Photoelectrocatalytic Surfactant Pollutant Degradation and Simultaneous Green Hydrogen Generation.

For the first time, we demonstrate a photoelectrocatalysis technique for simultaneous surfactant pollutant degradation and green hydrogen generation using mesoporous WO3/BiVO4 photoanode under simulated sunlight irradiation. The materials properties such as morphology, crystallite structure, chemical environment, optical absorbance, and bandgap energy of the WO3/BiVO4 films are examined and discussed. We have tested the anionic type (sodium 2-naphthalenesulfonate (S2NS)) and cationic type surfactants (benzyl alkyl dimethylammonium compounds (BAC-C12)) as model pollutants. A complete removal of S2NS and BAC-C12 surfactants at 60 and 90 min, respectively, by applying 1.75 V applied potential vs RHE to the circuit, under 1 sun was achieved. An interesting competitive phenomenon for photohole utilization was observed between surfactants and adsorbed water. This led to the formation of H2O2 from water alongside surfactant degradation (anode) and hydrogen evolution (cathode). No byproducts were observed after the direct photohole mediated degradation of surfactants, implying its advantage over other AOPs and biological processes. In the cathode compartment, 82.51 µmol/cm2 and 71.81 µmol/cm2 of hydrogen gas were generated during the BAC-C12 and S2NS surfactant degradation process, respectively, at 1.75 V RHE applied potential.

Is cavitation a truly sensible choice for intensifying photocatalytic oxidation processes? - Implications on phenol degradation using ZnO photocatalysts.

Phenols are recalcitrant compounds that constitute the majority of organic contaminants in industrial wastewaters. Their removal at large scales require a combination of various processes to reach the desired discharge quality. An extensive body of work has already been published in the area of phenol removal from wastewater, however none of them have focussed on a truly 'sensible' approach for coupling advanced oxidation processes (AOPs). Rather, a higher removal efficiency was targeted by unduly complicating the process by combining multiple AOPs. The most influential AOP as the primary method typically driven by the nature of the pollutant should form the basis for a hybrid AOP followed by a complementary AOP to intensify the oxidation process. This strategy is lacking in current literature. We address this knowledge gap directly by systematically identifying the best hybrid process for ZnO mediated photocatalysis of phenol. Either a cavitation mediated pre-treatment of ZnO or cavitation-photocatalysis-peroxide based hybrid AOP was investigated. While the pre-treatment approach led to >25% increase in phenol oxidation compared to bare ZnO photocatalysis, the hydrodynamic cavitation-photocatalysis-peroxide based system was found to have a cavitational yield 5 times higher than its acoustic cavitation counterpart. A new phenomenon known as the 'pseudo staggered effect' was also observed and established in hydrodynamic cavitation mediated photocatalysis-peroxide hybrid process for the first time. While we demonstrated that cavitation is a truly 'sensible' choice to enhance photocatalysis, the nature of the pollutant under investigation must always be the key driver when designing such hybrid AOPs.

Biofunctionalized CdS Quantum Dots: A Case Study on Nanomaterial Toxicity in the Photocatalytic Wastewater Treatment Process.

The toxic nature of inorganic nanostructured materials as photocatalysts is often not accounted for in traditional wastewater treatment reactions. Particularly, some inorganic nanomaterials employed as photocatalysts may release secondary pollutants in the form of ionic species that leach out due to photocorrosion. In this context, this work is a proof-of-concept study for exploring the environmental toxicity effect of extremely small-sized nanoparticles (<10 nm) like quantum dots (QDs) that are employed as photocatalysts, and in this study, cadmium sulfide (CdS) QDs are chosen. Typically, CdS is an excellent semiconductor with suitable bandgap and band-edge positions that is attractive for applications in solar cells, photocatalysis, and bioimaging. However, the leaching of toxic cadmium (Cd2+) metal ions due to the poor photocorrosion stability of CdS is a matter of serious concern. Therefore, in this report, a cost-effective strategy is devised for biofunctionalizing the active surface of CdS QDs by employing tea leaf extract, which is expected to hinder photocorrosion and prevent the leaching of toxic Cd2+ ions. The coating of tea leaf moieties (chlorophyll and polyphenol) over the CdS QDs (referred to hereafter as G-CdS QDs) was confirmed through structural, morphological, and chemical analysis. Moreover, the enhanced visible-light absorption and emission intensity of G-CdS QDs in comparison to that of C-CdS QDs synthesized through a conventional chemical synthesis approach confirmed the presence of chlorophyll/polyphenol coating. Interestingly, the polyphenol/chlorophyll molecules formed a heterojunction with CdS QDs and enabled the G-CdS QDs to exhibit enhanced photocatalytic activity in the degradation of methylene blue dye molecules over C-CdS QDs while effectively preventing photocorrosion as confirmed from cyclic photodegradation studies. Furthermore, detailed toxicity studies were conducted by exposing zebrafish embryos to the as-synthesized CdS QDs for 72 h. Surprisingly, the survival rate of the zebrafish embryos exposed to G-CdS QDs was equal to that of the control, indicating a significant reduction in the leaching of Cd2+ ions from G-CdS QDs in comparison to C-CdS QDs. The chemical environment of C-CdS and G-CdS before and after the photocatalysis reaction was examined by X-ray photoelectron spectroscopy. These experimental findings prove that biocompatibility and toxicity could be controlled by simply adding tea leaf extract during the synthesis of nanostructured materials, and revisiting green synthesis techniques can be beneficial. Furthermore, repurposing the discarded tea leaves may not only facilitate the control of toxicity of inorganic nanostructured materials but can also help in enhancing global environmental sustainability.

Oxidation of Sulphur pollutants in model and real fuels using hydrodynamic cavitation.

Hydrodynamic Cavitation (HC) offers an attractive platform for intensifying oxidative desulphurization of fuels. In the first part of this work, we present new results on oxidising single ring thiophene in a model fuel over the extended range of volume fraction of organic phase from 2.5 to 80 v/v %. We also present influence of type and scale of HC device on performance of oxidative desulphurization. Further experiments revealed that oxidising radicals generated in-situ by HC alone were not able to oxidise dual ring thiophenes. External catalyst (formic acid) and oxidising agents (hydrogen peroxide, H2O2) were therefore used with HC. Based on our prior work with acoustic cavitation (AC), the volumetric ratios for H2O2 and formic acid were identified as 0.95 v/v % and 6.25 v/v % respectively. The data of oxidation of dual ring thiophenes with n-dodecane and n-hexane as model fuels and typical transport fuels (diesel, kerosene, and petrol) using these oxidant and catalyst is presented. The observed performance with HC was compared with results obtained from a stirred tank and AC set-up. The presented data indicates that HC is able to intensify oxidation of sulphur species. The presented results provide a sound basis for further developments on HC based oxidative desulphurization processes.

Facile Synthesis of Gram-Scale Mesoporous Ag/TiO2 Photocatalysts for Pharmaceutical Water Pollutant Removal and Green Hydrogen Generation.

This work demonstrates a two-step gram-scale synthesis of presynthesized silver (Ag) nanoparticles impregnated with mesoporous TiO2 and evaluates their feasibility for wastewater treatment and hydrogen gas generation under natural sunlight. Paracetamol was chosen as the model pharmaceutical pollutant for evaluating photocatalytic performance. A systematic material analysis (morphology, chemical environment, optical bandgap energy) of the Ag/TiO2 photocatalyst powder was carried out, and the influence of material properties on the performance is discussed in detail. The experimental results showed that the decoration of anatase TiO2 nanoparticles (size between 80 and 100 nm) with 5 nm Ag nanoparticles (1 wt %) induced visible-light absorption and enhanced charge carrier separation. As a result, 0.01 g/L Ag/TiO2 effectively removed 99% of 0.01 g/L paracetamol in 120 min and exhibited 60% higher photocatalytic removal than pristine TiO2. Alongside paracetamol degradation, Ag/TiO2 led to the generation of 1729 µmol H2 g-1 h-1. This proof-of-concept approach for tandem pollutant degradation and hydrogen generation was further evaluated with rare earth metal (lanthanum)- and nonmetal (nitrogen)-doped TiO2, which also showed a positive response. Using a combination of ab initio calculations and our new theory model, we revealed that the enhanced photocatalytic performance of Ag/TiO2 was due to the surface Fermi-level change of TiO2 and lowered surface reaction energy barrier for water pollutant oxidation. This work opens new opportunities for exploiting tandem photocatalytic routes beyond water splitting and understanding the simultaneous reactions in metal-doped metal oxide photocatalyst systems under natural sunlight.

Quantifying OH radical generation in hydrodynamic cavitation via coumarin dosimetry: Influence of operating parameters and cavitation devices.

Hydrodynamic cavitation (HC) has been extensively investigated for effluent treatment applications. Performance of HC devices or processes is often reported in terms of degradation of organic pollutants rather than quantification of hydroxyl (OH) radicals. In this study, generation of OH radicals in vortex based cavitation device using coumarin dosimetry was quantified. Coumarin was used as the chemical probe with an initial concentration of 100 µM (15 ppm). Generation of OH radicals was quantified by analysing generated single hydroxylated products. The influence of operating parameters such as pH and type of acid used to adjust pH, dissolved oxygen, and inlet and outlet pressures was investigated. Acidic pH was found to be more conducive for generating OH radicals and therefore subsequent experiments were performed at pH of 3. Sulphuric acid was found to be more than three times effective than hydrochloric acid in generating OH radicals. Effect of initial levels of dissolved oxygen was found to influence OH radical generation. Performance of vortex based cavitation device was then compared with other commonly used cavitation devices based on orifice and venturi. The vortex based cavitation device was found to outperform the orifice and venturi based devices in terms of initial per-pass factor. Influence of device scale (nominal flow rate through the device) on performance was then evaluated. The results presented for these devices unambiguously quantifies their cavitational performance. The presented results will be useful for evaluating computational models and stimulate further development of predictive computational models in this challenging area.

Removal of single and dual ring thiophene's from dodecane using cavitation based processes.

Utilising cavitation for enhancing oxidative desulphurization has been investigated for nearly-two decades with recent investigations shifting focus from low-capacity acoustic cavitation (AC) to scalable hydrodynamic cavitation (HC). This work focuses on developing a viable means for removing thiophene's from fuels. In the first phase of this work, use of vortex based HC devices for removal of single and dual ring thiophenes from dodecane was investigated. HC was shown to be able to remove single ring thiophene from dodecane without using any external catalyst or additives. However, in absence of catalyst or additives, it was not possible to remove dual ring thiophenes such as dibenzothiophene using HC. Therefore, in the second phase of this work, various strategies based on use of catalyst or additives to augment cavitation based process were investigated. AC based experiments were opted for shortlisting suitable catalysts and additives for intensifying cavitation based processes. The influence of using oxidant (H2O2) and carboxylic acid catalysts on efficacy of removal of dual ring thiophenes is presented. Several conditions were tested, and the optimal volumetric ratios of 0.95 v/v % H2O2 and 6.25 v/v % HCOOH was identified and utilised throughout the remainder of the study. Regeneration of extractant which accumulates oxidised sulphur species from dodecane was also investigated using AC. The additives and process conditions reported in this work are useful for enhancing desulphurization performance.

Integrated biorefineries for repurposing of food wastes into value-added products.

Food waste (FW) generated through various scenarios from farm to fork causes serious environmental problems when either incinerated or disposed inappropriately. The presence of significant amounts of carbohydrates, proteins, and lipids enable FW to serve as sustainable and renewable feedstock for the biorefineries. Implementation of multiple substrates and product biorefinery as a platform could pursue an immense potential of reducing costs for bio-based process and improving its commercial viability. The review focuses on conversion of surplus FW into range of value-added products including biosurfactants, biopolymers, diols, and bioenergy. The review includes in-depth description of various types of FW, their chemical and nutrient compositions, current valorization techniques and regulations. Further, it describes limitations of FW as feedstock for biorefineries. In the end, review discuss future scope to provide a clear path for sustainable and net-zero carbon biorefineries.

Pretreatment of milled and unchopped sugarcane bagasse with vortex based hydrodynamic cavitation for enhanced biogas production.

Anaerobic digestion can potentially valorise sugarcane bagasse to biogas and fertiliser. Pretreatment is however required to overcome recalcitrance and enhance the biogas yields. Literature reporting the investigation of various biomass pretreatments often use milled biomass as substrate rather than as-received fibrous biomass. This does not establish the true influence of the pretreatment type on biogas generation. Additionally, milling energy is also ignored when calculating net energy gains from enhanced biogas yields and are thus misleading. In this work, a vortex-based hydrodynamic cavitation device was used to enhance the biomethane yields from fibrous as-received biomass for the first time. Clear justification on why milled biomass must not be used as substrates for demonstrating the effect of pretreatment on biogas production is also discussed. The net energy gain from milled hydrodynamic cavitation pre-treated bagasse can be similar to as-received bagasse only when the specific milling energy is ≤700 kWh/ton.

A simplified model for simulating anaerobic digesters: Application to valorisation of bagasse and distillery spent wash.

Current anaerobic digestion (AD) design methods rely on crude empirical models or sophisticated anaerobic digestion models (like ADM1) requiring a large number of parameters which are difficult to obtain experimentally. A simplified model for simulating AD was developed in this work. The model requires knowledge of CH4/CO2 ratio in biogas or indigestible fraction in substrate and batch biomethane potential (BMP) data for estimating three kinetic parameters (maximum specific growth rate, half velocity constant and cell death rate). Reported lab scale BMP data of sugarcane bagasse and spent wash were used to first estimate the kinetics and then to simulate corresponding largescale AD. Simulated results of specific methane yield and digester performance were consistent with available largescale AD data. The potential of the model to simulate single and multi-stage AD were illustrated. The presented approach and model will be useful for effectively valorising a variety of complex biomass substrates to biogas.

ANN based modelling of hydrodynamic cavitation processes: Biomass pre-treatment and wastewater treatment.

We have developed artificial neural network (ANN) based models for simulating two application examples of hydrodynamic cavitation (HC) namely, biomass pre-treatment to enhance biogas and degradation of organic pollutants in water. The first case reports data on influence of number of passes through HC reactor on bio-methane generation from bagasse. The second case reports data on influence of HC reactor scale on degradation of dichloroaniline (DCA). Similar to most of the HC based applications, the availability of experimental data for these two applications is rather limited. In this work a systematic methodology for developing ANN model is presented. The models were shown to describe the experimental data very well. The ANN models were then evaluated for their ability to interpolate and extrapolate. Despite the limited data, the ANN models were able to simulate and interpolate the data for two very different and complex HC applications very well. The extrapolated results of biomethane generation in terms of number of passes were consistent with the intuitive understanding. The extrapolated results in terms of elapsed time were however not consistent with the intuitive understanding. The ANN model was able to generate intuitively consistent extrapolated results for degradation of DCA in terms of number of passes as well as scale of HC reactor. The results will be useful for developing quantitative models of complex HC applications.

Scale-up of vortex based hydrodynamic cavitation devices: A case of degradation of di-chloro aniline in water.

Hydrodynamic cavitation (HC) is being increasingly used in a wide range of applications. Unlike ultrasonic cavitation, HC is scalable and has been used at large scale industrial applications. However, no information about influence of scale on performance of HC is available in the open literature. In this work, we present for the first time, experimental data on use of HC for degradation of complex organic pollutants in water on four different scales (~200 times scale-up in terms of capacity). Vortex based HC devices offer various advantages like early inception, high cavitational yield and significantly lower propensity to clogging and erosion. We have used vortex based HC devices in this work. 2,4 dichloroaniline (DCA) - an aromatic compound with multiple functional groups was considered as a model pollutant. Degradation of DCA in water was performed using vortex-based HC devices with characteristic throat dimension, dt as 3, 6, 12 and 38 mm with scale-up of almost 200 time based on the flow rates (1.3 to 247 LPM). Considering the experimental constraints on operating the largest scale HC device, the experimental data is presented here at only one value of pressure drop across HC device (280 kPa). A previously used per-pass degradation model was extended to describe the experimental data for the pollutant used in this study and a generalised form is presented. The degradation performance was found to decrease with increase in the scale and then plateaus. Appropriate correlation was developed based on the experimental data. The developed approach and presented results provide a sound basis and a data set for further development of comprehensive multi-scale modelling of HC devices.

Spatial Variations of the Methanogenic Communities in the Sediments of Tropical Mangroves.

Methane production by methanogens in mangrove sediments is known to contribute significantly to global warming, but studies on the shift of methanogenic community in response to anthropogenic contaminations were still limited. In this study, the effect of anthropogenic activities in the mangrove sediments along the north and south coastlines of Singapore were investigated by pyrosequencing of the mcrA gene. Our results showed that hydrogenotrophic, acetoclastic and methylotrophic methanogens coexist in the sediments. The predominance of the methylotrophic Methanosarcinales reflects the potential for high methane production as well as the possible availability of low acetate and high methylated C-1 compounds as substrates. A decline in the number of acetoclastic/methylotrophic methanogens in favor of hydrogenotrophic methanogens was observed along a vertical profile in Sungei Changi, which was contaminated by heavy metals. The diversity of methanogens in the various contaminated stations was significantly different from that in a pristine St. John's Island. The spatial variation in the methanogenic communities among the different stations was more distinct than those along the vertical profiles at each station. We suggest that the overall heterogeneity of the methanogenic communities residing in the tropical mangrove sediments might be due to the accumulated effects of temperature and concentrations of nitrate, cobalt, and nickel.

Anthropogenic impact on diazotrophic diversity in the mangrove rhizosphere revealed by nifH pyrosequencing.

Diazotrophs in the mangrove rhizosphere play a major role in providing new nitrogen to the mangrove ecosystem and their composition and activity are strongly influenced by anthropogenic activity and ecological conditions. In this study, the diversity of the diazotroph communities in the rhizosphere sediment of five tropical mangrove sites with different levels of pollution along the north and south coastline of Singapore were studied by pyrosequencing of the nifH gene. Bioinformatics analysis revealed that in all the studied locations, the diazotroph communities comprised mainly of members of the diazotrophic cluster I and cluster III. The detected cluster III diazotrophs, which were composed entirely of sulfate-reducing bacteria, were more abundant in the less polluted locations. The metabolic capacities of these diazotrophs indicate the potential for bioremediation and resiliency of the ecosystem to anthropogenic impact. In heavily polluted locations, the diazotrophic community structures were markedly different and the diversity of species was significantly reduced when compared with those in a pristine location. This, together with the increased abundance of Marinobacterium, which is a bioindicator of pollution, suggests that anthropogenic activity has a negative impact on the genetic diversity of diazotrophs in the mangrove rhizosphere.

An updated comprehensive techno-economic analysis of algae biodiesel.

Algae biodiesel is a promising but expensive alternative fuel to petro-diesel. To overcome cost barriers, detailed cost analyses are needed. A decade-old cost analysis by the U.S. National Renewable Energy Laboratory indicated that the costs of algae biodiesel were in the range of $0.53-0.85/L (2012 USD values). However, the cost of land and transesterification were just roughly estimated. In this study, an updated comprehensive techno-economic analysis was conducted with optimized processes and improved cost estimations. Latest process improvement, quotes from vendors, government databases, and other relevant data sources were used to calculate the updated algal biodiesel costs, and the final costs of biodiesel are in the range of $0.42-0.97/L. Additional improvements on cost-effective biodiesel production around the globe to cultivate algae was also recommended. Overall, the calculated costs seem promising, suggesting that a single step biodiesel production process is close to commercial reality.