In vitro digestion of microplastics in human digestive system: Insights into particle morphological changes and chemical leaching.

Despite the well-reported occurrences and established pathways for microplastics (MPs) ingestion by humans, the eventual fate of these particles in the human gastrointestinal system is poorly understood. The present study tries to gain a better understanding of the fate of four common food-borne MPs, i.e. Polystyrene (PS), Polypropylene (PP), Low-density Polyethylene (LDPE), and Nylon, in a simulated in vitro human digestive system. Firstly, the changes in the physicochemical properties of 20-210 µm sized MPs as well as the leaching of chemicals were monitored using fluorescence microscopy, FTIR, and LC-QTOF-MS. Thereafter, the mass loss and morphological alterations in 3-4 mm sized MPs were observed after removing the organic matter. The interaction of PS and PP MPs with duodenal and bile juices manifested in a corona formation. The increase in surface roughness in PP MPs aligned with MP-enzyme dehydrogenation reactions and the addition of NO groups. A few fragments ranging from 30 to 250 µm, with negligible mass loss, were released during the MP digestion process. In addition, the leaching of compounds, e.g. capsi-amide, butanamide, and other plasticizers and monomers was also observed from MPs during digestion, and which may have the potential to accumulate and get absorbed by the digestive organs, and to subsequently impart toxic effects.

Long-term presence of microplastics in aerobic and anaerobic sequential batch reactors: Effect on treatment, microbial diversity, and microplastics morphology.

Sewage treatment plants (STPs) are identified as the significant sink and source of microplastics (MPs) in aquatic bodies and terrestrial systems. A major fraction of MPs gets retained in STPs for a longer duration, and their potentiality for secondary MPs generation and additives leaching remain under investigated. Therefore, this study focussed on the effect of long-term exposure of aerobic and anaerobic biological sewage treatment units on MPs, along with the effect of MPs on treatment efficiency and microbial consortium. A mixture of polyvinyl chloride, polystyrene, and nylon MPs at 262 MPs/L was spiked in the aerobic and anaerobic sequential batch reactors (SBRs) for 120 days at the start of study. The study revealed a release of noteworthy fraction of secondary MPs into the reactors from spiked MPs. At the end of 120th day, the presence of secondary generated MPs was estimated as 1000 ± 71 MPs/L and 650±141 MPs/L in aerobic and anaerobic SBRs respectively. Most of the observed secondary MPs were of size < 300 µm. Leaching of additives, i.e. cyclohexylamine, cyclotetradecane, octadecanol, pipericine etc., into the SBR effluents were also observed. The depuration capacities of the reactors were not affected with the presence of MPs during the study. While the microbial diversity and abundance were negatively impacted in aerobic SBRs, no such impacts were observed in anaerobic SBRs due to MPs. These results do suggest such exposures to potentially cause secondary MPs and chemical pollution in receiving matrices for the treated effluent, as well as effect on the native microbial community.

A unified modelling framework for type I (discrete) settling and rising of microplastics in primary sedimentation tanks.

Sewage treatment plants (STPs) are considered as a significant source of microplastic pollution into the terrestrial and aquatic environment. Existing observations suggest that primary treatment accounts for major microplastics removal in STPs, though with high variability due to the complex nature of the polymer compositions, abundance, and sizes in the incoming sewage. Here, we develop a unified modelling framework to simulate the Type I (or discrete) settling or rising behaviour of microplastics to predict their eventual fate in Primary Sedimentation Tank (PST). The model was developed as per the conventional design protocol for PST involving Stokes equation and modifications as per flow regime for settling of nylon and polystyrene microplastics. It was subsequently validated with independent column experiments for both settling (nylon and polystyrene) and rising (low-density polyethylene and polypropylene) microplastics in different size ranges. The validated model was then applied for multiple realistic scenarios of polymer compositions, relative abundance, and size distributions in the incoming sewage. The model predicts removals ranging from 12% to 94% for a mixture of microplastics in the size fraction 0-500 µm. Model simulations also suggest better microplastics removal with the integration of skimming in PST, and optimization of surface overflow velocity.

Chlorophyll sensitized and salicylic acid functionalized TiO2 nanoparticles as a stable and efficient catalyst for the photocatalytic degradation of ciprofloxacin with visible light.

Developing efficient and stable visible light active photocatalyst has significant environmental applications. Though dye sensitization of TiO2 nanoparticles with natural chlorophyll pigments can potentially impart visible light activity, their long-term stability is a major concern. We investigated the functionalization of TiO2 with salicylic acid, and subsequent sensitization with chlorophylls to improve the catalyst stability for the photocatalytic degradation of Ciprofloxacin (CPX) under visible light. A significant improvement in the degradation efficiency and catalyst stability was observed for five reuse cycles. Further, an optimum CPX degradation of ∼75% was achieved with 0.75 g L-1 catalyst dosage of 0.1 chl/0.1 SA-TiO2, initial pH of 6, and 10 ppm of initial CPX for a visible light exposure of 2 h. The degradation followed the pseudo-second-order kinetics. In addition, the ciprofloxacin degradation was reduced in the wastewater matrix system due to the presence of other scavenging species such as chlorides, sulphates, and alkalinity. Significant reduction in the toxicity of degradation compounds after the photocatalytic degradation was observed in comparison to parent CPX. Further, the degradation pathway and plausible mechanism of degradation of CPX were also proposed.

Visible light responsive Cu-N/TiO2 nanoparticles for the photocatalytic degradation of bisphenol A.

Visible light active co-doped Cu-N/TiO2 photocatalyst was synthesized by the sol-gel method. The synthesized catalysts were characterized by X-ray diffraction (XRD), field-emission transmission electron microscope (FE-TEM), X-ray photoelectron spectroscopy (XPS), Fourier transform infrared spectroscopy (FTIR), and UV-visible diffuse reflectance spectrophotometry (UV-vis DRS). The co-doping with Cu-N reduced the bandgap (∼2.83 eV) and extended the optical absorption range of TiO2 catalysts to the visible region. The incorporation of Cu and N on TiO2 lattice results in sub-conduction and valence band formation, which enhanced the photoactivity and electron-hole generation rate. The visible light activity of Cu-N/TiO2 was evaluated via photocatalytic degradation of bisphenol A (BPA) under blue LED illumination. The maximum BPA degradation of 42.7% was observed at 0.5 g L-1 catalyst dosage, initial pH of BPA solution = 8.2, and initial BPA concentration of 10 ppm. Further, a possible mechanism of photocatalytic degradation of BPA was also established.

Estimation of microplastic exposure via the composite sampling of drinking water, respirable air, and cooked food from Mumbai, India.

Despite the established presence of microplastics in consumable products and inhalable air and the associated health hazards, the actual extent of human exposure to microplastics is currently unknown. We estimated exposure to microplastics through 24-h composite sampling of drinking water, cooked food, and respirable air. Daily average exposures of 382 ± 205, 594 ± 269, and 1036 ± 493 particles per person were observed through drinking water, air, and food, respectively. Our estimates suggest an average daily exposure of 2012 ± 598 microplastic particles per person via these dominant routes. Considering the variety of common consumer plastics, the plastic intake was calculated to be 122.25 ± 177.38 to 202.80 ± 294.25 mg per person per day. Food ingestion was observed to be the major pathway, with fragments as the dominant particle type, followed by fibers and spherical beads. The major polymers identified in the food samples were polyethylene terephthalate, polystyrene, polynorbornene, nylon, polychloroprene, and copolymer polyacrylamide. These results provide a realistic estimate of urban exposure to microplastics and may be helpful in their risk characterization.

Degradation of amoxicillin with sono, photo, and sonophotocatalytic oxidation under low-frequency ultrasound and visible light.

The presence of pharmaceutically active compounds in aquatic bodies is a global concern, and suitable treatment technologies are required. In this study, the efficacy of photocatalytic, sonocatalytic, and sonophotocatalytic oxidation processes for the degradation of amoxicillin (AMX) was investigated using visible light with N doped TiO2 (N-TiO2) nanoparticles as the catalyst and low-frequency ultrasound in a novel multifrequency reactor. The influence of different operational parameters on the extent of AMX degradation was studied. Sonophotocatalytic oxidation was found more efficient for AMX degradation when compared to photocatalysis or sonocatalysis alone, and may be due to the reduced bandgap of the catalyst, enhanced cavitation effect due to the presence of the solid catalyst, and improved mass transfer of pollutants. AMX degradation during sono, photo, and sonophotocatalytic oxidation processes was in good agreement with pseudo-first-order kinetics. Empirical kinetic models were also developed using multiple linear regression for predicting the degradation efficiency accounting for the operational parameters. Scavenger experiments suggested that •OH radicals largely contributed to AMX degradation, and a plausible mechanism for degradation was proposed. Further, possible degradation pathways for all three treatment processes are also proposed after identifying the degradation products.

Decolorization of methylene blue using Fe(III)-citrate complex in a solar photo-Fenton process: impact of solar variability on process optimization.

This study investigates the solar photo-Fenton based decolorization of a cationic dye methylene blue (MB) at circumneutral pH conditions. Water-soluble Fe(III)-citrate complex was used as a source of Fe(II) during the reaction by ligand-to-metal charge transfer under solar irradiation, and consequently, for the production of hydroxyl radicals. Solar decolorization of methylene blue was studied in sunny as well as cloudy weather, and further optimized using response surface methodology and Box-Behnken statistical experimental design. In this model, Fe(III) dose, citrate ion dose, and initial pH of the solution were used as independent parameters, and percentage decolorization of MB was used as a response. Better decolorization of MB was observed in sunny weather as compared to cloudy weather. A particular combination of parameters, i.e. pH of 7, Fe(III) of 0.5 mM, and citrate ion concentration of 10 mM, was found to achieve 89.19% and 51.22% decolorization in sunny and in cloudy weather respectively, which were the optimum/near-optimum performances for these weather conditions. Hence the process initiated with these parameters may potentially achieve better performance than any other parameter combination in all weathers, although the absolute removal would still depend on incident solar irradiation.

Contamination of Indian sea salts with microplastics and a potential prevention strategy.

This study reports the contamination of Indian sea salts with different microplastic particles, as a consequence of using contaminated sea water. Samples from all eight brands of investigated sea salts were found contaminated, and concentrations of these particles ranged from 103 ± 39 to 56 ± 49 particles kg-1 of salt. Both fibers and fragments were observed with large variation in size. Eighty percent of the extracted fibers and the fragments were smaller than 2000 µm and 500 µm respectively. Extracted particles were mostly polyesters, polyethylene terephthalate (PET), polyamide, polyethylene, and polystyrene. Their total mass concentration was also estimated as 63.76 µg kg-1 of salt. These results are significant, since India is a leading producer and exporter of sea salts. A simple sand filtration of artificially contaminated sea water could effectively (> 85% removal by weight and > 90% removal by number) remove these microplastics and has the potential for preventing the transfer of microplastics into the salt from contaminated sea waters.

A comprehensive mechanistic model for simulating algal-bacterial growth dynamics in photobioreactors.

A comprehensive mechanistic model with state of the art understanding and assumptions is presented to simulate major processes in a photobioreactor for describing the algal-bacterial growth dynamics. The model includes a total of 37 state variables that broadly cover all the essential physiological and physico-chemical processes in such a system. Model parameters are first calibrated with batch experimental data, and thereafter, extensive validation of the model is carried with long term independent experimental data in diverse conditions. The developed model is able to capture the complex system behavior with reasonable accuracy. Also, the comprehensive mathematical formulation with realistic assumptions make this model a valuable tool for gaining better insights into the complex system behavior.

Evaluation of various solvent systems for lipid extraction from wet microalgal biomass and its effects on primary metabolites of lipid-extracted biomass.

Microalgae have tremendous potential to grow rapidly, synthesize, and accumulate lipids, proteins, and carbohydrates. The effects of solvent extraction of lipids on other metabolites such as proteins and carbohydrates in lipid-extracted algal (LEA) biomass are crucial aspects of algal biorefinery approach. An effective and economically feasible algae-based oil industry will depend on the selection of suitable solvent/s for lipid extraction, which has minimal effect on metabolites in lipid-extracted algae. In current study, six solvent systems were employed to extract lipids from dry and wet biomass of Scenedesmus obliquus. To explore the biorefinery concept, dichloromethane/methanol (2:1 v/v) was a suitable solvent for dry biomass; it gave 18.75% lipids (dry cell weight) in whole algal biomass, 32.79% proteins, and 24.73% carbohydrates in LEA biomass. In the case of wet biomass, in order to exploit all three metabolites, isopropanol/hexane (2:1 v/v) is an appropriate solvent system which gave 7.8% lipids (dry cell weight) in whole algal biomass, 20.97% proteins, and 22.87% carbohydrates in LEA biomass. Graphical abstract: Lipid extraction from wet microalgal biomass and biorefianry approach.

A comprehensive mechanistic model for simulating algal growth dynamics in photobioreactors.

A comprehensive mechanistic model for describing algal growth dynamics in a photobioreactor was developed in this work with state of the art understanding and realistic assumptions for major associated processes. The model included 27 state variables related to various algal processes. This model was validated with extensive experimental data obtained from independent growth experiments in batch reactors, and was able to simulate system performance reasonably well. The comprehensive nature of the formulation also highlights the complex inter-relationship between all processes, and provides a tool for gaining more systematic insights into algal behavior in photobioreactors and other such systems.

Studies on Bacterial Proteins Corona Interaction with Saponin Imprinted ZnO Nanohoneycombs and Their Toxic Responses.

Molecular imprinting generates robust, efficient, and highly mesoporous surfaces for biointeractions. Mechanistic interfacial interaction between the surface of core substrate and protein corona is crucial to understand the substantial microbial toxic responses at a nanoscale. In this study, we have focused on the mechanistic interactions between synthesized saponin imprinted zinc oxide nanohoneycombs (SIZnO NHs), average size 80-125 nm, surface area 20.27 m(2)/g, average pore density 0.23 pore/nm and number-average pore size 3.74 nm and proteins corona of bacteria. The produced SIZnO NHs as potential antifungal and antibacterial agents have been studied on Sclerotium rolfsii (S. rolfsii), Pythium debarynum (P. debarynum) and Escherichia coli (E. coli), Staphylococcus aureus (S. aureus), respectively. SIZnO NHs exhibited the highest antibacterial (∼50%) and antifungal (∼40%) activity against Gram-negative bacteria (E. coli) and fungus (P. debarynum), respectively at concentration of 0.1 mol. Scanning electron spectroscopy (SEM) observation showed that the ZnO NHs ruptured the cell wall of bacteria and internalized into the cell. The molecular docking studies were carried out using binding proteins present in the gram negative bacteria (lipopolysaccharide and lipocalin Blc) and gram positive bacteria (Staphylococcal Protein A, SpA). It was envisaged that the proteins present in the bacterial cell wall were found to interact and adsorb on the surface of SIZnO NHs thereby blocking the active sites of the proteins used for cell wall synthesis. The binding affinity and interaction energies were higher in the case of binding proteins present in gram negative bacteria as compared to that of gram positive bacteria. In addition, a kinetic mathematical model (KMM) was developed in MATLAB to predict the internalization in the bacterial cellular uptake of the ZnO NHs for better understanding of their controlled toxicity. The results obtained from KMM exhibited a good agreement with the experimental data. Exploration of mechanistic interactions, as well as the formation of bioconjugate of proteins and ZnO NHs would play a key role to interpret more complex biological systems in nature.

Lipid extracted algae as a source for protein and reduced sugar: a step closer to the biorefinery.

The objective of this study was to investigate the feasibility of using lipid extracted algae (LEA) as a source for protein and reduced sugar, and the effects of various procedural treatments on their yields. LEA provided comparable yields of protein and reduced sugars to those from total algae. Oven drying provided highest yields of all products followed by freeze drying, while sun drying significantly lowered their yields. Effective cell disruption by microwave and autoclave increased the lipid yields from algae, but resulted in increased loss of other compounds with lipid extracting solvents lowering their yields during sequential extraction. Relatively inefficient cell disruption by ultrasonication and osmotic shock lowered the amount of cell protein lost to the lipid extracting solvents. These results highlight the complexity of concurrent extraction of all value added products from algae, and the need for proper selection of the processes to achieve the objectives of integrated biorefinery.

Adaptability of growth and nutrient uptake potential of Chlorella sorokiniana with variable nutrient loading.

Chlorella sorokiniana can sustain growth in conditions hostile to other species, and possesses good nutrient removal and lipid accumulation potentials. However, the effects of variable nutrient levels (N and P) in wastewaters on growth, productivity, and nutrient uptake by C. sorokiniana have not been studied in detail. This study demonstrates the ability of this alga to sustain uniform growth and productivity, while regulating the relative nutrient uptake in accordance to their availability in the bulk medium. These results highlight the potential of C. sorokiniana as a suitable candidate for fulfilling the coupled objectives of nutrient removal and biomass production for bio-fuel with wastewaters having great variability in nutrient levels.

Nutrient removal using algal-bacterial mixed culture.

Simultaneous nitrate (N), phosphate (P), and COD removal was investigated in photobioreactors containing both algae and bacteria. The reactors were operated in the semi-batch mode with a hydraulic retention time of 2 days. Reactors were operated in two phases, (1) with 33 % biomass recycle and (2) with no biomass recycle. In both phases, more than 90 % of N and P and 80 % of COD present in synthetic wastewaters with initial N and P concentrations of up to 110 and 25 mg/L, respectively, and initial COD of 45 mg/L could be removed. Biomass growth in reactors did not increase with the increase in initial N and P concentration in either phase. However, biomass growth was slightly more in reactors operated with no biomass recycle. In both phases, N and P uptake was greater in reactors with greater initial N and P concentrations. Also in all cases, N and P uptake in the reactors was far in excess of the stoichiometric requirements for the observed biomass growth. This "luxury uptake" of nitrogen and phosphorus by biomass was responsible for excellent nitrogen and phosphorus removal as observed. However, based on the results of this study, no advantage of biomass recycling could be demonstrated.