Response to "Comment on Bulk Nanobubbles or Not Nanobubbles: That is the Question".

Advanced techniques that combine high spatial resolution with chemical sensitivity to directly probe the observed nanoentities and provide direct evidence that they are truly gas-filled nanobubbles do not exist. Therefore, in our paper, we focused on providing, for the first time, multiple types of indirect evidence using a variety of physical and chemical techniques that the nanoentities are not due to contamination and, hence, they must be bulk nanobubbles (BNBs). It should be noted that such techniques require good experimental skills, sound protocols, good scientific expertise, and reliable equipment. While no single piece of indirect evidence on its own can be considered as conclusive proof, we estimate that our results combined provide strong evidence that bulk nanobubbles do exist and they are stable. The work presented in our paper is the culmination of a series of studies, and many authors have either directly or indirectly confirmed our findings. Nonetheless, in their Comment, Rak & Sedlak reject all of the work we reported. We here address their comments point by point and show that their criticisms are unwarranted and unfounded, as follows.

Bulk Nanobubbles or Not Nanobubbles: That is the Question.

Bulk nanobubbles are a novel nanoscale bubble system with unusual properties which challenge our understanding of bubble behavior. Because of their extraordinary longevity, their existence is still not widely accepted as they are often attributed to the presence of supramolecular structures or contaminants. Nonetheless, bulk nanobubbles are attracting increasing attention in the literature, but reports generally lack objective evidence that the observed nano-entities are indeed nanobubbles. In this paper, we use various physical and chemical analytical techniques to provide multiple evidence that the nano-entities produced mechanically in pure water by a continuous high-shear rotor-stator device or acoustic cavitation and spontaneously by water-ethanol mixing are indeed gas-filled domains. We estimate that the results presented here combined provide conclusive proof that bulk nanobubbles do exist and they are stable. This paper should help close the debate about the existence of bulk nanobubbles and, hence, enable the scientific community to rather focus on developing the missing fundamental science in this area.

Correction: Proving and interpreting the spontaneous formation of bulk nanobubbles in aqueous organic solvent solutions: effects of solvent type and content.

Correction for 'Proving and interpreting the spontaneous formation of bulk nanobubbles in aqueous organic solvent solutions: effects of solvent type and content' by Ananda J. Jadhav et al., Soft Matter, 2020, 16, 4502-4511, DOI: 10.1039/D0SM00111B.

Proving and interpreting the spontaneous formation of bulk nanobubbles in aqueous organic solvent solutions: effects of solvent type and content.

We show that the mixing of organic solvents with pure water leads to the spontaneous formation of suspended nano-entities which exhibit long-term stability on the scale of months. A wide range of solvents representing different functional groups are studied: methanol, ethanol, propanol, acetone, DMSO and formamide. We use various physical and chemical analytical techniques to provide compounded evidence that the nano-entities observed in all these aqueous solvent solutions must be gas-filled nanobubbles as they cannot be attributed to solvent nanodroplets, impurities or contamination. The nanobubble suspensions are characterized in terms of their bubble size distribution, bubble number density and zeta potential. The bubble number density achieved is a function of the type of solvent. It increases sharply with solvent content, reaching a maximum at an intermediate solvent concentration, before falling off to zero. We show that, whilst bulk nanobubbles can exist in pure water, they cannot exist in pure organic solvents and they disappear at some organic solvent-water ratio depending on the type of solvent. The gas solubility of the solvent relative to water as well as the molecular structure of the solvent are determining factors in the formation and stability of bulk nanobubbles. These phenomena are discussed and interpreted in the light of the experimental results obtained.

A critical review on textile wastewater treatments: Possible approaches.

Waste water is a major environmental impediment for the growth of the textile industry besides the other minor issues like solid waste and resource waste management. Textile industry uses many kinds of synthetic dyes and discharge large amounts of highly colored wastewater as the uptake of these dyes by fabrics is very poor. This highly colored textile wastewater severely affects photosynthetic function in plant. It also has an impact on aquatic life due to low light penetration and oxygen consumption. It may also be lethal to certain forms of marine life due to the occurrence of component metals and chlorine present in the synthetic dyes. So, this textile wastewater must be treated before their discharge. In this article, different treatment methods to treat the textile wastewater have been presented along with cost per unit volume of treated water. Treatment methods discussed in this paper involve oxidation methods (cavitation, photocatalytic oxidation, ozone, H2O2, fentons process), physical methods (adsorption and filtration), biological methods (fungi, algae, bacteria, microbial fuel cell). This review article will also recommend the possible remedial measures to treat different types of effluent generated from each textile operation.

On the clustering of bulk nanobubbles and their colloidal stability.

Bulk nanobubbles which are usually observed in pure water have a mean diameter typically around 100 nm. We use a combination of physical and chemical techniques to prove the hypothesis that the nanoentities observed in pure water are stable clusters of much smaller stable nanobubbles. The stability of bulk nanobubble clusters is affected by factors such as ionic strength or internal energy of the system. We show that bulk nanobubbles on the order of 100 nm exist in a stable cluster form in neutral or basic media, and dissociate into tiny primary nanobubbles on the order of 1 nm in acidic media, or in the presence of small amounts of salt. These new findings suggest that bulk nanobubbles which have a high surface energy unsurprisingly tend to behave in a similar manner to solid nanoparticles in terms of their agglomeration tendency, which is confirmed by the DLVO theory. The results will have important implications for our understanding and interpretation of the behaviour of bulk nanobubbles, in particular their interfacial and colloidal stability.

Acoustic and hydrodynamic cavitation assisted hydrolysis and valorisation of waste human hair for the enrichment of amino acids.

Hair waste in large amount is produced in India from temples and saloons, India alone exported approximately 1 million kg of hair in 2010. Incineration and degradation of waste human hair leads to environmental concerns. The hydrothermal process is a conventional method for the production of hair hydrolysate. The hydrothermal process is carried out at a very high temperature and pressure, which causes the degradation of heat-sensitive essential amino acids, thereby depleting the nutritional value. This work deals with alkaline hydrolysis of human hair using acoustic and hydrodynamic cavitation, and comparison with the conventional method. The optimal operating conditions for highest efficiency was observed, for the hydrolysis of 1 g of sample hairs in 100 mL of solution, at 4:1 (KOH: hair) ratio, soaking time of 24 h, the ultrasonic power density of 600 W dm-3 (20 KHz frequency and input power 200 W) or hydrodynamic cavitation inlet pressure of 4 or 7 bars. Cavitation results in rupture of disulfide linkages in proteins and mechanical effects lead to cleavage of several hydrogen bonds breaking the keratin sheet structure in hair. Breakdown of bonds leads to a decrease in viscosity of the solution. 10% and 6% reduction in viscosity is obtained at optimal conditions for ultrasonic and hydrodynamic cavitation treatment, respectively. FTIR analysis of produced hair hydrolysate confirmed that the disulfide bonds in hair proteins are broken down during cavitation. The amino acid of hair hydrolysate, prepared using cavitation, has a relatively higher digestibility and nutritional value due to the enhancement of amino-acid content, confirmed using amino acid analysis. Cavitation assisted hair hydrolysate has a potential application in agricultural engineering as a fertilizer for improvement of the quality of the soil and land. Cavitation based hair hydrolysate can also be used as an environmentally friendly and economical source of essential amino acids and digestibles for animal or poultry feed.

A Henry's law method for generating bulk nanobubbles.

A new technique for generating bulk nanobubble suspensions has been developed based on Henry's law which states that the amount of dissolved gas in a liquid is proportional to its partial pressure above the liquid. This principle which forms the basis of vacuum degasification has been exploited here to produce stable bulk nanobubbles in excess of 109 bubble mL-1 in pure water, through successive expansion/compression strokes inside a sealed syringe. We provide evidence that the observed nano-entities must be gas-filled nanobubbles by showing that: (i) they cannot be attributed to organic or inorganic impurities; (ii) they disappear gradually over time whilst their mean size remains unchanged; (iii) their number density depends on the concentration of dissolved gas in water and its solubility; and (iv) added sparging of gas enhances process yield. We study the properties of these nanobubbles including the effects of type of dissolved gas, water pH and the presence of different valence salts on their number density and stability. Given the potential of the technique for large scale production of nanobubble suspensions, we describe a successfully tested automated model and outline the basis for process scale-up.

Which Parameters Affect Biofilm Removal with Acoustic Cavitation? A Review.

Bacterial biofilms are a cause of contamination in a wide range of medical and biological areas. Ultrasound is a mechanical energy that can remove these biofilms using cavitation and acoustic streaming, which generate shear forces to disrupt biofilm from a surface. The aim of this narrative review is to investigate the literature on the mechanical removal of biofilm using acoustic cavitation to identify the different operating parameters affecting its removal using this method. The properties of the liquid and the properties of the ultrasound have a large impact on the type of cavitation generated. These include gas content, temperature, surface tension, frequency of ultrasound and acoustic pressure. For many of these parameters, more research is required to understand their mechanisms in the area of ultrasonic biofilm removal, and further research will help to optimise this method for effective removal of biofilms from different surfaces.