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ABSTRACT: The extensive use of nano-TiO2 in industry has led to growing concerns about its potential environmental impacts. However, negligible toxicity is commonly reported under insufficient illumination and artificial solution conditions in the literature, which rarely includes discussion of the regulating role of environmental factors. Herein, we report the results of a high-throughput screening assay to evaluate the acute cytotoxicity of six commercial nano-TiO2 materials to Escherichia coli (E. coli) using Lake Michigan water as a model for aquatic surface environments. In particular, we investigate the specific effects of illumination wavelength and natural organic matter (NOM) content. Under simulated solar irradiation, four anatase-based nano-TiO2 materials including Pigment White 6 exhibit significant bacterial toxicity (2 h-IC50 value of 2.7-9.1 mg/L), with toxicity thresholds much lower than previously reported. Negligible toxicity is caused either by pure-phase rutile or under dark condition. Formation of nano-TiO2 aggregates well beyond nano-scale does not eliminate their toxic effect, but photoactivity dominates over the primary size and extent of aggregation in determining the acute cytotoxicity of nano-TiO2. Under visible light irradiation (UVA&B blocked) the antibacterial activity of nano-TiO2 is essentially erased, whereas removing only UVB wavelengths slightly mitigates the toxicity. Suwannee River fulvic acid, acting as a natural dispersant, reverses the extent of nano-TiO2 aggregation, but also reduces its bacterial cytotoxicity. These results demonstrate that despite particle aggregation, the short-term cytotoxicity of nano-TiO2 is predominantly attributed to its phototoxicity, emphasizing the importance of illumination conditions in toxicological screening of photoactive nanomaterials. In the natural aquatic environment, however, this acute toxicity may be mitigated by the attenuation of UV irradiation and increased NOM concentration in the water column.
Water Research 02/2013; · 4.86 Impact Factor
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ABSTRACT: Within aquatic ecosystems, periphytic biofilms can be hot spots of denitrification, and previous work has suggested that algal taxa within periphyton can influence the species composition and activity of resident denitrifying bacteria. This study tested the hypothesis that algal species composition within biofilms influences the structure and function of associated denitrifying bacterial communities through the composition of organic exudates. A mixed population of bacteria was incubated with organic carbon isolated from one of seven algal species or from one of two streams that differed in anthropogenic inputs. Pyrolysis-gas chromatography-mass spectrometry (Py-GC/MS) revealed differences in the organic composition of algal exudates and stream waters, which, in turn, selected for distinct bacterial communities. Organic carbon source had a significant effect on potential denitrification rates (DNP) of the communities, with organics isolated from a stream with high anthropogenic inputs resulting in a bacterial community with the highest DNP. There was no correlation between DNP and numbers of denitrifiers (based on nirS copy numbers), but there was a strong relationship between the species composition of denitrifier communities (as indicated by tag pyrosequencing of nosZ genes) and DNP. Specifically, the relative abundance of Pseudomonas stutzeri-like nosZ sequences across treatments correlated significantly with DNP, and bacterial communities incubated with organic carbon from the stream with high anthropogenic inputs had the highest relative abundance of P. stutzeri-like nosZ sequences. These results demonstrate a significant relationship between bacterial community composition and function and provide evidence of the potential impacts of anthropogenic inputs on the structure and function of stream microbial communities.
Microbial Ecology 07/2012; 64(4):881-92. · 2.91 Impact Factor
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ABSTRACT: Due to arid conditions, population growth, and anthropogenic impacts from agricultural and urban development, wastewater effluent makes up an increasingly large percentage of surface water supplies promoting concerns about the potential ecological and human health effects associated with the organic quality of surface waters receiving treated wastewater discharge. Anthropogenic inputs alter the quality and quantity of organic carbon and also affect the ability of aquatic ecosystems to retain or transform carbon and other nutrients. In this paper, we use pyrolysis-GC/MS (Py-GC/MS) as a tool to examine whether the dissolved organic carbon (DOC) in suburban streams influenced by anthropogenic inputs displays an organic signature that is structurally different from natural organic material (NOM). Py-GC/MS was not only able to differentiate among stream sites that received discharge from upstream wastewater treatment plants and those that did not, but also distinguished stream sites influenced significantly by storm water. Distinct organic signatures were evident in stream waters with upstream wastewater treatment plant discharges regardless of the distance from effluent discharge, indicative of the persistent nature of effluent-derived organic material (EfOM). The pyrolysis fragments of 3-methyl-pyridine, 2-methyl-pyridine, pyrrole, and acetamide were identified as indicators of EfOM, supporting previous research that has suggested that protein and aminosugar derivitives are possible wastewater markers. Furthermore, pyrolysis fragments associated with soil polycarboxylic acids correlated highly with stream sites having the least anthropogenic influences.
Water Research 02/2012; 46(8):2515-24. · 4.86 Impact Factor
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ABSTRACT: The interaction of acetaldehyde with TiO(2) nanorods has been studied under low pressures (acetaldehyde partial pressure range 10(-4)-10(-8) Torr) using chemical ionization mass spectrometry (CIMS). We quantitatively separate irreversible adsorption, reversible adsorption, and an uptake of acetaldehyde assigned to a thermally activated surface reaction. We find that, at room temperature and 1.2 Torr total pressure, 2.1 ± 0.4 molecules/nm(2) adsorb irreversibly, but this value exhibits a sharp decrease as the analyte partial pressure is lowered below 4 × 10(-4) Torr, regardless of exposure time. The number of reversible binding sites at saturation amounts to 0.09 ± 0.02 molecules/nm(2) with a free energy of adsorption of 43.8 ± 0.2 kJ/mol. We complement our measurements with FTIR spectroscopy and identify the thermal dark reaction as a combination of an aldol condensation and an oxidative adsorption that converts acetaldehyde to acetate or formate and CO, at a measured combined initial rate of 7 ± 1 × 10(-4) molecules/nm(2) s. By characterizing binding to different types of sites under dark conditions in the absence of oxygen and gas phase water, we set the stage to analyze site-specific photoefficiencies involved in the light-assisted mineralization of acetaldehyde to CO(2).
Langmuir 12/2011; 27(24):14842-8. · 4.19 Impact Factor
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ABSTRACT: With its unique electronic and optical properties, graphene is proposed to functionalize and tailor titania photocatalysts for improved reactivity. The two major solution-based pathways for producing graphene, oxidation-reduction and solvent exfoliation, result in nanoplatelets with different defect densities. Herein, we show that nanocomposites based on the less defective solvent-exfoliated graphene exhibit a significantly larger enhancement in CO(2) photoreduction, especially under visible light. This counterintuitive result is attributed to their superior electrical mobility, which facilitates the diffusion of photoexcited electrons to reactive sites.
Nano Letters 06/2011; 11(7):2865-70. · 13.20 Impact Factor
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ABSTRACT: We compared the development of microalgal and bacterial-denitrifier communities within biofilms over 28 days in a restored-prairie stream (RP) and a stream receiving treated wastewater effluent (DER). Inorganic nutrient concentrations were an order of magnitude greater in DER, and stream waters differed in the quality of dissolved organics (characterized via pyrolysis-GC/MS). Biofilm biomass and the densities of algae and bacteria increased over time in both systems; however, algal and denitrifier community composition and the patterns of development differed between systems. Specifically, algal and denitrifier taxonomic composition stabilized more quickly in DER than RP, whereas the rates of algal and denitrifier succession were more closely coupled in RP than DER. We hypothesize that, under unenriched conditions, successional changes in algal assemblages influence bacterial denitrifiers due to their dependence on algal exudates, while under enriched conditions, this relationship is decoupled. Between-system differences in organic signatures supported this, as RP biofilms contained more labile, aliphatic compounds than DER. In addition, potential denitrification rates (DNP) were negatively correlated with the percentage of aromatic compounds within the biofilm organic signatures, suggesting a significant relationship between algal exudate composition and denitrification. These results are significant because anthropogenic factors that affect biofilm community composition may alter their capacity to perform critical ecosystem services.
FEMS Microbiology Ecology 05/2011; 77(3):477-92. · 3.41 Impact Factor
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ABSTRACT: Using the electron paramagnetic resonance technique, we have elucidated the multiple roles of water and carbonates in the overall photocatalytic reduction of carbon dioxide to methane over titania nanoparticles. The formation of H atoms (reduction product) and (•)OH radicals (oxidation product) from water, and CO(3)(-) radical anions (oxidation product) from carbonates, was detected in CO(2)-saturated titania aqueous dispersion under UV illumination. Additionally, methoxyl, (•)OCH(3), and methyl, (•)CH(3), radicals were identified as reaction intermediates. The two-electron, one-proton reaction proposed as an initial step in the reduction of CO(2) on the surface of TiO(2) is supported by the results of first-principles calculations.
Journal of the American Chemical Society 02/2011; 133(11):3964-71. · 9.91 Impact Factor
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ABSTRACT: Photoreactive and visible light responsive nonstoichiometric mixed-phase titania was prepared by reactive direct current magnetron sputtering. Trace amounts of nitrogen were added for process stabilization without being incorporated into the films. Based on the CO <sub>2</sub> photoreduction tests and structural and optical characterization, the influence of the trace nitrogen on the sputtered nonstoichiometric TiO <sub>2</sub> was studied and was compared to nitrogen-doped titania.
Journal of Vacuum Science & Technology A Vacuum Surfaces and Films 08/2009; · 1.25 Impact Factor
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ABSTRACT: ANDROGENIC-ANABOLIC STEROIDS (AAS), AND SIMILAR BODY IMAGE DRUGS, CONTINUE TO RECEIVE POPULAR MEDIA COVERAGE. ASIDE FROM SPORT, THE USE OF AAS IN MAINSTREAM SOCIETY HAS BECOME POPULAR FOR AESTHETIC PURPOSES, PARTICULARLY AMONG ADOLESCENTS AND YOUNG ADULTS. THIS ARTICLE WILL PROVIDE THE PRACTICING STRENGTH AND CONDITIONING AND HEALTH PROFESSIONAL WITH INSIGHT AND EFFECTIVE STRATEGIES FOR ADDRESSING AAS AND OTHER PERFORMANCE-ENHANCING DRUG USE IN ADOLESCENTS AND YOUNG ADULTS. THE TRANSTHEORETICAL MODEL IS USED AS A FRAMEWORK FOR DEVISING SPECIFIC STRATEGIES TO ADDRESS THIS GROWING PUBLIC HEALTH ISSUE.
Strength and conditioning journal 01/2009; 31(1):13-22. · 0.51 Impact Factor
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ABSTRACT: THIS ARTICLE PROVIDES THE STRENGTH AND CONDITIONING AND HEALTH PROFESSIONAL INSIGHT INTO THE POSSIBLE RATIONALE FOR USE OF ANDROGENIC-ANABOLIC STEROIDS AND OTHER PERFORMANCE-ENHANCING DRUGS USING THE TRANSTHEORETICAL MODEL. THIS MODEL IS OFTEN USED TO PROMOTE HEALTH-ADDITIVE BEHAVIORS, SUCH AS EXERCISE ADHERENCE. THE MODEL CAN BE USED TO EXAMINE HOW NEGATIVE CHOICES AND BEHAVIORS ARE MADE. THE MODEL CAN BE USED BY THE STRENGTH AND CONDITIONING PROFESSIONAL AND HEALTH PROFESSIONAL TO EXPLAIN THE SOCIOCULTURAL FACTORS FOR USING ANDROGENIC-ANABOLIC STEROIDS AND OTHER SUBSTANCES IN YOUNGER AGE CATEGORIES.
Strength and conditioning journal 11/2008; 30(6):47-54. · 0.51 Impact Factor
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ABSTRACT: We report that SWCNTs substantially improve the uniformity and coverage of TiO2 coatings on porous ZrO2 ceramic membrane filters. The ZrO2 filters were dip coated with 100 nm anatase TiO2, TiO2/SWCNT composites, a TiO2+SWCNT mixture, and a TiO2/MWCNT composite at pH 3, 5, and 8. Whereas the TiO2+SWCNT mixture and the TiO2/MWCNT composite promote better coverage and less clumping than TiO2 alone, the TiO2/SWCNT composite forms a complete uniform coating without cracking at pH 5 ( approximately 100% coverage). A combination of chemical and electrostatic effects between TiO2 and SWCNTs forming the composite as well as between the composite and the ZrO2 surface explains these observations.
Langmuir 08/2008; 24(14):7072-5. · 4.19 Impact Factor
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ABSTRACT: We conducted a field survey of periphyton cultivated on benthic mesh installations in freshwater aquatic systems, including two constructed wetlands and a pond, and also studied periphyton grown on a benthic mesh in laboratory mesocosms. The objectives of this study were to (1) determine if periphyton cultivated on benthic mesh denitrifies at higher rates than the underlying sediments and (2) determine if denitrification rates within periphyton vary with characteristics such as algal and bacterial community structure and biomass. We measured denitrification potential rates of field and laboratory periphyton by the acetylene inhibition method. We characterized algal community composition by algal identification and bacterial community composition by terminal restriction fragment length polymorphisms. Periphyton collected on benthic mesh from our field sites denitrified at significantly higher rates than the underlying sediments, regardless of sampling site or season. Results from both our field survey and laboratory studies indicated a significant, positive correlation between diatom presence and denitrification rate. In our laboratory studies, we found that periphyton with the highest diatom abundance showed the highest denitrification rates as well as a distinct bacterial community composition. These results suggest a synergistic relationship between diatoms and denitrifying bacteria that warrants further study.
Microbial Ecology 08/2008; 56(1):140-52. · 2.91 Impact Factor
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ABSTRACT: Electron-hole recombination limits the efficiency of TiO2 photocatalysis. We have investigated the efficacy with which anatase/carbon nanotube (CNT) composite materials reduce charge recombination and enhance reactivity. We synthesized nanostructured assemblies composed of different proportions of anatase (5 or 100 nm) and either single-or multi-walled CNTs. The composites were prepared using a simple low temperature process in which CNTs and anatase nanoparticles were dispersed in water, dehydrated at 80 degrees C, and dried at 104 degrees C. The structures of the various TiO2/CNT composites were characterized by scanning electron microscopy (SEM) and their function was tested by phenol oxidation. Charge recombination was compared by measuring the photoluminescence spectra of select composites. We found that a nanostructured composite assembled from the 100 nm anatase and single-walled CNTs (SWCNTs) exhibited enhanced and selective photocatalytic oxidation of phenol in comparison to both pure anatase and Degussa P25. A mechanism for the enhanced reactivity is proposed in which electrons are shuttled from TiO2 particles to the SWCNTs as a result of an optimal TiO2/ CNT arrangement that stabilizes charge separation and reduces charge recombination. In addition, the SWCNT assembly provides better catalyst-support (dispersal and connection) than multi-walled CNTs.
Environmental Science and Technology 08/2008; 42(13):4952-7. · 5.23 Impact Factor
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ABSTRACT: Highly photoactive, tetrahedral Ti4+ sites can be created, other than in zeolite cavities and on silica substrate, in mixed-phase TiO2 nanocomposites. The tetrahedral Ti4+ species was shown to be an intermediate formed during the thermally driven phase transformation from anatase to rutile.
Journal of the American Chemical Society 05/2008; 130(16):5402-3. · 9.91 Impact Factor
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ABSTRACT: The effects of substratum geometry and overlying velocity on nitrate use by periphyton were assessed. Periphyton was cultivated at an average current velocity of 0.5 cm s(-1) in laboratory mesocosms (120 cm long, 60 cm wide) on polyethylene nets of three different geometries, "1-lay er", "3-layer", and "bedform" structures, overlaying a thin bed of sand. Bulk nitrate use was then measured as the reduction of nitrate concentration in the overlying water under average velocities of 0.005, 0.05, and 0.5 cm s(-1). Periphyton structural characteristics were quantified as algal/bacterial biomass, algal species composition, and bacterial densities. Accrual of microbial biomass increased monotonically with increasing benthic net surface area, with upper sections of structures supporting the highest biomass. Maximum rates of nitrate removal were measured in the bedform geometry at intermediate velocity (173 mg NO3-N m(-2) d(-1)), and the lowest was measured with 1-layer geometry at the fastest velocity (11 mg NO3-N m(-2) d(-1)). Oxygen microprofiles within biofilms demonstrated that hydrodynamic conditions and benthic structure both play a key role in the regulation of microbial processing of nitrate delivered from the water column by promotion of denitrification in downstream sections of bedform substrata. Interactions between hydrodynamic conditions and substratum geometry are expected to regulate microbial activity in all surficial natural and engineered environments and must be parameterized to forecast long-term average biochemical transformation rates in rivers and other dynamic aquatic systems.
Environmental Science and Technology 01/2008; 41(23):8142-8. · 5.23 Impact Factor
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ABSTRACT: Mixed-phase titanium dioxide nanocrystals with varying phase composition were prepared by a low-temperature solvothermal process. We have re-examined the effect of hydrochloric acid on the formation of rutile phase and found that the proportion of the rutile phase in synthesized mixed-phase materials did not increase monotonically with increasing acidity. Rather, there was an optimum HCl/Ti molar ratio for rutile formation when titanium tetra-isopropoxide was used as the titanium precursor. At high HCl/Ti ratios, Cl- and H2O may act as charge-shielding agents, inhibiting the rutile formation during the solvothermal process. A low H2O/Ti molar ratio was necessary for preparing anatase−rutile composites, because the formation of photocatalytically inactive brookite phase was favored at relatively high H2O/Ti molar ratios. In addition, we found the solvothermal processing to be a possible approach to control interparticle connection. Mixed-phase TiO2 nanocrystals synthesized at relatively high H2O/Ti molar ratios possessed abundant surface hydroxyl groups and tended to form micrometer-sized aggregates. We suggest that hydrogen bonding can be utilized to bring TiO2 nanocrystals together, creating solid−solid interfaces upon calcination, thereby potentially facilitating interparticle charge transfer in photocatalytic processes.
02/2007;
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ABSTRACT: A traditional and popular Japanese house decorating lime tile, commercially available “Limix”, was used to photodecompose the formaldehyde after coating the tile with a titania sol, which solves the problem of sick-building syndrome. A total of five kinds of lime tile samples with titania sol coating and without coating were examined by using a flow-type photoreactor based on the JIS standard to test their photocatalytic activities. The photocatalytic mechanism in the coated lime tile was also analyzed by Electron Paramagnetic Resonance Spectroscopy (EPR). The results show that a high removal efficiency of formaldehyde was achieved when using the lime tile combined with commercially available zeolite compared to the lime tile immobilized titania photocatalyst. The EPR spectrum indicates that oxygen centered radicals and surface trapped holes are present in the titania sol, but it is much different from the spectrum observed in the pure anatase and Degussa P25 titania. It means that there are different characteristics among these systems on the photocatalysis mechanism.
Journal of Advanced Oxidation Technologies 12/2006; 10(1):11-16. · 0.81 Impact Factor
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ABSTRACT: In this study, the chemical reactivity with chlorine as measured by disinfection by-product formation potential (DBPFP) is compared among samples of a wastewater effluent and surface waters. Water samples that had higher anthropogenic impacts were found to have higher overall DBPFP due primarily to higher dissolve organic carbon (DOC) concentrations. Effluent-derived organic matter (EfOM), however, was found to be less reactive with chlorine on a per DOC concentration basis. Yet, EfOM had higher proportions of brominated DBP, which may be associated with greater health risks. In this research, pyrolysis-GC/MS was used to establish relationship between structural features of DOC and DBPFP. We show that there is a critical set of pyrolysis fragments that separates the waters based on the degree of anthropogenic influence. Even though no single chemical marker was found to be indicative of the formation potentials of different classes of DBP, combinations of chemical fragments were found to be associated with the formation potentials of total trihalomethane (THM), brominated THM, total haloacetic acid (HAA), and brominated HAA for this set of samples. In contrast to previous work, the phenolic signature of these samples was negatively correlated to DBPFP, whereas strong relationships were found between DBPFP and the organic nitrogen and halogenated signatures.
Water Research 04/2005; 39(6):1025-36. · 4.86 Impact Factor
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ABSTRACT: In potable water reuse, treated wastewater becomes part of the drinking water supply. An important question associated with this practice is whether or not the organic quality of the treated wastewater is chemically different from that of non-human impacted water. This question was addressed in a case study of indirect potable water reuse where the organic matrix of the South Platte River was analyzed upstream and downstream of the discharge of treated wastewater effluent using conventional water quality parameters combined with pyrolysis-GC/MS. Effluent-derived organic material (EfOM) was found to be more aliphatic and had higher organic nitrogen and halogen content compared to organic material derived from "natural" (non-anthropogenic) sources (NOM). Seasonal changes that resulted from the change in the contributions of aquatic and terrestrial sources were not observed in EfOM; but they were strongly observed in NOM under the control of natural processes. Using principal component and factor analyses, the pyrolysis fragments of phenol, alkyl-phenols, and acetic acid were identified as the seasonal indicators for the NOM set of samples. In contrast, benzaldehyde, benzonitrile, chlorobutanoic acid, furancarboxaldehyde, and methylfurancarboxaldehyde were identified as the indicators for wastewater inputs for the EfOM set of samples. Overall, the results from conventional water quality parameters and pyrolysis-GC/MS revealed that: (1) EfOM bears a chemical signature distinct from NOM and (2) under the conditions of this study, EfOM discharged to the South Platte River persisted and controlled organic quality at downstream points.
Water Research 04/2005; 39(6):1154-64. · 4.86 Impact Factor
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ABSTRACT: Charge migration between electron trapping sites within the mixed-phase titania photocatalyst Degussa P25 has been studied. In addition to previously described lattice electron trapping sites on both anatase and rutile phases, surface electron trapping sites and an anatase-rutile interface trapping site specific to Degussa P25 are identified. The relationship between these sites and recombination with surface hole trapping sites is also determined. It is experimentally shown that upon band-gap illumination holes appear at the surface and preferentially recombine with electrons in surface trapping sites. These findings indicate that in mixed-phase TiO2, such as Degussa P25, photogenerated holes are trapped exclusively on the particle surface, while photogenerated electrons are trapped within the nanoparticle lattice. Recombination reactions are dominated by surface reactions that follow charge migration. These findings indicate that, in mixed-phase TiO(2), such as Degussa P25, a random flight mechanism of recombination predominates. Such knowledge simplifies the mechanistic mathematical models used for process design and points the way for improving future oxidative titania catalysts.
The Journal of Physical Chemistry B 02/2005; 109(2):977-80. · 3.70 Impact Factor
