Treatment of polychlorinated biphenyls in two surface soils using catalyzed H₂O₂ propagations

Two surface soils contaminated with polychlorinated biphenyls (PCBs) collected from Superfund sites in the New England region of the United States, Fletcher Paints and Merrimack Industrial Metals, were evaluated for field treatment at the bench level using catalyzed H₂O₂ propagations (CHP—modified Fenton’s reagent). The two soils were first evaluated for the potential for in situ treatment based on two criteria: (1) temperature (<40 °C after CHP reagent addition), and (2) hydrogen peroxide longevity (>24 h). In situ CHP remediation was more applicable to the Fletcher soil, while the Merrimack soil was better suited to ex situ treatment based on temperature increases and hydrogen peroxide lifetimes. Using the highest hydrogen peroxide concentrations appropriate for in situ treatment in each soil, PCB destruction was 94% in the Fletcher soil but only 48% in the Merrimack soil. However, 98% PCB destruction was achieved in the Merrimack soil using conditions more applicable to ex situ treatment (higher hydrogen peroxide concentrations with temperatures >40 °C). Analysis of degradation products by gas chromatography/mass spectroscopy showed no detectable chlorinated degradation products, suggesting that the products of PCB oxidation were rapidly dechlorinated and degraded. The results of this research document that the two PCB-contaminated soils studied can be effectively treated using aggressive CHP conditions, and that such a detailed bench study provides important information before implementing field treatment.     

Photoelectrocatalytic degradation of 4,4'-dibromobiphenyl in aqueous solution on TiO₂ and doped TiO₂ nanotube arrays

Polybrominated biphenyls have been widely used as flameretardants in textile and electronic industries, and additives in plastics. Over the past few decades, much attention has been given to polybrominated biphenyls in the environment and their effects on humans. In this paper, we studied on the degradation of 4,4′-dibromobiphenyl, a typical one of polybrominated biphenyls, through photoelectrocatalytic process with TiO₂, Zr/TiO₂ and Zr, N/TiO₂ nanotube arrays. The results showed that the photoelectrocatalytic process was more efficient than photocatalytic and electrolytic process alone. The results exhibited that the photoelectrocatalytic efficiency was significantly affected by the properties of the catalysts and bias potential, and the highest photoelectrocatalytic degradation rate was achieved with Zr, N/TiO₂ at 1 V and the order was Zr, N/TiO₂ > Zr/TiO₂ > TiO₂. The mechanism was also discussed by detecting the changes of pH value, bromine anion, total organic carbon and intermediates during the process.     

Photocatalytic decomposition on nano-TiO₂: destruction of chloroaromatic compounds

Photocatalysis is applied increasingly in addressing and solving environmental and energy-related problems. Especially the TiO₂-derived catalysts attract attention because of their catalytic efficiency, wide range of applications, ease in use, and low cost (it costs about 150 Yuan a kilogram in China). This review first describes the principles of photocatalytic destruction by semiconductors and then focuses on degradation rates and reaction mechanisms in a variety of photocatalytic uses of modified TiO₂. Finally, these concepts are illustrated by selected examples relating to the photocatalytic degradation of organic persistent pollutants, such as polychlorinated benzenes (PCBz), biphenyls (PCB) and dibenzo-p-dioxins and dibenzofurans (PCDD/Fs). And some approaches towards industrial application are analyzed.     

Chromate-reducing activity of Hansenula polymorpha recombinant cells over-producing flavocytochrome b₂

In spite of the great interest to studies of the biological roles of chromium, as well as the toxic influence of Cr(VI)-species on living organisms, the molecular mechanisms of chromate bioremediation remain vague. A reductive pathway resulting in formation of less toxic Cr(III)-species is suggested to be the most important among possible mechanisms for chromate biodetoxification. The yeast l-lactate:cytochrome c-oxidoreductase (flavocytochrome b(2), FC b(2)) has absolute specificity for l-lactate, yet is non-selective with respect to its electron acceptor. These properties allow us to consider the enzyme as a potential candidate for chromate reduction by living cells in the presence of l-lactate. A recombinant strain of thermotolerant, methylotrophic yeast Hansenula polymorpha with sixfold increased FC b(2) enzyme activity (up to 3μmolmin(-1)mg(-1) protein in cell-free extract) compared to the parental strain was used for approval our suggestion. The recombinant cells, stored in dried state, as well as living yeast cells were tested for chromate-reducing activity in vitro in the presence of l-lactate (as an electron donor for chromate reduction) and different low molecular weight, redox-active mediators facilitating electron transfer from the reduced form of the enzyme to chromate (as a final electron acceptor): dichlorophenolindophenol (DCPIP), Methylene blue, Meldola blue, and Nile blue. It was shown that the highest chromate-reducing activity of the cells was achieved in the presence of DCPIP. The ability of chromate to catch electrons from the reduced flavocytochrome b(2) was confirmed using purified enzyme immobilized on the surface of a platinum electrode. The increasing concentration of Cr(VI) resulted in a decrease of enzyme-mediated current generated on the electrode during l-lactate oxidation. The shift and drop in amplitude of the peak in the cyclic voltammogram are indicative of Cr(VI)-dependent competition between reaction of chromate with reduced FC b(2) and direct electron transfer from the enzyme to the electrode surface. The application of the chromate-reducing ability of FC b(2)-over-producing recombinant cells of H. polymorpha toward chromate bioremediation and the construction of cells-based biosensor for chromate monitoring in the environment are discussed.     

Superior photodecomposition of pyrene by metal ion-loaded TiO₂ catalyst under UV light irradiation

BACKGROUND: The photocatalytic degradation of pyrene under UV (125 W Hg-Arc, 10.4 mW/cm2) irradiation of TiO2 aqueous suspension has been found to be highly improved with the dissolved transition metal ions like Cu2+, Fe3+, Ag+, and Au3+, etc. As the reduction potential of these metals lies below the conduction band (CB) position (?0.1 eV) of TiO2, the photoexcited electron transfer occurs more readily and reduces electron–hole recombination rate. Therefore, it has a beneficial influence on the photocatalytic ability of TiO2 because of rapid Fermi energy equilibrium between the CB of TiO2 and its surface adsorbed metal ions. RESULTS AND DISCUSSION: The Fermi level is referred to as the electrochemical potential and plays an important role in the band theory of solids. When metal and semiconductor are in contact, electron migration from photoirradiated semiconductor to the deposited metal occurs at the interface until two Fermi levels equilibrate and enhanced the photocatalytic activity of semiconductor photocatalyst. Ni2+ having more negative reduction potential (?0.25 eV) than the CB of TiO2 imparts negligible co-catalytic activity to TiO2 photoreaction. It also revealed that loading of Au3+ ions displayed higher degradation rate of pyrene than Au photodeposition. Furthermore, when the amount of dissolved Fe+3 and Au3+ ions gradually increases from 0.1 to 2 wt.%, the pyrene photodecomposition rate also become faster.     

An urban boreal lake basin as a source of CO₂ and CH₄

Up to now, carbon gas fluxes from urban lakes in the boreal zone have seldom been studied. In summer 2005 we investigated fluxes from an urban boreal lake basin in southern Finland with long history of eutrophication and anoxia. Hypolimnetic CO₂ and CH₄ concentrations were high compared to other boreal lakes. During the open-water period, the lake basin acted as a source of CO₂ and CH₄ with fluxes of 2.10 mol m⁻² and 0.04 mol m⁻², respectively. Despite the high oxidation rate (83%), CH₄ flux was higher than in other lakes and CH₄ contributed 60% to Global Warming Potential. The ratio of carbon emission to accumulation was 4, i.e. emissions were an important route for carbon departure but less so than in rural lakes. Since the lake oxygen conditions affected nutrient availability, there was a positive feedback from hypolimnion to carbon uptake, which was reflected in gas concentrations.     

Redistribution of free tropospheric chemical species over West Africa: radicals (OH and HO₂), peroxide (H₂O₂) and acids (HNO₃ and H₂SO₄)

The purpose of this paper is to study the redistribution of chemical species (OH, HO₂, H₂O₂, HNO₃ and H₂SO₄) over West Africa, where the cloud cover is ubiquitously present, and where deep convection often develops. In this area, because of these cloud systems, chemical species are redistributed by the ascending and descending flow, or leached if they are soluble. So, we carry out a mesoscale study using the Regional Atmospheric Modelling System (RAMS) coupled to a code of gas and aqueous chemistry (RAMS_Chemistry). It takes into account all processes under mesh. We examine several cases following the period (November and July), with inputs emissions (anthropogenic, biogenic and biomass burning). The radicals OH and HO₂ are an indicator of possibilities for chemical activity. They characterize the oxidizing power of the atmosphere and are very strong oxidants. The acids HNO₃ and H₂SO₄ are interesting in their transformation into nitrates and sulfates in precipitation. In November, when photochemistry is active during an event of biomass burning, concentrations of chemical species are higher than those of November in the absence of biomass burning. The concentrations of nitric acid double and sulfuric acid increases 70 times. In addition, the concentrations are even lower in July if there is a deep convection. Compared to measures of the African Monsoon Multidisciplinary Analysis (AMMA), the results and observations of radicals OH and HO₂ are the same order of magnitude. Emissions from biomass burning increase the concentrations of acid and peroxide, and a deep convection cloud allows the solubility and the washing out of species, reducing their concentration. Rainfalls play a major role in solubility and washing out acids, peroxides and radicals in this region.     

Disruption of zebrafish (Danio rerio) reproduction upon chronic exposure to TiO₂ nanoparticles

As common engineered nanomaterials, TiO(2) nanoparticles (nTiO(2)) are usually perceived as non-toxic, and have already been widely used in many products and applications. Such a perception might have been shaped by some short-term studies that revealed no/low toxicity of nTiO(2) to cells and eco-relevant organisms. However, given the ultimate release of nTiO(2) into the aquatic environment, which can act as a sink for engineered nanoparticles, their long-term impact on the environment and human health is still a concern and deserves more research efforts. Here, for the first time, we demonstrate that chronic exposure of zebrafish to 0.1 mg L(-1) nTiO(2), can significantly impair zebrafish reproduction. For instance, there was a 29.5% reduction in the cumulative number of zebrafish eggs after 13 weeks of nTiO(2) exposure. Thus, we provided timely information on indicating a serious risk of reproductive impairment of environments contaminated with low levels of nTiO(2) on aquatic organisms, leading to alterations in population dynamics and aquatic ecosystem balance, and thus warrants a careful scrutiny on toxicity assessment of nTiO(2), especially their long-term impact.     

H₂S abatement in a biotrickling filter using iron(III) foam media

Airstreams polluted with H(2)S at inlet loads ranging from 2.4 to 40.9 g H(2)Sm(-3)h(-1) were treated in a biotrickling reactor packed with hematite bearing, open pore foam units, at Empty Bed Residence Times (EBRT) ranging from 20 to 60s over a period of 80 d, with almost complete removal of the pollutant from the startup of the system. The media had been seeded with sludge from a local water works facility, and removal efficiencies in excess of 80% were consistently observed along the operation of the reactor, with an average of 98%. Based on section performance, being a section one third of the bed length, observed elimination capacities (EC) reached up to 88.7 g H(2)Sm(-3)h(-)(1) and 72.0 g H(2)Sm(-3)h(-1) at section EBRT of 10 and 7s, respectively. The observed EC values compared much better than data reported on other packed bed reactors using biological iron oxidization to treat H(2)S airstreams indirectly, and so did it when comparing the EC per unit of specific area in a similar study using polyurethane (PU) foams. Further, and unlike PU packed biofilters, no compaction occurred due to the iron foam rigidity, which translated in much better observed gas phase pressure drop as opposed to other conventional biofilters. Denaturing gel gradient electrophoresis was performed on the biomass collected in the packing after the biofilter service, and it was found that though a multi bacterial colony was seeded in the system via the sludge, the only surviving genus was the iron oxidizing Alicyclobacillus spp.     

Soil nitrogen transformations under elevated atmospheric CO₂ and O₃ during the soybean growing season

We investigated the influence of elevated CO₂ and O₃ on soil N cycling within the soybean growing season and across soil environments (i.e., rhizosphere and bulk soil) at the Soybean Free Air Concentration Enrichment (SoyFACE) experiment in Illinois, USA. Elevated O₃ decreased soil mineral N likely through a reduction in plant material input and increased denitrification, which was evidenced by the greater abundance of the denitrifier gene nosZ. Elevated CO₂ did not alter the parameters evaluated and both elevated CO₂ and O₃ showed no interactive effects on nitrifier and denitrifier abundance, nor on total and mineral N concentrations. These results indicate that elevated CO₂ may have limited effects on N transformations in soybean agroecosystems. However, elevated O₃ can lead to a decrease in soil N availability in both bulk and rhizosphere soils, and this likely also affects ecosystem productivity by reducing the mineralization rates of plant-derived residues.     

Capability of novel ZnFe₂O₄ nanotube arrays for visible-light induced degradation of 4-chlorophenol

Highly ordered ZnFe₂O₄ nanotube arrays were successfully prepared by anodic aluminum oxide templates from sol-gel solution. The results from environmental scanning electron microscopy and X-ray photoemission spectroscopy indicated that the as-prepared samples were vertically aligned spinel ZnFe₂O₄ nanotube arrays, and the nanotubes were uniform along the axial direction with an average diameter of approximately 200 nm. The absorption edge of ZnFe₂O₄ nanotube arrays shifted to a higher energy in the UV-Vis absorption spectrum compared with that of ZnFe₂O₄ nanoparticles film. The synthesized ZnFe₂O₄ nanotube arrays exhibited excellent photocatalytic capability for degradation of 4-chlorophenol under visible-light irradiation. The main intermediate degradation species of 4-chlorophenol identified by liquid chromatography-mass technique were benzoquinone, hydroquinone, hydroxybenzoquinone and 2-peroxy-o-dihydroxybenzene. The degradation pathways of 4-chlorophenol under visible-light irradiation was derived and discussed by interpreting the observations of the intermediate species in the photocatalytic reactions.     

Oxidative stress, endothelial dysfunction and inflammatory response in rat heart to NO₂ inhalation exposure

Epidemiological studies suggest that NO₂ inhalation is associated with adverse effects on heart-related health, however, existing experimental data lack relevant evidences. In this study, a role for oxidative stress, endothelial dysfunction and inflammatory responses in the heart of rats treated with different concentrations of NO₂ (0, 5, 10 and 20 mg m⁻³) was investigated. Mild heart pathology occurred after 7-d exposure (6 h d⁻¹). Marked oxidative stress were induced as evaluated by reduction/induction of antioxidants (Cu/Zn-SOD, Mn-SOD and GPx) activity and increasing formation of MDA and PCO. Also, mRNA and protein biomarkers of vasoconstriction (ET-1, eNOS) and inflammation (TNF-α, IL-1β and ICAM-1) were up-regulated, and p53 mRNA expression, bax/bcl-2 ratio and the mean number of TUNEL-positive myocytes were increased as well. All the results implicate that NO₂ exerted injuries to mammals’ heart, and the damage mechanisms were possibly associated with oxidative stress, endothelial dysfunction and inflammation.     

Acute effects of Fe₂O₃, TiO₂, ZnO and CuO nanomaterials on Xenopus laevis

Metal oxide nanomaterials have exhibited toxicity to a variety of aquatic organisms, especially microbes and invertebrates. To date, few studies have evaluated the toxicity of metal oxide nanomaterials on aquatic vertebrates. Therefore, this study examined effects of ZnO, TiO₂, Fe₂O₃, and CuO nanomaterials (20-100 nm) on amphibians utilizing the Frog Embryo Teratogenesis Assay Xenopus (FETAX) protocol, a 96 h exposure with daily solution exchanges. Nanomaterials were dispersed in reconstituted moderately hard test medium. These exposures did not increase mortality in static renewal exposures containing up to 1000 mg L⁻¹ for TiO₂, Fe₂O₃, CuO, and ZnO, but did induce developmental abnormalities. Gastrointestinal, spinal, and other abnormalities were observed in CuO and ZnO nanomaterial exposures at concentrations as low as 3.16 mg L⁻¹ (ZnO). An EC₅₀ of 10.3 mg L⁻¹ ZnO was observed for total malformations. The minimum concentration to inhibit growth of tadpoles exposed to CuO or ZnO nanomaterials was 10 mg L⁻¹. The results indicate that select nanomaterials can negatively affect amphibians during development. Evaluation of nanomaterial exposure on vertebrate organisms are imperative to responsible production and introduction of nanomaterials in everyday products to ensure human and environmental safety.     

TiO₂ supported over SBA-15: an efficient photocatalyst for the pesticide degradation using solar light

Photocatalytic degradation and mineralization of pesticides are studied over TiO(2) supported mesoporous SBA-15 composite system using solar light. TiO(2) is immobilized over SBA-15 by solid sate dispersion method. The catalysts are characterized by XRD, surface area, UV-Vis diffused reflectance spectra, SEM and TEM. The detailed photocatalytic degradation studies are carried out over TiO(2), SBA-15 and different TiO(2) wt% supported SBA-15. The activity evaluation parameters such as catalyst amount, pH, and pollutant initial concentration are studied taking isoproturon as a model compound and established conditions for pesticide degradation. The optimum degradation is achieved over 10 wt% TiO(2)/SBA-15 within 30 min and the reaction is following pseudo-first order kinetics. The isoproturon mineralization is monitored with TOC reduction and it takes around 9h for disappearance. The commercial pesticide solutions containing imidacloprid and phosphamidon are also successfully degraded over these composites with the established conditions. The data indicates that 10 wt% TiO(2)/SBA-15 composite is an effective and highly active system for the pesticide degradations.     

TiO₂-based nanoparticles released in water from commercialized sunscreens in a life-cycle perspective: structures and quantities

This work investigates the physical-chemical evolution during artificial aging in water of four commercialized sunscreens containing TiO₂-based nanocomposites. Sunscreens were analyzed in terms of mineralogy and TiO₂ concentration. The residues formed after aging were characterized in size, shape, chemistry and surface properties. The results showed that a significant fraction of nano-TiO₂ residues was released from all sunscreens, despite their heterogeneous behaviors. A stable dispersion of submicronic aggregates of nanoparticles was generated, representing up to 38 w/w% of the amount of sunscreen, and containing up to 30% of the total nano-TiO₂ initially present in the creams. The stability of the dispersion was tested as a function of salt concentration, revealing that in seawater conditions, a major part of these nano-TiO₂ residues will aggregate and sediment. These results were put in perspective with consumption and life cycle of sunscreens to estimate the amount of nano-TiO₂ potentially released into AQUATIC environment.     

Photocatalytic degradation of gaseous toluene over Ag-doping TiO₂ nanotube powder prepared by anodization coupled with impregnation method

In this work, Ag-doping TiO₂ nanotubes were prepared and employed as the photocatalyst for the degradation of toluene. The TiO₂ nanotube powder was produced by the rapid-breakdown potentiostatic anodization of Ti foil in chloride-containing electrolytes, and then doped with Ag through an incipient wetness impregnation method. The samples were characterized by scanning electron microscope, high-resolution transmission electron microscopy, X-ray diffraction, surface photovoltage measurements, X-ray photoelectron spectroscopy and N₂ adsorption. The nanotubular TiO₂ photocatalysts showed an outer diameter of approximately 40 nm, fine mesoporous structure and high specific surface area. The photocatalytic activity of Ag-doping TiO₂ nanotube powder was evaluated through photooxidation of gaseous toluene. The results indicated that the degradation efficiency of toluene could get 98% after 4 h reaction using the Ag-doping TiO₂ nanotubes as the photocatalyst under UV light illumination, which was higher than that of the pure TiO₂ nanotubes, Ag-doping P25 or P25. Benzaldehyde species could be observed during the photocatalytic oxidation monitored by in situ FTIR, and the formed benzaldehyde intermediate during reaction would be partially oxidized into CO₂ and H₂O.     

Processes and factors controlling N₂O production in an intensively managed low carbon calcareous soil under sub-humid monsoon conditions

An automated system for continuous measurement of N₂O fluxes on an hourly basis was employed to study N₂O emissions in an intensively managed low carbon calcareous soil under sub-humid temperate monsoon conditions. N₂O emissions occurred mainly within two weeks of application of NH₄⁺-based fertilizer and total N₂O emissions in wheat (average 0.35 or 0.21 kg N ha⁻¹ season⁻¹) and maize (average 1.47 or 0.49 kg N ha⁻¹ season⁻¹) under conventional and optimum N fertilization (300 and 50-122 kg N ha⁻¹, respectively) were lower than previously reported from low frequency measurements. Results from closed static chamber showed that N₂O was produced mainly from nitrification of NH₄⁺-based fertilizer, with little denitrification occurring due to limited readily oxidizable carbon and low soil moisture despite consistently high soil nitrate-N concentrations. Significant reductions in N₂O emissions can be achieved by optimizing fertilizer N rates, using nitrification inhibitors, or changing from NH₄⁺- to NO₃^ˉ-based fertilizers.     

Aggregation and ecotoxicity of CeO₂ nanoparticles in synthetic and natural waters with variable pH, organic matter concentration and ionic strength

The influence of pH (6.0-9.0), natural organic matter (NOM) (0-10 mg C/L) and ionic strength (IS) (1.7-40 mM) on 14 nm CeO₂ NP aggregation and ecotoxicity towards the alga Pseudokirchneriella subcapitata was assessed following a central composite design. Mean NP aggregate sizes ranged between 200 and 10000 nm. Increasing pH and IS enhanced aggregation, while increasing NOM decreased mean aggregate sizes. The 48 h-E_rC20s ranged between 4.7 and 395.8 mg CeO₂/L. An equation for predicting the 48 h-E_rC20 (48 h-E_rC20 = −1626.4 × (pH) + 109.45 × (pH)² + 116.49 × ([NOM]) − 14.317 × (pH) × ([NOM]) + 6007.2) was developed. In a validation study with natural waters the predicted 48 h-E_rC20 was a factor 1.08-2.57 lower compared to the experimental values.     

Removal of Rhodamine B under visible irradiation in the presence of Fe⁰, H₂O₂, citrate and aeration at circumneutral pH

A new Vis-Fe⁰-H₂O₂-citrate-O₂ system comprising zero-valent iron, hydrogen peroxide, citrate anion and aeration at circumneutral pH under visible irradiation was studied. 21 μmol L⁻¹ of Rhodamine B (RhB) was chosen as the substrate to be tested. Experiments were conducted under conditions of 2.9 mmol L⁻¹ of H₂O₂, 12.6 g of Fe⁰ and 1.0 mmol L⁻¹ of citrate at pH 7.5. Results showed that, in 1 h reaction, 54% of RhB was removed with corresponding 26% of COD reduced. Meanwhile, the amount of released dissolved irons from Fe⁰ surface was found to be at a very low level as <5.4 μmol L⁻¹. Extinguishing tests with isopropanol suggested that RhB oxidation by hydroxyl radicals was the main process taken place in Vis-Fe⁰-H₂O₂-citrate-O₂ system, which accounted for 75% of substrate removal in 3 h reaction. Control and factor influencing experiments showed that the prohibitive extents of individual factor importance on RhB removal followed a decreasing order of Fe⁰ > H₂O₂ > citrate > Vis > O₂. This study showed an excellent system that could remove refractory organic compounds from water in laboratory researches, and also provided a good idea to reduce secondary contamination by dissolved irons in future investigations.     

Study on reaction kinetics and selective precipitation of Cu, Zn, Ni and Sn with H₂S in single-metal and multi-metal systems

Determination of reaction kinetics and selective precipitation of Cu, Zn, Ni and Sn with H(2)S in single-metal and multi-metal systems were studied to develop a process of metal recovery from plating wastewater. As samples, single-metal model wastewaters containing Cu, Sn, Zn or Ni, and multi-metal model wastewater containing Cu-Zn-Ni or Sn-Zn mixtures were used. In both single-metal and multi-metal systems, the pH value was precisely controlled at a value of 1.5 for CuS and SnS precipitation, 4.5 for ZnS precipitation and 6.5-7.0 for NiS precipitation. Subsequently, the sulfidation of Cu, Sn, Zn and Ni was evaluated. It was found that an amount of H(2)S equimolar to a given metal was sufficient to achieve almost complete precipitation of the particular metal. Further, the selectivity of metal precipitation was found to be higher than 95% in the Cu-Zn-Ni multi-metal system and higher than 91% in the Sn-Zn system. It was also found that the sulfidation reaction proceeded in accordance with Higbie's penetration theory and reaction rate constants and mass-transfer coefficients under various experimental conditions were determined. Finally, the reaction rate constants obtained in single-metal and multi-metal systems were found to be almost the same indicating that the precipitation of a particular metal was not significantly affected by the presence of other components.