Transport of citrate-coated silver nanoparticles in saturated porous media.

In this study, the influences of physical and chemical factors [e.g., ionic strength (IS), pH, and flow rate] on the fate and transport of citrate-coated silver nanoparticles (AgNPs) were investigated through experiments using saturated columns. For the transport behavior of AgNPs under various conditions, retardation was confirmed with an increase in ionic strength (IS) while early elution developed with an increase in pH and flow rate. These transport experiment outcomes were simulated through Hydrus-1D, and the observed breakthrough curves were confirmed to have a significant correlation with the fitted results. Interestingly, the AgNPs and quartz sand used in this study showed a negative charge in the investigated experimental conditions. Although the reaction between AgNPs and quartz sand was expected to be unfavorable, AgNPs were observed to have been deposited onto the sand surface during the column test. To clarify the mechanism of the deposition of AgNPs even in unfavorable conditions, the interaction energy profiles were calculated based on the Derjaguin-Landau-Verwey-Overbeek (DLVO) theory. From the results, unfavorable interactions were expected in the NP-NP and NP-sand interactions in every condition. It was concluded that the deposition of AgNPs onto the sand surface under the unfavorable conditions in this study was mainly because of the physical roughness of the sand surface. Moreover, this hypothesis was supported by the zone of influence calculation in accordance with IS, the interpretation results of the fractional sand surface coverage in accordance with concentration changes of AgNPs, and series column tests.

Influence of Solution Chemistry and Soft Protein Coronas on the Interactions of Silver Nanoparticles with Model Biological Membranes.

The influence of solution chemistry and soft protein coronas on the interactions between citrate-coated silver nanoparticles (AgNPs) and model biological membranes was investigated by assembling supported lipid bilayers (SLBs) composed of zwitterionic 1,2-dioleoyl-sn-glycero-3-phosphocholine (DOPC) on silica crystal sensors in a quartz crystal microbalance with dissipation monitoring (QCM-D). Our results show that the deposition rates of AgNPs on unmodified silica surfaces increased with increasing electrolyte concentrations under neutral pH conditions. Similar trends were observed when AgNPs were deposited on SLBs, hence indicating that the deposition of AgNPs on model cell membranes was controlled by electrostatic interactions. In the presence of human serum albumin (HSA) proteins at both pH 7 and pH 2, the colloidal stability of AgNPs was considerably enhanced due to the formation of HSA soft coronas surrounding the nanoparticles. At pH 7, the deposition of AgNPs on SLBs was suppressed in the presence of HSA due to steric repulsion between HSA-modified AgNPs and SLBs. In contrast, pronounced deposition of HSA-modified AgNPs on SLBs was observed at pH 2. This observation was attributed to the reduction of electrostatic repulsion as well as conformation changes of adsorbed HSA under low pH conditions, resulting in the decrease of steric repulsion between AgNPs and SLBs.

Potential environmental implications of nanoscale zero-valent iron particles for environmental remediation.

OBJECTIVES: Nanoscale zero-valent iron (nZVI) particles are widely used in the field of various environmental contaminant remediation. Although the potential benefits of nZVI are considerable, there is a distinct need to identify any potential risks after environmental exposure. In this respect, we review recent studies on the environmental applications and implications of nZVI, highlighting research gaps and suggesting future research directions. METHODS: Environmental application of nZVI is briefly summarized, focusing on its unique properties. Ecotoxicity of nZVI is reviewed according to type of organism, including bacteria, terrestrial organisms, and aquatic organisms. The environmental fate and transport of nZVI are also summarized with regards to exposure scenarios. Finally, the current limitations of risk determination are thoroughly provided. RESULTS: The ecotoxicity of nZVI depends on the composition, concentration, size and surface properties of the nanoparticles and the experimental method used, including the species investigated. In addition, the environmental fate and transport of nZVI appear to be complex and depend on the exposure duration and the exposure conditions. To date, field-scale data are limited and only short-term studies using simple exposure methods have been conducted. CONCLUSIONS: In this regard, the primary focus of future study should be on 1) the development of an appropriate and valid testing method of the environmental fate and ecotoxicity of reactive nanoparticles used in environmental applications and 2) assessing their potential environmental risks using in situ field scale applications.

The effects of liquid height/volume, initial concentration of reactant and acoustic power on sonochemical oxidation.

Even though much knowledge on acoustic cavitation and its application has been accumulated over the past decades, further research is still required to develop industrial uses of acoustic cavitation. It is because the available information is mainly based on small-scale sonoreactors and the design and optimization of sonoreactors for large-scale applications have not been widely studied. In this study, the effects of liquid height/volume, initial concentration of the reactant and input acoustic power on sonochemical oxidation reactions including iodide ion oxidation, As(III) oxidation, and hydrogen peroxide generation were investigated using a 291kHz sonoreactor with various liquid height/volumes (50, 100, 200, 300, 500, and 1000mL) and input powers (23, 40, and 82W). As the liquid height/volume and the input power changed, the power density varied from 23 to 1640W/L and the maximum cavitation yields of triiodide ion for 23, 40, and 82W were observed at 0.05, 0.1, and 0.2/0.3L, respectively. It was found that low power was more effective for the small volume and the large volume required high power level and the moderate power density, approximately 400W/L, was suggested for the sonochemical oxidation of iodide ion in the 291kHz sonoreactor in this study. Similar results were observed in the generation of hydrogen peroxide and the sonochemical oxidation of As(III) to As(V). It was also revealed that KI dosimetry could be applicable for the estimation of the sonochemical reactions of non-volatile compounds such as As(III).

The effects of hydrogen peroxide on the sonochemical degradation of phenol and bisphenol A.

This report describes the effects of H2O2 concentration (0.01, 0.1, 1, and 10mM) on the sonochemical degradation of phenol and bisphenol A (BPA) using an ultrasonic source of 35kHz and 0.08W/mL. The concentration of the target pollutants (phenol or BPA), total organic carbon (TOC), and H2O2 were monitored for each input concentration of H2O2. The effects of H2O2 on the sonochemical degradation of phenol was more significant than that of BPA because phenol has a high solubility and low octanol-water partition coefficient (Kow) value and is subsequently very likely to remain in the aqueous phase, giving it a greater probability of reacting with H2O2. The removal of TOC was also enhanced by the addition of H2O2. Some intermediates of BPA have a high Kow value and subsequently have a greater probability of pyrolyzing by the high temperatures and pressures inside of cavitation bubbles. Thus the removal efficiency of TOC in BPA was higher than that of phenol. The removal efficiencies of TOC were lower than the degradation efficiencies of phenol and BPA. This result is due to the fact that some intermediates cannot readily degrade during the sonochemical reaction. The H2O2 concentration decreased but was not completely consumed during the sonochemical degradation of pollutants. The initial H2O2 concentration and the physical/chemical characteristics of pollutants were considered to be important factors in determining the formation rate of the H2O2. When high concentration of H2O2 was added to the solution, the formation rates were relatively low compared to when low concentrations of H2O2 were used.

Acoustic emission spectra and sonochemical activity in a 36 kHz sonoreactor.

During ultrasound-induced cavitation in liquids, acoustic emissions at fundamental and harmonic frequencies can be detected. The effect of acoustic emissions at harmonic frequencies on the sonochemical and sonophysical activities has not been explored, especially in large-scale sonoreactors. In this study, the acoustic emissions in the range, 0-250 kHz in a 36 kHz sonoreactor with varying liquid heights were studied and compared with the sonochemical activities. The acoustic pressures at both fundamental and harmonics decreased drastically as the liquid height was increased due to the attenuation of sound energy. It was observed that the increase in input power resulted in only an increase in the acoustic emissions at derivative frequencies such as, harmonics and subharmonics. The sonochemical activity, evaluated in terms of sonochemiluminescence and H2O2 yield, was not significantly enhanced at higher input power levels. This suggests that at higher power levels, the "extra" acoustic energy is not effectively used to generate primary cavitation activity; rather it is converted to generate acoustic emissions at harmonic and subharmonic frequencies. This is an important observation for the design of energy efficiency large-scale sonochemical reactors.

Frequency effects on the sonochemical degradation of chlorinated compounds.

The effects of frequency in chlorobenzene, chloroform, and carbon tetrachloride have been experimentally investigated in this study. The irradiation frequencies were 35, 74, 170, 300 and 1000 kHz. The degradation rates of chlorobenzene, chloroform, and carbon tetrachloride were highest at 300 kHz. The results of between formation of hydrogen peroxide concentration and degradation of chlorinated compounds were not a coincidence. Methods of the sonochemical efficiency were needed to review. The concentration of total organic carbon was remained after 4 h of sonication. High power intensity, longer sonication time, addition of catalysts and combination of the AOP process, were needed for the degradation of TOC. The formation of chloride ion in aqueous solution was evident for the degradation of chlorinated compounds. However, the theoretical concentration of chloride ion was higher than the measured concentration. This means that the remaining chlorinated contaminants in each solution cannot complete dechlorination and some intermediated were produced.

Investigation of acoustic cavitation energy in a large-scale sonoreactor.

Acoustic cavitation energy distributions were investigated for various frequencies such as 35, 72, 110 and 170 kHz in a large-scale sonoreactor. The energy analyses were conducted in three-dimensions and the highest and most stable cavitation energy distribution was obtained not in 35 kHz but in 72 kHz. However, the half-cavitation-energy distance was larger in the case of 35 kHz ultrasound than in the case of 72 kHz, demonstrating that cavitation energy for one cycle was higher for a lower frequency. This discrepancy was due to the large surface area of the cavitation-energy-meter probe. In addition, 110 and 170 kHz ultrasound showed a very low and poor cavitation energy distribution. Therefore larger input power was required to optimize the use of higher frequency ultrasound in the sonoreactor with long-irradiation distance. The relationship between cavitation energy and sonochemical efficiency using potassium iodide (KI) dosimetry was best fitted quadratically. From 7.77 x 10(-10) to 4.42 x 10(-9)mol/J of sonochemical efficiency was evaluated for the cavitation energy from 31.76 to 103. 67 W. In addition, the cavitation energy attenuation was estimated under the assumption that cavitation energy measured in this study would be equivalent to sound intensity, resulting in 0.10, 0.18 and 2.44 m(-1) of the attenuation coefficient (alpha) for 35, 72 and 110 kHz, respectively. Furthermore, alpha/(frequency)(2) was not constant, as some previous studies have suggested.