Adsorption and leaching of fluorotelomer compounds and perfluoroalkyl acids in aqueous media by activated carbon prepared from municipal biosolids.

Perfluoroalkyl acids (PFAAs) are ubiquitous in nature and pose serious health risks to humans and animals. Limiting PFAA exposure requires novel technology for their effective removal from water. We investigated the efficacy of biosolid-based activated carbon (Bio-SBAC) in removing frequently detected PFAAs and their precursor fluorotelomer compounds at environmentally relevant concentrations (∼50 µg/L). Batch experiments were performed to investigate adsorption kinetics, isotherms, and leachability. Bio-SBAC achieved >95% removal of fluorotelomeric compounds, indicating that the need for PFAA removal from the environment could be minimised if the precursors were targeted. Kinetic data modelling suggested that chemisorption is the dominant PFAA adsorption mechanism. As evidenced by the isotherm modelling results, Freundlich adsorption intensity, n-1, values of <1 (0.707-0.938) indicate chemisorption. Bio-SBAC showed maximum capacities for the adsorption of perfluorooctanoic acid (1429 µg/g) and perfluorononanoic acid (1111 µg/g). Batch desorption tests with 100 mg/L humic acid and 10 g/L NaCl showed that Bio-SBAC effectively retained the adsorbed PFAA with little or no leaching, except perfluorobutanoic acid. Overall, this study revealed that Bio-SBAC is a value-added material with promising characteristics for PFAA adsorption and no leachability. Additionally, it can be incorporated into biofilters to remove PFAAs from stormwater, presenting a sustainable approach to minimise biosolid disposal and improve the quality of wastewater before discharge into receiving waters.

2D Ni2P/N-doped graphene heterostructure as a Novel electrocatalyst for hydrogen evolution reaction: A computational study.

The main prerequisite for designing electrocatalysts with favorable performance is to examine the links between electronic structural features and catalytic activity. In this work, Ni2P as a model electrocatalyst and one of the most potent catalysts for hydrogen evolution reaction (HER) was utilized to develop various Ni2P and carbon-based (graphene and N-doped graphene) heterostructures. The characteristics of such structures (Ni2P, graphene, N-doped graphene, Ni2P/graphene, and Ni2P/N-doped graphene), including binding energies, the projected density of states (PDOS), band structure, charge density difference, charge transfer, Hirshfeld charge analysis, and minimum-energy path (MEP) towards HER were calculated and analyzed by density functional theory (DFT) approach. The coupling energy values of hybrid systems were correlated with the magnitude of charge transfer. The main factors driving a promising water-splitting reaction were explained by the data of PDOS, band structures, and charge analysis, including the inherent electronegativity of the N species alongside shifting the Fermi level toward the conductive band. It was also shown that a significant drop occurs in the HER energy barrier on Ni2P/graphene compared to the pristine Ni2P due to N doping on the graphene layer in the Ni2P/N-doped graphene heterostructure.

Removal of perfluoroalkyl acids from aqueous media by surfactant-modified clinoptilolites.

Perfluoroalkyl and polyfluoroalkyl substances (PFASs) are environmentally persistent, bioaccumulating, and toxic compounds that have attracted global attention. It is challenging to reduce the residual concentrations of these compounds to safe discharge limits. In this study, batch experiments were performed to evaluate natural clinoptilolite and clinoptilolites modified (MC) with cetylpyridinium chloride (CPC-MC), didodecyldimethylammonium bromide (DDAB-MC), hexadecyltrimethylammonium bromide (HDTMA-MC), and tetramethylammonium chloride (TMA-MC) as cost-effective aqueous PFAS adsorbents. The removal capacities of the adsorbents for the majority of the PFASs decreased in the following order: DDAB-MC > CPC-MC ≫ modified natural clinoptilolite with hexadecyltrimethyl ammonium bromide (HDTMA-MC) ≫ modified natural clinoptilolite with tetramethylammonium chloride (TMA-MC) ≈ natural clinoptilolite modified with NaCl (NC). In particular, CPC-MC and DDAB-MC reduced PFASs concentration in 50 µg/L by up to 98% for perfluorooctane sulphonate. Within 30 min, CPC-MC (30.5 µg/L) and DDAB-MC (32.1 µg/L) met the PFOS water quality criterion of 36 µg/L in inland surface waters. Both adsorbents met this criterion at the highest solution volume (40 mL) and 0.125 g/L (solid-to-liquid ratio of 1:8). PFASs with short hydrocarbon chains competed more for adsorption. PFASs with sulphonate functional groups were also adsorbed more than carboxyl groups in single- and multi-PFAS solutions. The modified surfaces of clinoptilolites controlled PFAS adsorption through hydrophobic and electrostatic interactions. PFAS removal with surfactant-modified clinoptilolites is cost-effective and protects aquatic environments by using surplus natural materials.

Estimating hydrogen absorption energy on different metal hydrides using Gaussian process regression approach.

Hydrogen is a promising alternative energy source due to its significantly high energy density. Also, hydrogen can be transformed into electricity in energy systems such as fuel cells. The transition toward hydrogen-consuming applications requires a hydrogen storage method that comes with pack hydrogen with high density. Among diverse methods, absorbing hydrogen on host metal is applicable at room temperature and pressure, which does not provide any safety concerns. In this regard, AB2 metal hydride with potentially high hydrogen density is selected as an appropriate host. Machine learning techniques have been applied to establish a relationship on the effect of the chemical composition of these hosts on hydrogen storage. For this purpose, a data bank of 314 data point pairs was used. In this assessment, the different A-site and B-site elements were used as the input variables, while the hydrogen absorption energy resulted in the output. A robust Gaussian process regression (GPR) approach with four kernel functions is proposed to predict the hydrogen absorption energy based on the inputs. All the GPR models' performance was quite excellent; notably, GPR with Exponential kernel function showed the highest preciseness with R2, MRE, MSE, RMSE, and STD of 0.969, 2.291%, 3.909, 2.501, and 1.878, respectively. Additionally, the sensitivity of analysis indicated that ZR, Ti, and Cr are the most demining elements in this system.

Recent advances in aqueous virus removal technologies.

The COVID-19 outbreak has triggered a massive research, but still urgent detection and treatment of this virus seems a public concern. The spread of viruses in aqueous environments underlined efficient virus treatment processes as a hot challenge. This review critically and comprehensively enables identifying and classifying advanced biochemical, membrane-based and disinfection processes for effective treatment of virus-contaminated water and wastewater. Understanding the functions of individual and combined/multi-stage processes in terms of manufacturing and economical parameters makes this contribution a different story from available review papers. Moreover, this review discusses challenges of combining biochemical, membrane and disinfection processes for synergistic treatment of viruses in order to reduce the dissemination of waterborne diseases. Certainly, the combination technologies are proactive in minimizing and restraining the outbreaks of the virus. It emphasizes the importance of health authorities to confront the outbreaks of unknown viruses in the future.

An insight into tetracycline photocatalytic degradation by MOFs using the artificial intelligence technique.

Tetracyclines (TCs) have been extensively used for humans and animal diseases treatment and livestock growth promotion. The consumption of such antibiotics has been ever-growing nowadays due to various bacterial infections and other pathologic conditions, resulting in more discharge into the aquatic environments. This brings threats to ecosystems and human bodies. Up to now, several attempts have been made to reduce TC amounts in the wastewater, among which photocatalysis, an advanced oxidation process, is known as an eco-friendly and efficient technology. In this regard, metal organic frameworks (MOFs) have been known as the promising materials as photocatalysts. Thus, studying TC photocatalytic degradation by MOFs would help scientists and engineers optimize the process in terms of effective parameters. Nevertheless, the costly and time-consuming experimental methods, having instrumental errors, encouraged the authors to use the computational method for a more comprehensive assessment. In doing so, a wide-ranging databank including 374 experimental data points was gathered from the literature. A powerful machine learning method of Gaussian process regression (GPR) model with four kernel functions was proposed to estimate the TC degradation in terms of MOFs features (surface area and pore volume) and operational parameters (illumination time, catalyst dosage, TC concentration, pH). The GPR models performed quite well, among which GPR-Matern model shows the most accurate performance with R2, MRE, MSE, RMSE, and STD of 0.981, 12.29, 18.03, 4.25, and 3.33, respectively. In addition, an analysis of sensitivity was carried out to assess the effect of the inputs on the TC photodegradation by MOFs. It revealed that the illumination time and the surface area play a significant role in the decomposition activity.

Exploratory study of removing nutrients from aqueous environments employing a green synthesised nano zero-valent iron.

This study explores the green synthesis of nano zero-valent iron (nZVI) extracted from the peel of selected waste fruits: banana (BP), mango (MP), and pomegranate (GP), for the removal of nutrients from aqueous environments. The extract was prepared by heating de-ionised water at 60°C for 5 min, adding a reducing and a stabilising agent, FeCl3, then stirring with a N2 gas flush solution to form iron nanoparticles, with a final drying step under N2 conditions. Using a variety of characterisation techniques, it was determined that nZVI particles were successfully synthesised via the reduction of iron (III) to iron (0) and stabilised by the presence of phenolic compounds in the extract. The removal of 20 mg/L nutrients from an aqueous solution carried out using the nZVIs resulted in nitrate removal of 92% (nZVI-GP), 88% (nZVI-BP), and 72% (nZVI-MP) within 5 min, whereas ∼98% phosphate was removed by all three nZVIs within 60 min. The aging effect was also tested. Aging the nZVIs for >20 days resulted in less efficient phosphate adsorption after exposure for 250 min; ∼70% phosphate removal was achieved using the nZVIs under these conditions. The mechanisms and pathways of nitrate reduction, including the adsorption of phosphate by nZVI were demonstrated, and discussed. Leachability tests of the phosphate-loaded nZVIs revealed that 10%, 28%, and 48% phosphate was released from the nZVI-GP, nZVI-BP, and nZVI-MP particles, respectively. Using waste fruit is, therefore, a viable and sustainable alternative to the traditional sodium borohydride method to produce nZVIs for environmental application.

Encapsulation of an anticancer drug Isatin inside a host nano-vehicle SWCNT: a molecular dynamics simulation.

The use of carbon nanotubes as anticancer drug delivery cargo systems is a promising modality as they are able to perforate cellular membranes and transport the carried therapeutic molecules into the cellular components. Our work describes the encapsulation process of a common anticancer drug, Isatin (1H-indole-2,3-dione) as a guest molecule, in a capped single-walled carbon nanotube (SWCNT) host with chirality of (10,10). The encapsulation process was modelled, considering an aqueous solution, by a molecular dynamics (MD) simulation under a canonical NVT ensemble. The interactions between the atoms of Isatin were obtained from the DREIDING force filed. The storage capacity of the capped SWCNT host was evaluated to quantify its capacity to host multiple Isatin molecules. Our results show that the Isatin can be readily trapped inside the volume cavity of the capped SWCNT and it remained stable, as featured by a reduction in the van der Waals forces between Isatin guest and the SWCNT host (at approximately - 30 kcal mol-1) at the end of the MD simulation (15 ns). Moreover, the free energy of encapsulation was found to be - 34 kcal mol-1 suggesting that the Isatin insertion procedure into the SWCNT occurred spontaneously. As calculated, a capped SWCNT (10,10) with a length of 30 Å, was able to host eleven (11) molecules of Isatin, that all remained steadily encapsulated inside the SWCNT volume cavity, showing a potential for the use of carbon nanotubes as drug delivery cargo systems.

Towards estimation of CO2 adsorption on highly porous MOF-based adsorbents using gaussian process regression approach.

In recent years, new developments in controlling greenhouse gas emissions have been implemented to address the global climate conservation concern. Indeed, the earth's average temperature is being increased mainly due to burning fossil fuels, explicitly releasing high amounts of CO2 into the atmosphere. Therefore, effective capture techniques are needed to reduce the concentration of CO2. In this regard, metal organic frameworks (MOFs) have been known as the promising materials for CO2 adsorption. Hence, study on the impact of the adsorption conditions along with the MOFs structural properties on their ability in the CO2 adsorption will open new doors for their further application in CO2 separation technologies as well. However, the high cost of the corresponding experimental study together with the instrument's error, render the use of computational methods quite beneficial. Therefore, the present study proposes a Gaussian process regression model with four kernel functions to estimate the CO2 adsorption in terms of pressure, temperature, pore volume, and surface area of MOFs. In doing so, 506 CO2 uptake values in the literature have been collected and assessed. The proposed GPR models performed very well in which the exponential kernel function, was shown as the best predictive tool with R2 value of 1. Also, the sensitivity analysis was employed to investigate the effectiveness of input variables on the CO2 adsorption, through which it was determined that pressure is the most determining parameter. As the main result, the accurate estimate of CO2 adsorption by different MOFs is obtained by briefly employing the artificial intelligence concept tools.

Theoretical Encapsulation of Fluorouracil (5-FU) Anti-Cancer Chemotherapy Drug into Carbon Nanotubes (CNT) and Boron Nitride Nanotubes (BNNT).

INTRODUCTION: Chemotherapy with anti-cancer drugs is considered the most common approach for killing cancer cells in the human body. However, some barriers such as toxicity and side effects would limit its usage. In this regard, nano-based drug delivery systems have emerged as cost-effective and efficient for sustained and targeted drug delivery. Nanotubes such as carbon nanotubes (CNT) and boron nitride nanotubes (BNNT) are promising nanocarriers that provide the cargo with a large inner volume for encapsulation. However, understanding the insertion process of the anti-cancer drugs into the nanotubes and demonstrating drug-nanotube interactions starts with theoretical analysis. METHODS: First, interactions parameters of the atoms of 5-FU were quantified from the DREIDING force field. Second, the storage capacity of BNNT (8,8) was simulated to count the number of drugs 5-FU encapsulated inside the cavity of the nanotubes. In terms of the encapsulation process of the one drug 5-FU into nanotubes, it was clarified that the drug 5-FU was more rapidly adsorbed into the cavity of the BNNT compared with the CNT due to the higher van der Waals (vdW) interaction energy between the drug and the BNNT. RESULTS: The obtained values of free energy confirmed that the encapsulation process of the drug inside the CNT and BNNT occurred spontaneously with the free energies of -14 and -25 kcal·mol-1, respectively. DISCUSSION: However, the lower value of the free energy in the system containing the BNNT unraveled more stability of the encapsulated drug inside the cavity of the BNNT comparing the system having CNT. The encapsulation of Fluorouracil (5-FU) anti-cancer chemotherapy drug (commercial name: Adrucil®) into CNT (8,8) and BNNT (8,8) with the length of 20 Å in an aqueous solution was discussed herein applying molecular dynamics (MD) simulation.

Thermal conductivity of random polycrystalline BC3 nanosheets: A step towards realistic simulation of 2D structures.

Boron carbide nanosheets (BC3NSs) are semiconductors possessing non-zero bandgap. Nevertheless, there is no estimation of their thermal conductivity for practical circumstances, mainly because of difficulties in simulation of random polycrystalline structures. In the real physics world, BC3NS with perfect monocrystalline is rare, for the nature produces structures with disordered grain regions. Therefore, it is of crucial importance to capture a more realistic picture of thermal conductivity of these nanosheets. Polycrystalline BC3NS (PCBC3NSs are herein simulated by Molecular Dynamics simulation to take their thermal conductivity fingerprint applying ΔT of 40 K. A series of PCBC3NSs were evaluated for thermal conductivity varying the number of grains (3, 5, and 10). The effect of grain rotation was also modeled in terms of Kapitza thermal resistance per grain, varying the rotation angle (θ/2 = 14.5, 16, 19, and 25°). Overall, a non-linear temperature variation was observed for PCBC3NS, particularly by increasing grain number, possibly because of more phonon scattering (shorter phonon relaxation time) arising from more structural defects. By contrast, the heat current passing across the slab decreased. The thermal conductivity of nanosheet dwindled from 149 W m-1 K-1 for monocrystalline BC3NS to the values of 129.67, 121.32, 115.04, and 102.78 W m-1 K-1 for PCBC3NSs having 2, 3, 5, and 10 grains, respectively. The increase of the grain̛s rotation angle (randomness) from 14.5° to 16°, 19° and 25° led to a rise in Kapitza thermal resistance from 2⨯10-10 m2 K·W-1 to the values of 2.3⨯ 10-10, 2.9⨯10-10, and 4.7⨯ 10-10 m2 K·W-1, respectively. Thus, natural 2D structure would facilitate phonon scattering rate at the grain boundaries, which limits heat transfer across polycrystalline nanosheets.

Adsorption of polycyclic aromatic hydrocarbons by surfactant-modified clinoptilolites for landfill leachate treatment.

The authors report the potential adsorption capacities of three surfactant-modified clinoptilolites (MC)-cetylpyridinium chloride (CPC)-MC, didodecyldimethylammonium bromide (DDAB)-MC, and hexadecyltrimethylammonium bromide (HDTMA)-MC-for the removal of polycyclic aromatic hydrocarbons (PAHs) from aquatic environments and landfill leachate. A liquid-liquid extraction method was used to extract PAHs from water and GC/MS was used to analyse the PAHs. PAH accumulations on CPC-MC, DDAB-MC, and HDTMA-MC were linear over 21 successive batch adsorption tests for anthracene (708, 737, and 750 µg/g), fluoranthene (1355, 1583, and 1303 µg/g), fluorene (973, 1060, and 1147 µg/g), phenanthrene (844, 1057, and 989 µg/g), and pyrene (1343, 1569, and 1269 µg/g). The leachability after 21 successive accumulations was <2% for anthracene, <4% for fluoranthene, <3% for fluorene, <4% for pyrene, and <5% for phenanthrene for each adsorbent. PAH removals from landfill leachate for anthracene, fluoranthene, fluorene, phenanthrene, and pyrene were 97.8%, 98.6%, 95.7%, 97.0%, and 98.5% for CPC-MC and 99.0%, 99.6%, 98.0%, 99.0%, and 99.6% for DDAB-MC, respectively, meeting the fresh water quality standards established by British Columbia and the World Health Organization (WHO) for anthracene, fluoranthene, and fluorene. The molecular weight and molecular structure of PAHs and the hydrophobicity of adsorbents can fundamentally influence the PAH adsorption mechanism based on π-π stacking.

Insights into the estimation of capacitance for carbon-based supercapacitors.

Carbon-based materials are broadly used as the active component of electric double layer capacitors (EDLCs) in energy storage systems with a high power density. Most of the reported computational studies have investigated the electrochemical properties under equilibrium conditions, limiting the direct and practical use of the results to design electrochemical energy systems. In the present study, for the first time, the experimental data from more than 300 published papers have been extracted and then analyzed through an optimized support vector machine (SVM) by a grey wolf optimization (GWO) algorithm to obtain a correlation between carbon-based structural features and EDLC performance. Several structural features, including calculated pore size, specific surface area, N-doping level, I D/I G ratio, and applied potential window were selected as the input variables to determine their impact on the respective capacitances. Sensitivity analysis, which has only been performed in this study for approximating the EDLC capacitance, indicated that the specific surface area of the carbon-based supercapacitors is of the greatest effect on the corresponding capacitance. The proposed SVM-GWO, with an R 2 value of 0.92, showed more accuracy than all the other proposed machine learning (ML) models employed for this purpose.

Microwave enhanced advanced oxidation treatment of fat, oil and grease (FOG) with organic co-substrates.

Mixtures of fats, oils and grease (FOG) either with dairy manure or with thickened waste secondary sludge (TWSS) were treated using microwave enhanced advanced oxidation process (MW-AOP). For both dairy manure and TWSS mixtures, the maximum increase in soluble COD (SCOD) resulted from the 1:1 mixture by total solids (TS) weight. In the TWSS mixtures, production of volatile fatty acid (VFA) increased with greater FOG content, while there was a decreasing production trend in VFA in dairy manure mixtures. Nutrients and metals were also released for all sets. The degradation followed peroxidation mechanism to produce lower molecular weight substrates such as short-chain fatty acids which would be less inhibitory to microbes. Nutrients and metals in the treated solution would sustain microbial growth in a biological system. FOG content for the mixtures in the MW-AOP treatment should be less than 75% by TS weight to prevent oxidation to CO2.

Insight into the Self-Insertion of a Protein Inside the Boron Nitride Nanotube.

Nanotubes have been considered as promising candidates for protein delivery purposes due to distinct features such as their large enough volume of cavity to encapsulate the protein, providing the sustain and target release. Moreover, possessing the properties of suitable cell viabilities, and biocompatibility on the wide range of cell lines as a result of structural stability, chemical inertness, and noncovalent wrapping ability, boron nitride nanotubes (BNNTs) have caught further attention as protein nanocarriers. However, to assess the encapsulation process of the protein into the BNNT, it is vital to comprehend the protein-BNNT interaction. In the present work, the self-insertion process of the protein SmtA, metallothionein, into the BNNT has been verified by means of the molecular dynamics (MD) simulation under NPT ensemble. It was revealed that the protein was self-inserted into the BNNT through the protein-BNNT van der Waals (vdW) interaction, which descended and reached the average value of -189.63 kcal·mol-1 at 15 ns of the simulation time. The potential mean force (PMF) profile of the encapsulated protein with increasing trend, which was obtained via the pulling process unraveled that the encapsulation of the protein into the BNNT cavity proceeded spontaneously and the self-inserted protein had reasonable stability. Moreover, due to the strong hydrogen interactions between the nitrogen atoms of BNNT and hydrogen atoms of SmtA, there was no evidence of an energy barrier in the vicinity of the BNNT entrance, which resulted in the rapid adsorption of this protein into the BNNT.

Waste-to-resources: Exploratory surface modification of sludge-based activated carbon by nitric acid for heavy metal adsorption.

Sewage sludge has the potential to be utilised as a sorbent for dissolved pollutant removal. This study investigated metal removal efficiency of carbonised sewage sludges obtained via pyrolysis at 500 °C: biochar/carbonised sludge (CS), ZnCl2-activated sludge-based active carbon (SBAC), and three SBACs modified by nitric acid at different concentration and temperature (MSBACs). Batch adsorption kinetic tests indicated that the Pb2+ adsorption equilibrated in <5 min. Efficiencies of these sludge-based sorbents for Pb2+ adsorption followed the order MSBAC > SBAC > CS. Metal leachabilities were low or negligible for the SBAC and MSBACs. A comparison of 5-min adsorption of the best-performing MSBAC with different sorbents indicates that performance followed the trend MSBAC > grundite (illite) > zeolite (clinoptilolite) > commercial activated carbon (CAC) > kaolinite > perlite. Furthermore, MSBAC achieved 98.9%, 42.6%, and 34.6% removal of Cu, Zn, and Al, respectively, from spiked natural acid rock drainage in <5 min. The modified sludge-based activated carbon is an effective and sustainable sorbent for removing metals from aqueous environments.

Degradation of 4-chlorophenol in aqueous solution photoinduced by Fe(III)-citrate complex.

The 4-chlorophenol (4-CP) degradation photoinduced by Fe(III)-citrate complex was investigated upon irradiation at 365 nm at different pHs (2.0, 3.0, 4.0 and 6.0). The best efficiency for 4-CP degradation in the presence of Fe(III)-citrate was at pH 3.0 with a value of quantum yield equal to 0.026. This effect is mainly attributed to speciation of Fe(III)-citrate complex which is very sensitive to the pH. Quantum yields of 4-CP degradation, Fe(III)-citrate disappearance and Fe(II) formation were carried out at wavelength 365 nm at different pHs (3.0 and 6.0). The effect of the pH is less pronounced for the quantum yields of 4-CP than for Fe(III)-citrate complex and Fe(II) quantum yields which are species involved in the initial photochemical process. The effect of oxygen, isopropanol and Fe(III)-citrate concentrations on the quantum yields of 4-CP degradation and also on kinetics of 4-CP disappearance was also studied. Indeed, 4-CP requires the presence of oxygen to be degraded. The disappearance of 4-CP was totally inhibited without oxygen dissolved in the solution. Oxygen is essential for the formation of oxidative species and, as a consequence, for the degradation of the pollutant.

Parahalogenated phenols accelerate the photochemical release of nitrogen oxides from frozen solutions containing nitrate.

The photolysis of nitrate anion (NO(3)(-)) contained in surface ice and snow can be a regionally significant source of gas-phase nitrogen oxides and affect the composition of the planetary boundary layer. In this study, the photochemical release of nitrogen oxides from frozen solutions containing NO(3)(-) in the presence of organic compounds was investigated. Gas-phase nitrogen oxides were quantified primarily by NO-O(3) chemiluminescence detection of NO and NO(y) (=NO + NO(2) + HONO + HNO(3) + ∑PAN + ∑AN ...) and cavity ring-down spectroscopy of NO(2) and total alkyl nitrates (∑AN). The photochemical production of gas-phase NO(y) was suppressed by the presence of formate, methanesulfonate, toluene, or phenol. In contrast, para-halogenated phenols (in the order of Cl > Br > F) promoted the conversion of NO(3)(-) to gas-phase NO(y), rationalized by acidification of the ice surface.

Photoinduced reduction of chromium(VI) by iron aminopolycarboxylate complex (FeNTA).

Chromium(VI) reduction photoinduced by iron(III) nitrilotriacetate (FeNTA) was investigated under monochromatic excitation. 313 nm was used as the irradiation wavelength in order to minimize the absorption of the light by chromium(VI): 91% of the photons were absorbed by FeNTA at pH = 7.0. Quantum yields of FeNTA and chromium(VI) disappearance and iron(II) formation were measured at pH 2.0, 4.0 and 7.0. In all the cases, chromium(VI) reduction follows first order kinetics with maximum efficiency at pH 2.0. The observed rate constant is proportional to FeNTA concentrations up to a maximum of 6.0 x 10(-4) mol L(-1). The effect of oxygen was also investigated. If there is no large pH effect and no effect of oxygen on the quantum yields of chromium(VI) and FeNTA disappearance, the pH strongly influences the nature of the reduced chromium species. At pH 2.0, only chromium(III) was detected, whereas at pH 4.0 and 7.0 no chromium(III) resulting from chromium(VI) reduction was observed. Chromium(V) is supposed to be formed and stabilized by the chelating groups of NTA or NTA photoproducts.

Impact of iron-complex (Fe(III)-NTA) on photoinduced degradation of 4-chlorophenol in aqueous solution.

In this research work, the photochemical impact of Fe(III)-nitrilotriacetic acid complex (FeNTA) on the fate of an organic pollutant (4-chlorophenol (4-CP)) was investigated in natural waters. The quantum yields of the photodecomposition of the FeNTA complex and of Fe(II) formation, by an intra-molecular photoredox process (the first stage of the reaction) are high. This photoredox reaction represents the first step of the process leading to 4-CP disappearance. Whereas oxygen does not affect FeNTA photodegradation, 4-CP depletion requires the presence of oxygen. The radical species HO and CO3*- responsible of the degradation were identified by ESR spectroscopy under irradiation. Two different wavelength-dependent mechanisms of 4-chlorophenol degradation are proposed. It clearly appears that under solar irradiation, iron organic complexes like FeNTA can play a significant role on the fate of the organic compounds present in natural waters.