Influence of desorption process and pH adjustement on the efficiency of O3, O3/H2O2 and O3/UV treatment of water and soil samples contaminated by crude petroleum.

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.

Lethal and sub-lethal evaluation of Indigo Carmine dye and byproducts after TiO2 photocatalysis in the immune system of Eisenia andrei earthworms.

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.

Effect of Abiotic Factors on Degradation of Imidacloprid.

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.

Complete and Partial Photo-oxidation of Dissolved Organic Matter Draining Permafrost Soils.

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.

Investigating Role of Abiotic Factors on Spinosad Dissipation.

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.

UV-visible degradation of boscalid--structural characterization of photoproducts and potential toxicity using in silico tests.

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.

Photodegradation of dioxin in contaminated soil in the presence of solvents and nanoscale TiO2 particles.

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.

Integrated electrokinetics-adsorption remediation of saline-sodic soils: effects of voltage gradient and contaminant concentration on soil electrical conductivity.

In this study, an integrated in situ remediation technique which couples electrokinetics with adsorption, using locally produced granular activated carbon from date palm pits in the treatment zones that are installed directly to bracket the contaminated soils at bench-scale, is investigated. Natural saline-sodic clay soil, spiked with contaminant mixture (kerosene, phenol, Cr, Cd, Cu, Zn, Pb, and Hg), was used in this study to investigate the effects of voltage gradient, initial contaminant concentration, and polarity reversal rate on the soil electrical conductivity. Box-Behnken Design (BBD) was used for the experimental design and response surface methodology (RSM) was employed to model, optimize, and interpret the results obtained using Design-Expert version 8 platform. The total number of experiments conducted was 15 with voltage gradient, polarity reversal rate, and initial contaminant concentration as variables. The main target response discussed in this paper is the soil electrical conductivity due to its importance in electrokinetic remediation process. Responses obtained were fitted to quadratic models whose R (2) ranges from 84.66% to 99.19% with insignificant lack of fit in each case. Among the investigated factors, voltage gradient and initial contaminant concentration were found to be the most significant influential factors.

Coupled electrokinetics-adsorption technique for simultaneous removal of heavy metals and organics from saline-sodic soil.

In situ remediation technologies for contaminated soils are faced with significant technical challenges when the contaminated soil has low permeability. Popular traditional technologies are rendered ineffective due to the difficulty encountered in accessing the contaminants as well as when employed in settings where the soil contains mixed contaminants such as petroleum hydrocarbons, heavy metals, and polar organics. In this study, an integrated in situ remediation technique that couples electrokinetics with adsorption, using locally produced granular activated carbon from date palm pits in the treatment zones that are installed directly to bracket the contaminated soils at bench-scale, is investigated. Natural saline-sodic soil, spiked with contaminant mixture (kerosene, phenol, Cr, Cd, Cu, Zn, Pb, and Hg), was used in this study to investigate the efficiency of contaminant removal. For the 21-day period of continuous electrokinetics-adsorption experimental run, efficiency for the removal of Zn, Pb, Cu, Cd, Cr, Hg, phenol, and kerosene was found to reach 26.8, 55.8, 41.0, 34.4, 75.9, 92.49, 100.0, and 49.8%, respectively. The results obtained suggest that integrating adsorption into electrokinetic technology is a promising solution for removal of contaminant mixture from saline-sodic soils.

Application of microwave-irradiated manganese dioxide in the removal of polychlorinated biphenyls from soil contaminated by capacitor oil.

The removal of polychlorinated biphenyls (PCBs) from soil contaminated with capacitor oil, using microwave (MW)-irradiated manganese dioxide (MnO2), was examined under different conditions. The effects of different types of MnO2 added as oxidant, as well as the initial amount of water, MnO2, and sulphuric acid solution, were also investigated. The removal efficiencies for dichlorobiphenyls, trichlorobiphenyls, tetrachlorobiphenyls, pentachlorobiphenyls, hexachloro-biphenyls, heptachlorobiphenyls, and octachlorobiphenyls were approximately 95.9%, 82.5%, 52.0%, 71.6%, 62.5%, 28.6%, and 16.1%, respectively, by 800 W MW irradiation for 45 min with the assistance of 0.1 g delta-MnO2 and 0.2 mL water in 1.0 g severely PCB-contaminated soil (sigma PCB = 1560.82 mg/kg); meanwhile, the concentrations of Mn2+ ions detected were from 10.6 +/- 1.9 mg/kg at 0 min to 108.2 +/- 7.8 mg/kg after 45 min MW irradiation, indicating that MnO2 acted as not only a MW absorber but also an oxidizer. Removal efficiencies of PCBs from contaminated soil increased with increasing the amounts of water and MnO2 added. The type of MnO2 also affected the removal of PCBs, following an order of delta-MnO2 > alpha-MnO2 > beta-MnO2. The addition of low concentration of sulphuric acid (such as 1.0 mol/L) solution was favourable for the removal of low chloro-substituted PCBs, but the addition of more than 1.0 mol/L sulphuric acid reduced the removal of all PCBs. The pronounced removal of PCBs from contaminated soil in a short treatment time indicates that MW irradiation with the assistance of MnO2 is an efficient and promising technology for the remediation of PCB-contaminated soil.

Impedance matching of a coaxial antenna for microwave in-situ processing of polluted soils.

The present paper is focused on the minimization of return loss of a slotted coaxial radiator proposed for a decontamination system for soils contaminated by volatile or semi-volatile organic compounds such as oils or fuels. The antenna upgrade is achieved by coating it with a 5 mm thick Teflon layer. The electromagnetic characteristics reflection coefficient and power density distribution around the antenna surrounded by soils with different moisture levels are analyzed numerically. Simplified analytical approaches are employed to accelerate the optimization of the given antenna for microwave heating systems. The improved antenna design shows a good matching of the antenna to the surrounding soil with varying moisture levels. This ensures a high efficiency of the proposed in-situ soil decontamination system.

Effect of light and pH on persistence of flubendiamide.

Persistence of flubendiamide in soil as affected by UV and sunlight exposure and in water as affected by pH was studied. At field capacity moisture regime, soil was treated with flubendiamide and exposed to UV and sunlight. Dissipation for the pesticide followed mono-phasic first order kinetics. Residues of flubendiamide, as thin film on petri-plates and soil thin film, dissipated with half-lives of 7.0 and 9.1 days under UV light and 12.0 and 19.1 days under sunlight, respectively. Residues of flubendiamide dissipated faster under UV light as compared to sunlight. Persistence study in aqueous medium under different pH condition indicated that flubendiamide residues persisted in water beyond 250 days with half-lives ranging from 250.8 to 301.0 days. Dissipation in water was faster at pH 4.0 (T(1/2) 250.8 days), followed by pH 9.2 (T(1/2) 273.6 days) and 7.0 (T(1/2) 301.0 days).

Effects of light and microbial activity on the degradation of two fluoroquinolone antibiotics in pond water and sediment.

Enrofloxacin (ENR) and ciprofloxacin (CIP) are two fluoroquinolone (FQ) antibiotics widely used to treat diseases of human beings and cultured animals. These two FQs are usually detected in the effluent of municipal sewage plants and related aquatic environments. The purpose of this study was to understand the fates of ENR and CIP in aquaculture pond water and a sediment slurry in a laboratory-scale experiment. Effects of light and microbial activity on the degradation of these two FQs were investigated. Results indicated that natural irradiation plays a major role in the degradation of ENR and CIP in pond water and the sediment slurry. The 50 % dissipation times (DT(50)) with non-sterile treatment were 0.01 and 18.4 d for ENR, and 0.04 and 17.3 d for CIP in the water and sediment slurry, respectively. On the other hand, the degradation of ENR and CIP under dark conditions was slow or even hindered, and all of their DT(50) values exceeded 100 d. These two FQs degraded faster in the sediment slurry than in pond water under dark conditions. Artificial ultraviolet (UV) and fluorescence light had similar effects on the degradation of ENR in the pond water and sediment slurry. Degradation of CIP was faster with UV than with fluorescence light treatment, while no such difference was found for ENR degradation. CIP was a degradation product of ENR under both light and dark conditions, and DT(50) values for both compounds were shorter in the presence of light. The phenomenon of biodegradation was observed during degradation of CIP in the sediment slurry under natural light.

Evaluation of degradation of antibiotic tetracycline in pig manure by electron beam irradiation.

This study was carried out to evaluate the degradation efficiency and intermediate products of the tetracycline from artificially contaminated pig manure using of electron beam irradiation as a function of the absorbed dose. The degradation efficiency of tetracycline was 42.77% at 1 kGy, 64.20% at 3 kGy, 77.83% at 5 kGy, and 90.50% at 10 kGy. The initial concentration of tetracycline (300 mg kg(-1)) in pig manure decreased significantly to 24.2 +/- 5.3 mg kg(-1) after electron beam irradiation at 10 kGy. The radiolytic degradation products of tetracycline were 1,4-benzenedicarboxylic acid, hexadecanoic acid, 9-octadecenamide, 11-octadecenamide, and octadecanoic acid.

Remediation of petroleum hydrocarbon contaminated soil by using activated persulfate with ultrasound and ultrasound/Fe.

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.

Leachability and potential ecotoxic impact of trifluralin-impregnated mulch.

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.

Photodegradation of clothianidin and thiamethoxam in agricultural soils.

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.

Fluoroquinolone antibiotics in the environment.

Fluoroquinolones (FQs) are used in large amounts for human and animal medical care. They are excreted as parent compound, as conjugates, or as oxidation, hydroxylation, dealkylation, or decarboxylation products of the parent compound. A considerable amount of FQs and their metabolites may reach the soil as constituents of urine, feces, or manure. The residues of FQs in foods of animal origin may pose hazards to consumers through emergence of drug-resistant bacteria. FQs bind strongly to topsoil, reducing the threat of surface water and groundwater contamination. The strong binding of FQs to soil and sediments delays their biodegradation and explains the recalcitrance of FQs. Wastewater treatment is an efficient elimination step (79%-87% removal) for FQs before they enter rivers. FQs are susceptible to photodegradation in aqueous medium, involving oxidation, dealkylation, and cleavage of the piperazine ring.

Explosives: fate, dynamics, and ecological impact in terrestrial and marine environments.

An explosive or energetic compound is a chemical material that, under the influence of thermal or chemical shock, decomposes rapidly with the evolution of large amounts of heat and gas. Numerous compounds and compositions may be classified as energetic compounds; however, secondary explosives, such as TNT, RDX, and HMX pose the largest potential concern to the environment because they are produced and used in defense in the greatest quantities. The environmental fate and potential hazard of energetic compounds in the environment is affected by a number of physical, chemical, and biological processes. Energetic compounds may undergo transformation through biotic or abiotic degradation. Numerous organisms have been isolated with the ability to degrade/transform energetic compounds as a sole carbon source, sole nitrogen source, or through cometabolic processes under aerobic or anaerobic conditions. Abiotic processes that lead to the transformation of energetic compounds include photolysis, hydrolysis, and reduction. The products of these reactions may be further transformed by microorganisms or may bind to soil/sediment surfaces through covalent binding or polymerization and oligomerization reactions. Although considerable research has been performed on the fate and dynamics of energetic compounds in the environment, data are still gathering on the impact of TNT, RDX, and HMX on ecological receptors. There is an urgent need to address this issue and to direct future research on expanding our knowledge on the ecological impact of energetic transformation products. In addition, it is important that energetic research considers the concept of bioavailability, including factors influencing soil/sediment aging, desorption of energetic compounds from varying soil and sediment types, methods for modeling/predicting energetic bioavailability, development of biomarkers of energetic exposure or effect, and the impact of bioavailability on ecological risk assessment.

The stability of butyltin compounds in a dredged heavily-contaminated sediment.

A treatment process for marine sediment heavily contaminated with tributyltin (TBT) was designed that included dehydrating, sunlight drying and dumping processes. The time course in butyltin (BTs) compounds, TBT, dibutyltin (DBT) and monobutyltin concentrations were investigated in the sediment treated under various conditions (light (UV, sunlight and light exclusion), moisture (air-drying and water saturation) and wetting and drying cycles). Significant changes in all the BT compound concentrations with time were not found regardless of the sediment conditions for light and moisture. The results indicated the high stabilities of TBT and DBT in the sediments versus light and moisture condition changes, probably taking place in the treatment process. It is also estimated that the BTs in the sediment are resistant to photo-degradation and biochemical degradation and their half lives are relatively long. In contrast, the decreases in the TBT and DBT were observed during the wetting and drying cycle treatment for the water saturated sediment both during exposure to sunlight and under a dark condition. This result suggested the hypothesis that the TBT degradation could be accelerated by the high microbial activity induced by the moisture changing treatments.