Dionysios D. Dionysiou

The use of zero-valent iron for groundwater remediation and wastewater treatment: A review

Recent industrial and urban activities have led to elevated concentrations of a wide range of contaminants in groundwater and wastewater, which affect the health of millions of people worldwide. In recent years, the use of zero-valent iron (ZVI) for the treatment of toxic contaminants in groundwater and wastewater has received wide attention and encouraging treatment efficiencies have been documented. This paper gives an overview of the recent advances of ZVI and progress obtained during the groundwater remediation and wastewater treatment utilizing ZVI (including nanoscale zero-valent iron (nZVI)) for the removal of: (a) chlorinated organic compounds, (b) nitroaromatic compounds, (c) arsenic, (d) heavy metals, (e) nitrate, (f) dyes, and (g) phenol. Reaction mechanisms and removal efficiencies were studied and evaluated. It was found that ZVI materials with wide availability have appreciable removal efficiency for several types of contaminants. Concerning ZVI for future research, some suggestions are proposed and conclusions have been drawn.

New Insights into the Mechanism of Visible Light Photocatalysis

In recent years, the area of developing visible-light-active photocatalysts based on titanium dioxide has been enormously investigated due to its wide range of applications in energy and environment related fields. Various strategies have been designed to efficiently utilize the solar radiation and to enhance the efficiency of photocatalytic processes. Building on the fundamental strategies to improve the visible light activity of TiO2-based photocatalysts, this Perspective aims to give an insight into many contemporary developments in the field of visible-light-active photocatalysis. Various examples of advanced TiO2 composites have been discussed in relation to their visible light induced photoconversion efficiency, dynamics of electron-hole separation, and decomposition of organic and inorganic pollutants, which suggest the critical need for further development of these types of materials for energy conversion and environmental remediation purposes.

Size-tunable hydrothermal synthesis of SnS2 nanocrystals with high performance in visible light-driven photocatalytic reduction of aqueous Cr(VI).

SnS(2) nanocrystals with adjustable sizes were synthesized via a hydrothermal method from the aqueous solution of common and inexpensive SnCl(4)·5H(2)O, thioacetamide and citric acid, simply by varying the reaction temperature and reaction time. The structures, Brunauer-Emmett-Teller (BET) specific surface areas and optical properties of the resultant SnS(2) nanocrystals were characterized by X-ray diffraction, transmission electron microscopy, N(2) adsorption/desorption isotherms, and UV-vis diffuse reflectance spectra. Besides, their photocatalytic properties were tested for the reduction of aqueous Cr(VI) under visible light (λ > 420 nm) irradiation. It was found that the photocatalytic activities of SnS(2) nanocrystals in aqueous suspension depended on their synthesis conditions. The product synthesized under suitable hydrothermal conditions (for example, at 150 °C for 12 h) not only showed high visible light-driven photocatalytic activity in the reduction of aqueous Cr(VI), but also showed good photocatalytic stability. Our photocatalytic results suggested that SnS(2) nanocrystals are a promising photocatalyst in the efficient utilization of solar energy for the treatment of Cr(VI)-containing wastewater.

Effect of inorganic, synthetic and naturally occurring chelating agents on Fe(II) mediated advanced oxidation of chlorophenols

This study examines the feasibility and application of Advanced Oxidation Technologies (AOTs) for the treatment of chlorophenols that are included in US EPA priority pollutant list. A novel class of sulfate/hydroxyl radical-based homogeneous AOTs (Fe(II)/PS, Fe(II)/PMS, Fe(II)/H2O2) was successfully tested for the degradation of series of chlorophenols (4-CP, 2,4-CP, 2,4,6-CP, 2,3,4,5-CP). The major objective of the present study was to evaluate the effectiveness of three representative chelating agents (citrate, ethylenediaminedisuccinate (EDDS), and pyrophosphate) on Fe(II)-mediated activation of three common peroxide (peroxymonosulfate (PMS), persulfate (PS), and hydrogen peroxide (H2O2)) at neutral pH conditions. Short term (4 h) and long term (7 days) experiments were conducted to evaluate the kinetics and longevity of different oxidative systems for 4-chlorophenol degradation. Results showed that each of the iron-chelating agent couple was superior in activating a particular oxidant and consequently for 4-CP degradation. In case of Fe(II)/PMS system, the inorganic chelating agent pyrophosphate showed effective activation of PMS whereas very fast dissociation of PMS was recorded in the case of EDDS without any apparent 4-CP degradation. In Fe(II)/H2O2 system, EDDS was proven to be the most effective whereas pyrophosphate showed negligible activation of H2O2. Fe(II)/Citrate system showed moderate activation of all three oxidants. PMS was found to be the most universal oxidant, which was activated by all three iron-chelating agent systems and Fe(II)/Citrate was the most universal chelating agent system, which was able to activate all three oxidants to a certain extent.

High-Performance Visible-Light-Driven SnS2/SnO2 Nanocomposite Photocatalyst Prepared via In situ Hydrothermal Oxidation of SnS2 Nanoparticles

SnS₂/SnO₂ nanocomposites with tunable SnO₂ contents were prepared via in situ hydrothermal oxidation of SnS₂ nanoparticles in 0.375-4.5 mass% H₂O₂ aqueous solutions at 180 °C for 0-12 h. The structure, composition and optical properties of the as-prepared SnS₂/SnO₂ nanocomposites were characterized by X-ray diffraction, transmission electron microscopy, high-resolution transmission electron microscopy, Brunauer-Emmett-Teller (BET) surface area analysis, energy-dispersive X-ray spectroscopy, X-ray photoelectron spectroscopy, and UV-vis diffuse reflectance spectra. Furthermore, their photocatalytic properties were tested for the degradation of methyl orange in water under visible light (λ > 420 nm) irradiation. It was found that the as-prepared SnS₂/SnO₂ nanocomposites with suitable SnO₂ content not only demonstrated superior photocatalytic activity to both SnS₂ nanoparticles and physically mixed SnS₂/SnO₂ composite nanoparticles, but also had remarkable photocatalytic stability. The tight attachment of SnO₂ nanoparticles to SnS₂ nanoparticles, which can facilitate interfacial electron transfer and reduce the self-agglomeration of two components, was considered to play an important role in achieving the high photocatalytic performances exhibited by the as-prepared SnS₂/SnO₂ nanocomposites.

Intermediates and Reaction Pathways from the Degradation of Microcystin-LR with Sulfate Radicals

Degradation of the cyanotoxin microcystin-LR (m/z 995.5) using sulfate radical-based advanced oxidation technologies (AOTs) and identification of reaction intermediates formed during treatment were investigated in this study. To the best of our knowledge this is the first study on the degradation and identification of reaction intermediates for any cyanotoxin with SO(4)(•-). Tandem mass spectrometry designated the formation of nine (as m/z) reaction intermediates with four of them (m/z 1011.5, 1027.5, 1029.5, and 1045.5) having multiple peaks in the TIC chromatogram. New peaks that were not observed with hydroxyl radical formed during photocatalytic oxidation (PCO) have been detected such as m/z 1045.5. The initially formed intermediates involved the oxidation of the unsaturated bonds of MC-LR especially the diene bonds located on the chain of the Adda amino acid. Subsequent intermediates implicated the oxidative cleavage of small functional groups (i.e., -COOH), up to the complete removal of the Adda chain. The electrophilic character of SO(4)(•-) is proven by the multihydroxylation of the aromatic ring. Toward the end of treatment, simultaneous oxidation of the Adda chain and the cyclic structure occurred without the formation of linear products.

Efficient removal of microcystin-LR by UV-C/H2O2 in synthetic and natural water samples

The destruction of the commonly found cyanobacterial toxin, microcystin-LR (MC-LR), in surface waters by UV-C/H(2)O(2) advanced oxidation process (AOP) was studied. Experiments were carried out in a bench scale photochemical apparatus with low pressure mercury vapor germicidal lamps emitting at 253.7 nm. The degradation of MC-LR was a function of UV fluence. A 93.9% removal with an initial MC-LR concentration of 1 μM was achieved with a UV fluence of 80 mJ/cm(2) and an initial H(2)O(2) concentration of 882 μM. When increasing the concentration of MC-LR only, the UV fluence-based pseudo-first order reaction rate constant generally decreased, which was probably due to the competition between by-products and MC-LR for hydroxyl radicals. An increase in H(2)O(2) concentration led to higher removal efficiency; however, the effect of HO scavenging by H(2)O(2) became significant for high H(2)O(2) concentrations. The impact of water quality parameters, such as pH, alkalinity and the presence of natural organic matter (NOM), was also studied. Field water samples from Lake Erie, Michigan and St. Johns River, Florida were employed to evaluate the potential application of this process for the degradation of MC-LR. Results showed that the presence of both alkalinity (as 89.6-117.8 mg CaCO(3)/L) and NOM (as ∼2 to ∼9.5 mg/L TOC) contributed to a significant decrease in the destruction rate of MC-LR. However, a final concentration of MC-LR bellow the guideline value of 1 μg/L was still achievable under current experimental conditions when an initial MC-LR concentration of 2.5 μg/L was spiked into those real water samples.

Cr(VI) Adsorption and Reduction by Humic Acid Coated on Magnetite

Easily separable humic acid coated magnetite (HA-Fe3O4) nanoparticles are employed for effective adsorption and reduction of toxic Cr(VI) to nontoxic Cr(III). The adsorption and reduction of Cr(VI) is effective under acidic, neutral, and basic pH conditions. The chromium adsorption nicely fits the Langmuir isotherm model, and the removal of Cr(VI) from aqueous media by HA-Fe3O4 particles follows pseudo-second-order kinetics. Characterization of the Cr-loaded HA-Fe3O4 materials by X-ray absorption near edge structure spectroscopy (XANES) indicates Cr(VI) was reduced to Cr(III) while the valence state of the iron core is unchanged. Fe K-edge extended X-ray absorption fine structure spectroscopy (EXAFS) and X-ray diffraction measurements also indicate no detectable transformation of the Fe3O4 core occurs during Cr(VI) adsorption and reduction. Thus, suggesting HA on the surface of HA-Fe3O4 is responsible for the reduction of Cr(VI) to Cr(III). The functional groups associated with HA act as ligands leading to the Cr(III) complex via a coupled reduction-complexation mechanism. Cr K-edge EXAFS demonstrates the Cr(III) in the Cr-loaded HA-Fe3O4 materials has six neighboring oxygen atoms likely in an octahedral geometry with average bond lengths of 1.98 Å. These results demonstrate that easily separable HA-Fe3O4 particles have promising potential for removal and detoxification of Cr(VI) in aqueous media.

Dissolved effluent organic matter: Characteristics and potential implications in wastewater treatment and reuse applications

Wastewater reuse is currently considered globally as the most critical element of sustainable water management. The dissolved effluent organic matter (dEfOM) present in biologically treated urban wastewater, consists of a heterogeneous mixture of refractory organic compounds with diverse structures and varying origin, including dissolved natural organic matter, soluble microbial products, endocrine disrupting compounds, pharmaceuticals and personal care products residues, disinfection by-products, metabolites/transformation products and others, which can reach the aquatic environment through discharge and reuse applications. dEfOM constitutes the major fraction of the effluent organic matter (EfOM) and due to its chemical complexity, it is necessary to utilize a battery of complementary techniques to adequately describe its structural and functional character. dEfOM has been shown to exhibit contrasting effects towards various aquatic organisms. It decreases metal uptake, thus potentially reducing their bioavailability to exposed organisms. On the other hand, dEfOM can be adsorbed on cell membranes inducing toxic effects. This review paper evaluates the performance of various advanced treatment processes (i.e., membrane filtration and separation processes, activated carbon adsorption, ion-exchange resin process, and advanced chemical oxidation processes) in removing dEfOM from wastewater effluents. In general, the literature findings reveal that dEfOM removal by advanced treatment processes depends on the type and the amount of organic compounds present in the aqueous matrix, as well as the operational parameters and the removal mechanisms taking place during the application of each treatment technology.

Titania powder modified sol-gel process for photocatalytic applications

Thick films of TiO2 were prepared on glass and stainless steel substrates using an alkoxide sol-gel process modified by addition of Degussa P-25 powder. The prepared films were characterized by SEM, EDS, XRD and other methods. The TiO2 films obtained from the powder modified sol were compared to films obtained from the alkoxide sol-gel without modification. The films obtained from the modified sol-gel were about ten times thicker for a single dip coating/heat treatment cycle than the films obtained from the sol without powder addition. The prepared thick films were smooth and free of macrocracking, fracture or flaking. The grain size of these films was uniform and in the range 100–150 nm and the films were a mixture of anatase and rutile TiO2. The films obtained from the powder modified sol on the stainless steel substrate were also much harder compared to the films obtained from sols without modification and displayed excellent adhesion to the substrate.