Manoranjan Sahu

Role of Surface Area, Primary Particle Size, and Crystal Phase on Titanium Dioxide Nanoparticle Dispersion Properties

Characterizing nanoparticle dispersions and understanding the effect of parameters that alter dispersion properties are important for both environmental applications and toxicity investigations. The role of particle surface area, primary particle size, and crystal phase on TiO2 nanoparticle dispersion properties is reported. Hydrodynamic size, zeta potential, and isoelectric point (IEP) of ten laboratory synthesized TiO2 samples, and one commercial Degussa TiO2 sample (P25) dispersed in different solutions were characterized. Solution ionic strength and pH affect titania dispersion properties. The effect of monovalent (NaCl) and divalent (MgCl2) inert electrolytes on dispersion properties was quantified through their contribution to ionic strength. Increasing titania particle surface area resulted in a decrease in solution pH. At fixed pH, increasing the particle surface area enhanced the collision frequency between particles and led to a higher degree of agglomeration. In addition to the synthesis method, TiO2 isoelectric point was found to be dependent on particle size. As anatase TiO2 primary particle size increased from 6 nm to 104 nm, its IEP decreased from 6.0 to 3.8 that also results in changes in dispersion zeta potential and hydrodynamic size. In contrast to particle size, TiO2 nanoparticle IEP was found to be insensitive to particle crystal structure.

Single-step processing of copper-doped titania nanomaterials in a flame aerosol reactor.

Synthesis and characterization of long wavelength visible-light absorption Cu-doped TiO2 nanomaterials with well-controlled properties such as size, composition, morphology, and crystal phase have been demonstrated in a single-step flame aerosol reactor. This has been feasible by a detailed understanding of the formation and growth of nanoparticles in the high-temperature flame region. The important process parameters controlled were: molar feed ratios of precursors, temperature, and residence time in the high-temperature flame region. The ability to vary the crystal phase of the doped nanomaterials while keeping the primary particle size constant has been demonstrated. Results indicate that increasing the copper dopant concentration promotes an anatase to rutile phase transformation, decreased crystalline nature and primary particle size, and better suspension stability. Annealing the Cu-doped TiO2 nanoparticles increased the crystalline nature and changed the morphology from spherical to hexagonal structure. Measurements indicate a band gap narrowing by 0.8 eV (2.51 eV) was achieved at 15-wt.% copper dopant concentration compared to pristine TiO2 (3.31 eV) synthesized under the same flame conditions. The change in the crystal phase, size, and band gap is attributed to replacement of titanium atoms by copper atoms in the TiO2 crystal.

Assessing the Relevance of in vitro Studies in Nanotoxicology by Examining Correlations between in vitro and in vivo Data

There is an urgent need for in vitro screening assays to evaluate nanoparticle (NP) toxicity. However, the relevance of in vitro assays is still disputable. We administered doses of TiO(2) NPs of different sizes to alveolar epithelial cells in vitro and the same NPs by intratracheal instillation in rats in vivo to examine the correlation between in vitro and in vivo responses. The correlations were based on toxicity rankings of NPs after adopting NP surface area as dose metric, and response per unit surface area as response metric. Sizes of the anatase TiO(2) NPs ranged from 3 to 100 nm. A cell-free assay for measuring reactive oxygen species (ROS) was used, and lactate dehydrogenase (LDH) release, and protein oxidation induction were the in vitro cellular assays using a rat lung Type I epithelial cell line (R3/1) following 24 h incubation. The in vivo endpoint was number of PMNs in bronchoalveolar lavage fluid (BALF) after exposure of rats to the NPs via intratracheal instillation. Slope analyses of the dose response curves shows that the in vivo and in vitro responses were well correlated. We conclude that using the approach of steepest slope analysis offers a superior method to correlate in vitro with in vivo results of NP toxicity and for ranking their toxic potency.

Chemical compositions and source identification of PM2.5 aerosols for estimation of a diesel source surrogate

Exposure to traffic-related pollution during childhood has been associated with asthma exacerbation, and asthma incidence. The objective of the Cincinnati Childhood Allergy and Air Pollution Study (CCAAPS) is to determine if the development of allergic and respiratory disease is associated with exposure to diesel engine exhaust particles. A detailed receptor model analyses was undertaken by applying positive matrix factorization (PMF) and UNMIX receptor models to two PM₂.₅ data sets: one consisting of two carbon fractions and the other of eight temperature-resolved carbon fractions. Based on the source profiles resolved from the analyses, markers of traffic-related air pollution were estimated: the elemental carbon attributed to traffic (ECAT) and elemental carbon attributed to diesel vehicle emission (ECAD). Application of UNMIX to the two data sets generated four source factors: combustion related sulfate, traffic, metal processing and soil/crustal. The PMF application generated six source factors derived from analyzing two carbon fractions and seven factors from temperature-resolved eight carbon fractions. The source factors (with source contribution estimates by mass concentrations in parentheses) are: combustion sulfate (46.8%), vegetative burning (15.8%), secondary sulfate (12.9%), diesel vehicle emission (10.9%), metal processing (7.5%), gasoline vehicle emission (5.6%) and soil/crustal (0.7%). Diesel and gasoline vehicle emission sources were separated using eight temperature-resolved organic and elemental carbon fractions. Application of PMF to both datasets also differentiated the sulfate rich source from the vegetative burning source, which are combined in a single factor by UNMIX modeling. Calculated ECAT and ECAD values at different locations indicated that traffic source impacts depend on factors such as traffic volumes, meteorological parameters, and the mode of vehicle operation apart from the proximity of the sites to highways. The difference in ECAT and ECAD, however, was less than one standard deviation. Thus, a cost benefit consideration should be used when deciding on the benefits of an eight or two carbon approach.

Evaluation of mass and surface area concentration of particle emissions and development of emissions indices for cookstoves in rural India.

Mass-based dose parameters (for example, PM(2.5)) are most often used to characterize cookstove particulate matter emissions. Particle surface area deposition in the tracheobronchial (TB) and alveolar (A) regions of the human lung is also an important metric with respect to health effects, though very little research has investigated this dose parameter for cookstove emissions. Field sampling of cookstove emissions was performed in two regions of rural India, wherein PM(2.5), particulate surface area concentration in both TB and A regions, and carbon monoxide (CO) were measured in 120 households and two roadside restaurants. Novel indices were developed and used to compare the emissions and efficiency of several types of household and commercial cookstoves, as well as to compare mass-based (PM(2.5)) and surface area-based measurements of particle concentration. The correlation between PM(2.5) and surface area concentration was low to moderate: Pearsons correlation coefficient (R) for PM(2.5) vs surface area concentration in TB region is 0.38 and for PM(2.5) vs surface area concentration in A region is 0.47, indicating that PM(2.5) is not a sufficient proxy for particle surface area concentration. The indices will also help communicate results of cookstove studies to decision makers more easily.

Comparison of Measured Particle Lung-Deposited Surface Area Concentrations by an Aerotrak 9000 Using Size Distribution Measurements for a Range of Combustion Aerosols

Surface area in addition to mass concentration is increasingly being emphasized as an important metric representing potential adverse health effects from exposure to inhaled particles. Lung-deposited surface area (SA) concentrations for a variety of aerosols: coal, biomass, cigarette, incense, candle, and TiO2 were measured using an AeroTrak 9000 (TSI Incorporated) and compared with those calculated from number size distributions from a scanning mobility particle sizer (SMPS). Three methodologies to compute the SA concentrations using the International Commission on Radiological Protections (ICRP) Lung Deposition model and an SMPS were compared. The first method calculated the SA from SMPS size distributions, while the second method used lognormal size distribution functions. A third method generated a closed-form equation using the method of moments. All calculated SMPS SA data against which the measured SA data were compared were generated using the first method only; however, the SA concentrations calculated from each of the three methods demonstrated strong correlations with each other. Overall, results between measured and calculated lung-deposited SA indicated strong positive linear associations (R 2 0.78 - >0.99), moderately dependent on the type of aerosol. In all cases, the measured SA concentrations slightly underestimated those calculated from the SMPS data, with the exception of coal combustion particles. Although some dependency on aerosol material exists, the instrument measuring lung-deposited SA demonstrated consistent reliability across a range of concentrations for a range of materials. For optimal results however, applying a correction factor (CF) before taking the instrument to the field is recommended. Copyright 2013 American Association for Aerosol Research

Social, Economic, and Resource Predictors of Variability in Household Air Pollution from Cookstove Emissions

We examine if social and economic factors, fuelwood availability, market and media access are associated with owning a modified stove and variation in household emissions from biomass combustion, a significant environmental and health concern in rural India. We analyze cross-sectional household socio-economic data, and PM2.5 and particulate surface area concentration in household emissions from cookstoves (n = 100). This data set combines household social and economic variables with particle emissions indexes associated with the household stove. The data are from the Foundation for Ecological Society, India, from a field study of household emissions. In our analysis, we find that less access to ready and free fuelwood and higher wealth are associated with owning a replacement/modified stove. We also find that additional kitchen ventilation is associated with a 12% reduction in particulate emissions concentration (p<0.05), after we account for the type of stove used. We did not find a significant association between replacement/modified stove on household emissions when controlling for additional ventilation. Higher wealth and education are associated with having additional ventilation. Social caste, market and media access did not have any effect on the presence of replacement or modified stoves or additional ventilation. While the data available to us does not allow an examination of direct health outcomes from emissions variations, adverse environmental and health impacts of toxic household emissions are well established elsewhere in the literature. The value of this study is in its further examination of the role of social and economic factors and available fuelwood from commons in type of stove use, and additional ventilation, and their effect on household emissions. These associations are important since the two direct routes to improving household air quality among the poor are stove type and better ventilation.

Role of dopant concentration, crystal phase and particle size on microbial inactivation of Cu-doped TiO2 nanoparticles

The properties of Cu-doped TiO(2) nanoparticles (NPs) were independently controlled in a flame aerosol reactor by varying the molar feed ratios of the precursors, and by optimizing temperature and time history in the flame. The effect of the physico-chemical properties (dopant concentration, crystal phase and particle size) of Cu-doped TiO(2) nanoparticles on inactivation of Mycobacterium smegmatis (a model pathogenic bacterium) was investigated under three light conditions (complete dark, fluorescent light and UV light). The survival rate of M. smegmatis (in a minimal salt medium for 2 h) exposed to the NPs varied depending on the light irradiation conditions as well as the dopant concentrations. In dark conditions, pristine TiO(2) showed insignificant microbial inactivation, but inactivation increased with increasing dopant concentration. Under fluorescent light illumination, no significant effect was observed for TiO(2). However, when TiO(2) was doped with copper, inactivation increased with dopant concentration, reaching more than 90% (>3 wt% dopant). Enhanced microbial inactivation by TiO(2) NPs was observed only under UV light. When TiO(2) NPs were doped with copper, their inactivation potential was promoted and the UV-resistant cells were reduced by over 99%. In addition, the microbial inactivation potential of NPs was also crystal-phase-and size-dependent under all three light conditions. A lower ratio of anatase phase and smaller sizes of Cu-doped TiO(2) NPs resulted in decreased bacterial survival. The increased inactivation potential of doped TiO(2) NPs is possibly due to both enhanced photocatalytic reactions and leached copper ions.