Nanostructured metal oxides as adsorbents and photocatalysts

This research underlines the extensive application of nanostructured metal oxides in environmental systems such as hazardous waste remediation and water purification. This study tries to forge a new understanding of the complexity of adsorption and photocatalysis in the process of water treatment. Sodium niobate doped with a different amount of tantalum, was prepared via a hydrothermal reaction and was observed to be able to adsorb highly hazardous bivalent radioactive isotopes such as Sr2+ and Ra2+ions. This study facilitates the preparation of Nb-based adsorbents for efficiently removing toxic radioactive ions from contaminated water and also identifies the importance of understanding the influence of heterovalent substitution in microporous frameworks. Clay adsorbents were prepared via a two-step method to remove anionic and non-ionic herbicides from water. Firstly, layered beidellite clay was treated with acid in a hydrothermal process; secondly, common silane coupling agents, 3-chloro-propyl trimethoxysilane or triethoxy silane, were grafted onto the acid treated samples to prepare the adsorption materials. In order to isolate the effect of the clay surface, we compared the adsorption property of clay adsorbents with ƒ×-Al2O3 nanofibres grafted with the same functional groups. Thin alumina (£^-Al2O3) nanofibres were modified by the grafting of two organosilane agents 3-chloropropyltriethoxysilane and octyl triethoxysilane onto the surface, for the adsorptive removal of alachlor and imazaquin herbicides from water. The formation of organic groups during the functionalisation process established super hydrophobic sites along the surfaces and those non-polar regions of the surfaces were able to make close contact with the organic pollutants. A new structure of anatase crystals linked to clay fragments was synthesised by the reaction of TiOSO4 with laponite clay for the degradation of pesticides. Based on the Ti/clay ratio, these new catalysts showed a high degradation rate when compared with P25. Moreover, immobilized TiO2 on laponite clay fragments could be readily separated out from a slurry system after the photocatalytic reaction. Using a series of partial phase transition methods, an effective catalyst with fibril morphology was prepared for the degradation of different types of phenols and trace amount of herbicides from water. Both H-titanate and TiO2-(B) fibres coated with anatase nanocrystal were studied. When compared with a laponite clay photocatalyst, it was found that anatase dotted TiO2-(B) fibres prepared by a 45 h hydrothermal treatment followed by calcination were not only superior in performance in photocatalysis but could also be readily separated from a slurry system after photocatalytic reactions. This study has laid the foundation for the development of the ability to fabricate highly efficient nanostructured solids for the removal of radioactive ions and organic pollutants from contaminated water. These results now seem set to contribute to the development of advanced water purification devices in the future. These modified nanostructured materials with unusual properties have broadened their application range beyond their traditional use as adsorbents, to also encompass the storage of nuclear waste after concentrating from contaminated water.

Nitrate reduction over nanoscale zero-valent iron prepared by hydrogen reduction of goethite

Nitrate reduction with nanoscale zero-valent iron (NZVI) was reported as a potential technology to remove nitrate from nitrate-contaminated water. In this paper, nitrate reduction with NZVI prepared by hydrogen reduction of natural goethite (NZVI-N, -N represents natural goethite) and hydrothermal goethite (NZVI-H, -H represents hydrothermal goethite) was conducted. Besides, the effects of reaction time, nitrate concentration, iron-to-nitrate ratio on nitrate removal rate over NZVI-H and NZVI-N were investigated. To prove their excellent nitrate reduction capacities, NZVI-N and NZVI-H were compared with ordinary zero-valent iron (OZVI-N) through the static experiments. Based on all above investigations, the mechanism of nitrate reduction with NZVI-N was proposed. The result showed that reaction time, nitrate concentration, iron-to-nitrate ratio played an important role in nitrate reduction by NZVI-N and NZVI-H. Compared with OZVI, NZVI-N and NZVI-H showed little relationship with pH. And NZVI-N for nitrate composition offers a higher stability than NZVI-H because of the existence of Al-substitution. Furthermore, NZVI-N, prepared by hydrogen reduction of goethite, has higher activity for nitrate reduction and the products contain hydrogen, nitrogen, NH 4 +, a little nitrite, but no NOx, meanwhile NZVI-N was oxidized to Fe 2+. It is a relatively easy and cost-effective method for nitrate removal, so NZVI-N reducing nitrate has a great potential application in nitrate removal of groundwater. © 2012 Elsevier B.V.

Adsorption of the herbicide 2,4-D on organo-palygorskite

Among the clay minerals, montmorillonite is the most extensively studied material using as adsorbents, but palygorskite and its organically modified products have been least explored for their potential use in contaminated water remediation. In this study, an Australian palygorskite was modified with cationic surfactants octadecyl trimethylammonium bromide and dioctadecyl dimethylammonium bromide at different doses. A full structural characterization of prepared organo-palygorskite by X-ray diffraction, infrared spectroscopy, surface analysis and thermogravimetric analysis was performed. The morphological changes of palygorskite before and after modification were recorded using scanning electron microscopy, which showed the surfactant molecules can attach on the surface of rod-like crystals and thus can weaken the interactions between palygorskite single crystals. Real surfactants loadings on organo-palygorskites were also calculated based on thermogravimetric analysis. 1 CEC, 2 CEC octadecyl trimethylammonium bromide modified palygorskites, 1 CEC and 2 CEC dioctadecyl dimethylammonium bromide modified palygorskites absorbed as much as 12 mg/g, 42 mg/g, 9 mg/g and 25 mg/g of 2,4- dichlorophenoxyacetic acid respectively. This study has shown a potential on organo-palygorskites for organic herbicide adsorption especially anionic ones from waste water. In addition, equilibration time effects and the Langmuir and Freundlich models fitting were also investigated in details.

Application of organo-beidellites for the adsorption of atrazine

The surfaces of natural beidellite were modified with cationic surfactant octadecyl trimethylammonium bromide at different concentrations. The organo-beidellite adsorbent materials were then used for the removal of atrazine with the goal of investigating the mechanism for the adsorption of organic triazine herbicide from contaminated water. Changes on the surfaces and structure of beidellite were characterised by X-ray diffraction (XRD), thermogravimetric analysis (TGA), Fourier transform infrared (FTIR) spectroscopy, scanning electron microscopy (SEM) and BET surface analysis. Kinetics of the adsorption studies were also carried out which show that the adsorption capacity of the organoclays increases with increasing surfactant concentration up until 1.0 CEC surfactant loading, after which the adsorption capacity greatly decreases. TG analysis reveals that although the 2.0 CEC sample has the greatest percentage of surfactant by mass, most of it is present on external sites. The 0.5 CEC sample has the highest proportion of surfactant exchanged into the internal active sites and the 1.0 CEC sample accounts for the highest adsorption capacity. The goodness of fit of the pseudo-second order kinetic confirms that chemical adsorption, rather than physical adsorption, controls the adsorption rate of atrazine.

Abatement of aqueous anionic contaminants by thermo-responsive nanocomposites: (Poly(N-isopropylacrylamide))-co-silylanized Magnesium/Aluminun layered double hydroxides

A series of novel thermo-responsive composite sorbents, were prepared by free-radical co-polymerization of N-isopropylacrylamide (NIPAm) and the silylanized Mg/Al layered double hydroxides (SiLDHs), named as PNIPAm-co-SiLDHs. For keeping the high affinity of Mg/Al layered double hydroxides towards anions, the layered structure of LDHs was assumed to be reserved in PNIPAm-co-SiLDHs by the silanization of the wet LDH plates as evidenced by the X-ray powder diffraction. The sorption capacity of PNIPAm-co-SiLDH (13.5 mg/g) for Orange-II from water was found to be seven times higher than that of PNIPAm (2.0 mg/g), and the sorption capacities of arsenate onto PNIPAm-co-SiLDH are also greater than that onto PNIPAm, for both As(III) and As(V). These sorption results suggest that reserved LDH structure played a significant role in enhancing the sorption capacities. NO3− intercalated LDHs composite showed the stronger sorption capacity for Orange-II than that of CO32−. After sorption, the PNIPAm-co-SiLDH may be removed from water because of its gel-like nature, and may be easily regenerated contributing to the accelerated desorption of anionic contaminants from PNIPAm-co-SiLDHs by the unique phase-transfer feature through slightly heating (to 40 °C). These recyclable and regeneratable properties of thermo-responsive nanocomposites facilitate its potential application in the in-situ remediation of organic and inorganic anions from contaminated water.

Atomic Layer Deposition and Photocatalytic Properties of Titanium Dioxide Thin Films

Photocatalytic TiO2 thin films can be highly useful in many environments and applications. They can be used as self-cleaning coatings on top of glass, tiles and steel to reduce the amount of fouling on these surfaces. Photocatalytic TiO2 surfaces have antimicrobial properties making them potentially useful in hospitals, bathrooms and many other places where microbes may cause problems. TiO2 photocatalysts can also be used to clean contaminated water and air. Photocatalytic oxidation and reduction reactions proceed on TiO2 surfaces under irradiation of UV light meaning that sunlight and even normal indoor lighting can be utilized. In order to improve the photocatalytic properties of TiO2 materials even further, various modification methods have been explored. Doping with elements such as nitrogen, sulfur and fluorine, and preparation of different kinds of composites are typical approaches that have been employed. Photocatalytic TiO2 nanotubes and other nanostructures are gaining interest as well. Atomic Layer Deposition (ALD) is a chemical gas phase thin film deposition method with strong roots in Finland. This unique modification of the common Chemical Vapor Deposition (CVD) method is based on alternate supply of precursor vapors to the substrate which forces the film growth reactions to proceed only on the surface in a highly controlled manner. ALD gives easy and accurate film thickness control, excellent large area uniformity and unparalleled conformality on complex shaped substrates. These characteristics have recently led to several breakthroughs in microelectronics, nanotechnology and many other areas. In this work, the utilization of ALD to prepare photocatalytic TiO2 thin films was studied in detail. Undoped as well as nitrogen, sulfur and fluorine doped TiO2 thin films were prepared and thoroughly characterized. ALD prepared undoped TiO2 films were shown to exhibit good photocatalytic activities. Of the studied dopants, sulfur and fluorine were identified as much better choices than nitrogen. Nanostructured TiO2 photocatalysts were prepared through template directed deposition on various complex shaped substrates by exploiting the good qualities of ALD. A clear enhancement in the photocatalytic activity was achieved with these nanostructures. Several new ALD processes were also developed in this work. TiO2 processes based on two new titanium precursors, Ti(OMe)4 and TiF4, were shown to exhibit saturative ALD-type of growth when water was used as the other precursor. In addition, TiS2 thin films were prepared for the first time by ALD using TiCl4 and H2S as precursors. Ti1-xNbxOy and Ti1-xTaxOy transparent conducting oxide films were prepared successfully by ALD and post-deposition annealing. Highly unusual, explosive crystallization behaviour occurred in these mixed oxides which resulted in anatase crystals with lateral dimensions over 1000 times the film thickness.

Cyclodextrin functionalized magnetic iron oxide nanocrystals: a host-carrier for magnetic separation of non-polar molecules and arsenic from aqueous media

A single-step magnetic separation procedure that can remove both organic pollutants and arsenic from contaminated water is clearly a desirable goal. Here we show that water dispersible magnetite nanoparticles prepared by anchoring carboxymethyl-beta-cyclodextrin (CMCD) cavities to the surface of magnetic nanoparticles are suitable host carriers for such a process. Monodisperse, 10 nm, spherical magnetite, Fe3O4, nanocrystals were prepared by the thermal decomposition of FeOOH. Trace amounts of antiferromagnet, FeO, present in the particles provides an exchange bias field that results in a high superparamagnetic blocking temperature and appreciable magnetization values that facilitate easy separation of the nanocrystals from aqueous dispersions on application of modest magnetic fields. We show here that small molecules like naphthalene and naphthol can be removed from aqueous media by forming inclusion complexes with the anchored cavities of the CMCD-Fe3O4 nanocrystals followed by separation of the nanocrystals by application of a magnetic field. The adsorption properties of the iron oxide surface towards As ions are unaffected by the CMCD capping so it too can be simultaneously removed in the separation process. The CMCD-Fe3O4 nanocrystals provide a versatile platform for magnetic separation with potential applications in water remediation.

Toxicidade aguda sobre Daphnia similis decorrente de contaminação aquática recente e antiga por gasolina, etanol e suas misturas: simulações em escala de bancada.

A contaminação de ambientes aquáticos decorrente de acidentes com gasolina, álcool combustível e misturas binárias representa um risco crescente, tendo em vista as projeções do setor para os próximos 50 anos. O objetivo do presente estudo foi avaliar a toxicidade aguda da Gasolina C, Gasolina P e álcool combustível isoladamente e em misturas binárias, assim como de suas respectivas Frações Solúveis em Água (FSA) e Frações Dispersas em Água (FDA) sobre Daphnia similis. O estudo ainda incluiu a avaliação da toxicidade aguda remanescente na matriz água de uma contaminação antiga (intemperismo) com a Gasolina C. Paralelamente, foram conduzidos ensaios de toxicidade aguda com amostras ambientais (água subterrânea, superficial e elutriato a partir de sedimentos) de uma área alagada com histórico de contaminação antiga. O cultivo e os ensaios com D. similis foram de acordo com a NBR 12.713 (2009). Tanto a gasolina C quanto a P foram extremamente tóxicas para os organismos, apresentando valores médios de CE50% em 48 h de 0,00113% e 0,058% respectivamente. As diferenças entre os resultados obtidos com a Gasolina C e aqueles obtidos com suas frações FSA e FDA foram significativas (p < 0,05), sendo que não houve diferença significativa entre a toxicidade aguda da FSA e da FDA (p < 0,05). Os resultados obtidos com os ensaios com Gasolina P e FDA não apresentaram diferenças significativas entre si (p < 0,05), mas, foram significativamente diferentes daqueles obtidos com FSA (p < 0,05). Os resultados dos ensaios de toxicidade aguda com misturas binárias sugeriram efeito menos que aditivo (antagonismo). Os resultados da simulação de uma contaminação antiga demonstraram redução acentuada da toxicidade para D. similis ao longo de apenas 28 dias. Entretanto, com relação aos ensaios com as amostras ambientais da área com histórico de contaminação, apesar da ausência ou baixa toxicidade nas amostras de água superficial (sugerindo intemperismo), toxicidade alta foi observada em amostras de água subterrânea e no elutriato de sedimentos, sugerindo condições de adsorção aos sedimentos com alto teor de argila e/ou aprisionamento dos compostos em zona saturada.

Phytoremediation of triazophos by Canna indica Linn. in a hydroponic system

The phytoremediation of triazophos (O, O-diethyl-O-(1-phenyl-1, 2, 4-triazole-3-base) sulfur phosphate, TAP) by Canna indica Linn. in a hydroponic system was studied. After 21 d of exposure, the removal kinetic constant (K) of TAP was 0.0229-0.0339 d(-1) and the removal percentage of TAP was 41-55% in the plant system and the K and removal percentage of TAP were about 0.002 d(-1) and 1%, respectively, in darkness and disinfected control. However, the K and removal percentage of TAP were 0.006 d(-1) and approximately 11%, respectively, in the treatment with eluate from the media of constructed wetland. The contribution of plant to the remediation of TAP was 74% and C. indica played the most important role in the hydroponic system. Under the stress of TAP and without inorganic phosphorus nutrient, the activity of phosphatase in the plant system increased and phytodegradation was observed. The production and release of phosphatase is seen as the key mechanism for C. indica to degrade TAP. C. indica, which showed the potential of phytoremediation of TAP, and is commonly used in constructed wetland, so the technique of phytoremediation of TAP from contaminated water can be developed with the combination of constructed wetland.

A comparison between ultraviolet disinfection and copper alginate beads within a vortex bioreactor for the deactivation of bacteria in simulated waste streams with high levels of colour, humic acid and suspended solids

We show in this study that the combination of a swirl flow reactor and an antimicrobial agent (in this case copper alginate beads) is a promising technique for the remediation of contaminated water in waste streams recalcitrant to UV-C treatment. This is demonstrated by comparing the viability of both common and UV-C resistant organisms in operating conditions where UV-C proves ineffective - notably high levels of solids and compounds which deflect UV-C. The swirl flow reactor is easy to construct from commonly available plumbing parts and may prove a versatile and powerful tool in waste water treatment in developing countries.

Presence of arsenic in agricultural products from arsenic-endemic areas and strategies to reduce arsenic intake in rural villages

About 100 million rural people in Asia are exposed to arsenic (As)-polluted drinking water and agricultural products. Total and inorganic arsenic (t-As and i-As) intake mainly depend on the quality of drinking and cooking waters, and amounts of seafood and rice consumed. The main problems occur in countries with poor water quality where the population depends on rice for their diet, and their t-As and i-As intake is high as a result of growing and cooking rice in contaminated water. Workable solutions to remove As from water and breeding rice cultivars with low As accumulation are being sought. In the meantime, simple recommendations for processing and cooking foods will help to reduce As intake. For instance, cooking using high volumes of As-free water may be a cheap way of reducing As exposure in rural populations. It is necessary to consider the effects of cooking and processing on t-As and i-As to obtain a realistic view of the risks associated with intake of As in Asendemic areas.

Haematite in Lateritic Soils Aids Groundwater Disinfection

Microbiologically contaminated water severely impacts public health in low-income countries, where treated water supplies are often inaccessible to much of the population. Groundwater represents a water source that commonly has better microbiological quality than surface water. A 2-month intensive flow and quality monitoring programme of a spring in a densely settled, unsewered parish of Kampala, Uganda, revealed the persistent presence of high chloride and nitrate concentrations that reflect intense loading of sewage in the spring’s catchment. Conversely, thermotolerant coliform bacteria counts in spring water samples remained very low outside of periods of intense rainfall. Laboratory investigations of mechanisms responsible for this behavior, achieved by injecting a pulse of H40/1 bacteriophage tracer into a column packed with locally derived granular laterite, resulted in near-total tracer adsorption. X-ray diffraction (XRD) analysis showed the laterite to consist predominantly of quartz and kaolinite, with minor amounts (<5%) of haematite. Batch studies comparing laterite adsorption capacity with a soil having comparable mineralogy, but with amorphous iron oxide rather than haematite, showed the laterite to have a significantly greater capacity to adsorb bacteriophage. Batch study results using pure haematite confirmed that its occurrence in laterite contributes substantially to micro-organism attenuation observed and serves to protect underlying groundwater.

SULFADIMIDINE IN DRINKING TROUGHS AT BACON FACTORIES

Water troughs in the lairages of three bacon factories were examined. Pigs were observed drinking from the troughs, some of which were contaminated with faeces. Some of the troughs contained detectable concentrations of sulphadimidine, and the highest concentration recorded was 17 mu-g/ml. Pigs which drank this contaminated water before slaughter could contain tissue residues of sulphadimidine above the permitted concentration.

Uptake kinetics of arsenic species in rice plants

Arsenic (As) finds its way into soils used for rice (Oryza sativa) cultivation through polluted irrigation water, and through historic contamination with As-based pesticides. As is known to be present as a number of chemical species in such soils, so we wished to investigate how these species were accumulated by rice. As species found in soil solution from a greenhouse experiment where rice was irrigated with arsenate contaminated water were arsenite, arsenate, dimethylarsinic acid, and monomethylarsonic acid. The short-term uptake kinetics for these four As species were determined in 7-d-old excised rice roots. High-affinity uptake (0-0.0532 mM) for arsenite and arsenate with eight rice varieties, covering two growing seasons, rice var. Boro (dry season) and rice var. Aman (wet season), showed that uptake of both arsenite and arsenate by Boro varieties was less than that of Aman varieties. Arsenite uptake was active, and was taken up at approximately the same rate as arsenate. Greater uptake of arsenite, compared with arsenate, was found at higher substrate concentration (low-affinity uptake system). Competitive inhibition of uptake with phosphate showed that arsenite and arsenate were taken up by different uptake systems because arsenate uptake was strongly suppressed in the presence of phosphate, whereas arsenite transport was not affected by phosphate. At a slow rate, there was a hyperbolic uptake of monomethylarsonic acid, and limited uptake of dimethylarsinic acid.

Effect of cooking method and rice type on arsenic concentration in cooked rice and the estimation of arsenic dietary intake in a rural village in West Bengal, India

Arsenic (As) contamination of rice plants can result in high total As concentrations (t-As) in cooked rice, especially if As-contaminated water is used for cooking. This study examines two variables: (1) the cooking method (water volume and inclusion of a washing step); and (2) the rice type (atab and boiled). Cooking water and raw atab and boiled rice contained 40 g As l-1 and 185 and 315 g As kg-1, respectively. In general, all cooking methods increased t-As from the levels in raw rice; however, raw boiled rice decreased its t-As by 12.7% when cooked by the traditional method, but increased by 15.9% or 23.5% when cooked by the intermediate or contemporary methods, respectively. Based on the best possible scenario (the traditional cooking method leading to the lowest level of contamination, and the atab rice type with the lowest As content), t-As daily intake was estimated to be 328 g, which was twice the tolerable daily intake of 150 g.