditions of temperature (20 °C) and light (9.6 W m(-2)) for 28 days, simulating a climate change base scenario. PAH concentrations in soils were analyzed throughout the experiment, and correlated with data obtained by means of Microtox(®) ecotoxicity test. Photodegradation was found to be dependent on exposure time, molecular weight of each hydrocarbon, and soil texture. Fine-textured soil was able to enhance sorption, being PAHs more photodegraded than in coarse-textured soil. According to the EC50 values reported by Microtox(®), a higher detoxification was observed in fine-textured soil, being correlated with the outcomes of the analytical study. Significant photodegradation rates were detected for a number of PAHs, namely phenanthrene, anthracene, benzo(a)pyrene, and indeno(123-cd)pyrene. Benzo(a)pyrene, commonly used as an indicator for PAH pollution, was completely removed after 7 days of light exposure. In addition to the PAH chemical analysis and the ecotoxicity tests, a hydrogen isotope analysis of benzo(a)pyrene was also carried out. The degradation of this specific compound was associated to a high enrichment in (2)H, obtaining a maximum δ(2)H isotopic shift of +232‰. This strong isotopic effect observed in benzo(a)pyrene suggests that compound-specific isotope analysis (CSIA) may be a powerful tool to monitor in situ degradation of PAHs. Moreover, hydrogen isotopes of benzo(a)pyrene evidenced a degradation process of unknown origin occurring in the darkness.


Subject(s)
Climate Change , Polycyclic Aromatic Hydrocarbons/radiation effects , Soil Pollutants/radiation effects , Deuterium/analysis , Photolysis , Polycyclic Aromatic Hydrocarbons/analysis , Polycyclic Aromatic Hydrocarbons/toxicity , Soil/chemistry , Soil Pollutants/analysis , Soil Pollutants/toxicity , Toxicity Tests
10.
Environ Int ; 89-90: 155-65, 2016.
Article in English | MEDLINE | ID: mdl-26859521

ABSTRACT

Polycyclic aromatic hydrocarbons (PAHs) are airborne pollutants that are deposited on soils. As climate change is already altering temperature and solar radiation, the global warming is suggested to impact the environmental fate of PAHs. This study was aimed at evaluating the effect of climate change on the PAH photodegradation in soils. Samples of Mediterranean soils were subjected to different temperature and light radiation conditions in a climate chamber. Two climate scenarios were considered according to IPCC projections: 1) a base (B) scenario, being temperature and light intensity 20°C and 9.6W/m(2), respectively, and 2) a climate change (CC) scenario, working at 24°C and 24W/m(2), respectively. As expected, low molecular weight PAHs were rapidly volatilized when increasing both temperature and light intensity. In contrast, medium and high molecular weight PAHs presented different photodegradation rates in soils with different texture, which was likely related to the amount of photocatalysts contained in both soils. In turn, the hydrogen isotopic composition of some of the PAHs under study was also investigated to verify any degradation process. Hydrogen isotopes confirmed that benzo(a)pyrene is degraded in both B and CC scenarios, not only under light but also in the darkness, revealing unknown degradation processes occurring when light is lacking. Potential generation pathways of PAH photodegradation by-products were also suggested, being a higher number of metabolites formed in the CC scenario. Consequently, in a more or less near future, although humans might be less exposed to PAHs, they could be exposed to new metabolites of these pollutants, which might be even more toxic.


Subject(s)
Climate Change , Photolysis , Polycyclic Aromatic Hydrocarbons/analysis , Soil Pollutants/analysis , Soil/chemistry , Catalysis , Humans , Light , Models, Theoretical , Polycyclic Aromatic Hydrocarbons/radiation effects , Soil Pollutants/radiation effects , Temperature , Time Factors
11.
Environ Sci Technol ; 50(7): 3545-53, 2016 Apr 05.
Article in English | MEDLINE | ID: mdl-26910810

ABSTRACT

Photochemical degradation of dissolved organic matter (DOM) to carbon dioxide (CO2) and partially oxidized compounds is an important component of the carbon cycle in the Arctic. Thawing permafrost soils will change the chemical composition of DOM exported to arctic surface waters, but the molecular controls on DOM photodegradation remain poorly understood, making it difficult to predict how inputs of thawing permafrost DOM may alter its photodegradation. To address this knowledge gap, we quantified the susceptibility of DOM draining the shallow organic mat and the deeper permafrost layer of arctic soils to complete and partial photo-oxidation and investigated changes in the chemical composition of each DOM source following sunlight exposure. Permafrost and organic mat DOM had similar lability to photomineralization despite substantial differences in initial chemical composition. Concurrent losses of carboxyl moieties and shifts in chemical composition during photodegradation indicated that photodecarboxylation could account for 40-90% of DOM photomineralized to CO2. Permafrost DOM had a higher susceptibility to partial photo-oxidation compared to organic mat DOM, potentially due to a lower abundance of phenolic moieties with antioxidant properties. These results suggest that photodegradation will likely continue to be an important control on DOM fate in arctic freshwaters as the climate warms and permafrost soils thaw.


Subject(s)
Organic Chemicals/radiation effects , Permafrost/chemistry , Soil/chemistry , Sunlight , Arctic Regions , Fresh Water/chemistry , Magnetic Resonance Spectroscopy , Mass Spectrometry , Minerals/chemistry , Oxidation-Reduction/radiation effects , Photolysis/radiation effects , Soil Pollutants/radiation effects , Solid Phase Extraction
12.
Environ Sci Pollut Res Int ; 23(6): 5654-66, 2016 Mar.
Article in English | MEDLINE | ID: mdl-26578379

ABSTRACT

Ivermectin (IVM) is a broad-spectrum antiparasitic drug that is regularly employed in veterinary medicine. In this work, the sorption and desorption of IVM in two Brazilian soils (N1-sand and S2-clay) as well as its leaching capacity, dissipation under aerobic conditions, and degradation in aqueous solution by photocatalysis with TiO2 in suspension were evaluated. The kinetic sorption curves of IVM were adjusted to a pseudo-second-order model. The sorption and desorption data were well fitted with the Freundlich isotherms in the log form (r > 0.96). The Freundlich sorption coefficient (K F (ads) ) and the Freundlich desorption coefficient (K F (des) ) were 77.7 and 120 µg(1-1/n) (cm(3))(1/n) g(-1) and 74.5 and 138 µg(1-1/n) (cm(3))(1/n) g(-1), for soils N1 and S2, respectively. A greater leaching capacity of IVM was observed for the sandy soil N1 than for the clay soil S2. Under aerobic conditions, the dissipation (DT50) at 19.3 °C was 15.5 days (soil N1) and 11.5 days (soil S2). Photocatalysis with UVC and TiO2 in suspension resulted in the degradation of 98 % of IVM (500 µg L(-1)) in water in 600 s. The toxicity (Daphnia similis) of the solutions submitted to the photocatalytic process was completely eliminated after 10 min.


Subject(s)
Antiparasitic Agents/analysis , Daphnia/drug effects , Ivermectin/analysis , Soil Pollutants/analysis , Water Pollutants, Chemical/analysis , Aerobiosis , Aluminum Silicates/chemistry , Animals , Antiparasitic Agents/radiation effects , Antiparasitic Agents/toxicity , Biodegradation, Environmental , Brazil , Clay , Ivermectin/radiation effects , Ivermectin/toxicity , Kinetics , Soil/chemistry , Soil Pollutants/radiation effects , Soil Pollutants/toxicity , Titanium/chemistry , Ultraviolet Rays , Water Pollutants, Chemical/radiation effects , Water Pollutants, Chemical/toxicity
13.
Environ Sci Pollut Res Int ; 23(5): 4473-80, 2016 Mar.
Article in English | MEDLINE | ID: mdl-26507736

ABSTRACT

The influences of Cu(2+) and Fe(2+) on the photodegradation of soil-incorporated chlorpyrifos were investigated in the present study. The soil samples spiked with chlorpyrifos and selected metal ions were irradiated with UV light for different intervals of time and analyzed by HPLC. The unsterile and sterile control soil samples amended with pesticides and selected metals were incubated in the dark at 25 °C for the same time intervals. The results of the study evidenced that photodegradation of chlorpyrifos followed the first-order kinetics. The dissipation t0.5 of chlorpyrifos was found to decrease from 41 to 20 days under UV irradiation. The rate of chlorpyrifos photodegradation was increased in the presence of both metals, i.e., Cu(2+) and Fe(2+). Thus, initially observed t0.5 of 19.8 days was decreased to 4.39 days in the case of Cu(+2) and 19.25 days for Fe(+2). Copper was found to increase the rate of photodegradation by 4.5 orders of magnitude while the microbial degradation of chlorpyrifos was increased only twofold. The microbial degradation of chlorpyrifos was only negligibly affected by Fe(2+) amendment. The studied trace metals also affected the abiotic degradation of the pesticide in the order Cu(2+) > Fe(2+).


Subject(s)
Chlorpyrifos/radiation effects , Photolysis , Soil Pollutants/radiation effects , Soil , Ultraviolet Rays , Chlorpyrifos/chemistry , Copper/chemistry , Iron/chemistry , Pesticides/radiation effects , Soil Pollutants/chemistry
14.
Bull Environ Contam Toxicol ; 96(1): 125-9, 2016 Jan.
Article in English | MEDLINE | ID: mdl-26350899

ABSTRACT

The effect of abiotic factors on dissipation of spinosad (soil moisture regimes, pH, and light) was studied. Spinosad residues were estimated using high performance liquid chromatography fitted with a UV detector. Under laboratory conditions, half-lives of spinosad were 9.0 and 7.7 days for air dried and field capacity soils, respectively. Percent dissipation of spinosad after 30 days was 47.02, 22.35, 62.5, 68.23 and 76.47 in solution with an aqueous pH of 10.85, 9.15, 6.97, 3.90 and 2.04, respectively. The half-life of spinosad in UV and sunlight was only 1.6 and 5.2 h, respectively. Light, especially the UV component, is an important factor for degradation of spinosad compared to other abiotic conditions.


Subject(s)
Insecticides/chemistry , Macrolides/chemistry , Soil Pollutants/chemistry , Chromatography, High Pressure Liquid , Drug Combinations , Half-Life , Hydrogen-Ion Concentration , Insecticides/radiation effects , Light , Macrolides/radiation effects , Soil , Soil Pollutants/radiation effects , Sunlight
15.
PLoS One ; 10(8): e0134298, 2015.
Article in English | MEDLINE | ID: mdl-26241043

ABSTRACT

Cu(II) and organic carboxylic acids, existing extensively in soil and aquatic environments, can form complexes that may play an important role in the photodegradation of organic contaminants. In this paper, the catalytic role of Cu(II) in the removal of methyl orange (MO) in the presence of tartaric acid with light was investigated through batch experiments. The results demonstrate that the introduction of Cu(II) could markedly enhance the photodegradation of MO. In addition, high initial concentrations of Cu(II) and tartaric acid benefited the decomposition of MO. The most rapid removal of MO assisted by Cu(II) was achieved at pH 3. The formation of Cu(II)-tartaric acid complexes was assumed to be the key factor, generating hydroxyl radicals (•OH) and other oxidizing free radicals under irradiation through a ligand-to-metal charge-transfer pathway that was responsible for the efficient degradation of MO. Some intermediates in the reaction system were also detected to support this reaction mechanism.


Subject(s)
Azo Compounds/radiation effects , Cations, Divalent/pharmacology , Copper/pharmacology , Tartrates/pharmacology , Catalysis , Chromogenic Compounds/analysis , Colorimetry , Coloring Agents/radiation effects , Free Radicals , Hydrogen-Ion Concentration , Hydroxyl Radical , Oxidation-Reduction , Photolysis , Quinolines/analysis , Soil Pollutants/radiation effects
16.
Chemosphere ; 138: 924-31, 2015 Nov.
Article in English | MEDLINE | ID: mdl-25576129

ABSTRACT

Photocatalytic decay profiles of polycyclic aromatic hydrocarbon (PAH) benzo[a]pyrene (B[a]P) have been investigated on various synthesized iron oxides and on soil surfaces under a set of diverse conditions. Samples were analysed using the developed HPLC procedure. Results of the present study demonstrate fastest photodisintegration of B[a]P on goethite followed by haematite, magnetite, akaganeite and maghemite, respectively. The effect of soil pH, irradiation wavelength and iron oxide and oxalic acid dose on the degradation of B[a]P was evaluated. The studies revealed enhancement in photodegradation in the presence of oxalic acid due to the occurrence of fenton like reaction. The results showed faster B[a]P degradation under short wavelength UV radiation. Rate constants in acidic, neutral and alkaline soils under optimum dissipation conditions were 1.11×10(-2), 7.69×10(-3) and 9.97×10(-3) h(-1), respectively. The study indicates that iron oxides along with oxalic acid are effective photocatalyst for the remediation of benzo[a]pyrene contaminated soil surfaces. The degradation products of B[a]P in the soils of different pH in presence of goethite were identified and degradation pathways proposed. Peaks due to toxic metabolites such as diones, diols and epoxides disappear after 120 h in all the three soils.


Subject(s)
Benzo(a)pyrene/analysis , Ferric Compounds/chemistry , Photolysis , Soil Pollutants/analysis , Ultraviolet Rays , Benzo(a)pyrene/radiation effects , Catalysis , Chromatography, High Pressure Liquid , Ferric Compounds/analysis , Iron Compounds/analysis , Mass Spectrometry , Minerals/analysis , Oxalic Acid/chemistry , Soil Pollutants/radiation effects
17.
J Hazard Mater ; 285: 208-11, 2015 Mar 21.
Article in English | MEDLINE | ID: mdl-25497313

ABSTRACT

This work developed an immediate and high-performance remediation method for Cr(VI) contaminated soil (CCS) using high energy electron beam (HEEB) irradiation. The result indicated that, compared with γ-ray irradiation, HEEB irradiation displayed a significant reduction efficiency on Cr(VI) in CCS to Cr(III) with substantially lower toxicity, which was mainly attributed to the reduction effects of electrons, hydrated electrons, and reductive radicals generated in the irradiation process of HEEB. This work could provide a one-step and effective method for the remediation of heavy metal contaminated soil (HMCS).


Subject(s)
Chromium/radiation effects , Electrons , Environmental Restoration and Remediation/methods , Soil Pollutants/radiation effects , Gamma Rays , Oxidation-Reduction
18.
Environ Technol ; 35(9-12): 1121-32, 2014.
Article in English | MEDLINE | ID: mdl-24701907

ABSTRACT

Decomposition of 2,3,7,8-Tetrachlorodibenzo-p-dioxin (2,3,7,8-TCDD) present in soil under ultraviolet (UV) illumination (350-400nm) was investigated using a combination of nontoxic solvents mixed in soil and nanoscale anatase TiO2 (nTiO2) distributed on 2mm top soil surface. Three types of UV-exposure experiments were conducted: intermittent exposure (8 h/day) for 90 days and 120 days, sequential intermittent (120 days) and continuous (24 h/day) for the next 55 days, and continuous exposure for 55 days. The influence of several factors on dioxin photodegradation efficiency was investigated, including the UV absorption by the targeted dioxin, presence of catalytic nTiO2 on soil surface, solvent evaporation rate, as well as vertical gradients of solvents added into the soil columns. Results of dioxin analysis for the soil samples collected at the end of every experiment condition show that the photodegradation enhanced by the nTiO2 presence on the soil surface considerably increased the dioxin removal. Higher removal efficiencies were found for treatments with 15%wt of nTiO2 mixed in the 2-mm surface soil as compared to the 5%wt nTiO2 treatments. The highest removal efficiency (79.6%) was for the sequential intermittent-continuous UV-exposure experiment with nTiO2. Dechlorinated products of 2,3,7,8-TCDD were generally not detected which suggests degradation of targeted dioxin by C-Cl cleavage was negligible. Further modifications to improve removal efficiencies were proposed. Large-scale engineered systems may employ this integrated treatment approach which can also incorporate the reuse of the top soil containing nTiO2 and solvent vapours. With the utilization of natural sunlight such systems would be promisingly suitable for tropical conditions.


Subject(s)
Dioxins/chemistry , Dioxins/radiation effects , Photolysis , Soil Pollutants/chemistry , Soil Pollutants/radiation effects , 1-Butanol/chemistry , Alkanes/chemistry , Nanoparticles/chemistry , Olive Oil , Plant Oils/chemistry , Solvents/chemistry , Titanium/chemistry , Ultraviolet Rays
19.
Rapid Commun Mass Spectrom ; 28(10): 1153-63, 2014 May 30.
Article in English | MEDLINE | ID: mdl-24711278

ABSTRACT

RATIONALE: Boscalid is a carboximide fungicide mainly used for vineyard protection as well as for tomato, apple, blueberry and various ornamental cultivations. The structural elucidation of by-products arising from the UV-visible photodegradation of boscalid has been investigated by gas chromatography/multi-stage mass spectrometry (GC/MS(n) ) and liquid chromatography/tandem mass spectrometry (LC/MS/MS) couplings. The potential toxicities of transformation products were estimated by in silico calculations. METHODS: Aqueous solutions of boscalid were irradiated up to 150 min in a self-made reactor equipped with a mercury lamp. Analyses were carried out using a gas chromatograph coupled with an ion trap mass spectrometer operated in both electron ionization (EI) and chemical ionization (CI) modes and a liquid chromatograph coupled with a quadrupole time-of-flight (Q-TOF) mass spectrometer operated in electrospray ionization (ESI) mode. Multiple-stage collision-induced dissociation (CID) experiments were performed to establish dissociation pathways of ions. The QSAR (Quantitative Structure-Activity Relationship) T.E.S.T. program allowed the estimation of the toxicities of the by-products. RESULTS: Eight photoproducts were investigated. Chemical structures were proposed not only on the interpretation of multi-stage CID experiments, but also on kinetics data. These structures led us to suggest photodegradation pathways. Three photoproducts were finally detected in Lebanon in a real sample of grape leaves for which routine analysis had led to the detection of boscalid at 4 mg kg(-1). CONCLUSIONS: With one exception, the structures proposed for the photoproducts on the basis of mass spectra interpretation have not been reported in previous studies. In silico toxicity predictions showed that two photoproducts are potentially more toxic than the parent compound considering oral rat LD50 while five photoproducts may induce mutagenic toxicity. With the exception of one compound, all photoproducts may potentially induce developmental toxicity.


Subject(s)
Biphenyl Compounds/radiation effects , Biphenyl Compounds/toxicity , Niacinamide/analogs & derivatives , Soil Pollutants/radiation effects , Soil Pollutants/toxicity , Animals , Biphenyl Compounds/chemistry , Chromatography, Liquid , Computer Simulation , Environmental Restoration and Remediation , Gas Chromatography-Mass Spectrometry , Niacinamide/chemistry , Niacinamide/radiation effects , Niacinamide/toxicity , Photolysis , Rats , Soil Pollutants/chemistry , Tandem Mass Spectrometry , Ultraviolet Rays
20.
Environ Sci Pollut Res Int ; 21(5): 3443-51, 2014 Mar.
Article in English | MEDLINE | ID: mdl-24243162

ABSTRACT

In the present study, the photolysis of carbofuran has been undertaken under sunlight conditions and at the surface of model supports such as clay films and different soils collected from two different sites in Morocco (Tirs and Dahs). In all conditions, an efficient degradation occurred owing to direct light absorption and also to photoinduced processes involving either clays or natural organic matter moities. On kaolin films, the photodegradation kinetics appears to follow a first-order process that clearly depends on the film thickness. The diffusion of carbofuran from the lower part to the illuminated surface was found to be negligible when compared to the photolysis process within the range of 20-70 µm. Thus, the photolysis rate constant at the surface of the solid support, k (0), was evaluated to be 7.0 × 10(-3) min(-1). Under these experimental conditions, the quantum yield was found equal to 2.1 × 10(-4). On soil surfaces, the disappearance rate constant was mainly attributed to photoinduced processes arising from natural organic matter. From the analytical point of view, the products were formed through (1) hydroxylation on the aromatic ring, (2) homolytic scission of the carbamate C-O bond leading to radical species formation, and (3) photohydrolysis of the carbamate C-O bond.


Subject(s)
Carbofuran/radiation effects , Insecticides/radiation effects , Kaolin/radiation effects , Soil Pollutants/radiation effects , Carbofuran/chemistry , Insecticides/chemistry , Photolysis , Soil Pollutants/chemistry , Sunlight
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