The Effect of Cellulose Nanocrystal Reassembly on Latex-Based Pressure-Sensitive Adhesive Performance.

Different cellulose nanocrystal (CNC) forms (dried vs never-dried) can lead to different degrees of CNC reassembly, the formation of nanofibril-like structures, in nanocomposite latex-based pressure-sensitive adhesive (PSA) formulations. CNC reassembly is also affected by CNC sonication and loading as well as the protocol used for CNC addition to the polymerization. In this study, carboxylated CNCs (cCNCs) were incorporated into a seeded, semibatch, 2-ethylhexyl acrylate/methyl methacrylate/styrene emulsion polymerization and cast as pressure-sensitive adhesive (PSA) films. The addition of CNCs led to a simultaneous increase in tack strength, peel strength, and shear adhesion, avoiding the typical trade-off between the adhesive and cohesive strength. Increased CNC reassembly resulted from the use of dried, redispersed, and sonicated cCNCs, along with increased cCNC loading and addition of the cCNCs at the seed stage of the polymerization. The increased degree of CNC reassembly was shown to significantly increase the shear adhesion by enhancing the elastic modulus of the PSA films.

Native microalgal-bacterial consortia from the Ecuadorian Amazon region: an alternative to domestic wastewater treatment.

In low-middle income countries (LMIC), wastewater treatment using native microalgal-bacterial consortia has emerged as a cost-effective and technologically-accessible remediation strategy. This study evaluated the effectiveness of six microalgal-bacterial consortia (MBC) from the Ecuadorian Amazon in removing organic matter and nutrients from non-sterilized domestic wastewater (NSWW) and sterilized domestic wastewater (SWW) samples. Microalgal-bacterial consortia growth, in NSWW was, on average, six times higher than in SWW. Removal rates (RR) for NH4 +- N and PO4 3--P were also higher in NSWW, averaging 8.04 ± 1.07 and 6.27 ± 0.66 mg L-1 d-1, respectively. However, the RR for NO3 - -N did not significantly differ between SWW and NSWW, and the RR for soluble COD slightly decreased under non-sterilized conditions (NSWW). Our results also show that NSWW and SWW samples were statistically different with respect to their nutrient concentration (NH4 +-N and PO4 3--P), organic matter content (total and soluble COD and BOD5), and physical-chemical parameters (pH, T, and EC). The enhanced growth performance of MBC in NSWW can be plausibly attributed to differences in nutrient and organic matter composition between NSWW and SWW. Additionally, a potential synergy between the autochthonous consortia present in NSWW and the native microalgal-bacterial consortia may contribute to this efficiency, contrasting with SWW where no active autochthonous consortia were observed. Finally, we also show that MBC from different localities exhibit clear differences in their ability to remove organic matter and nutrients from NSWW and SWW. Future research should focus on elucidating the taxonomic and functional profiles of microbial communities within the consortia, paving the way for a more comprehensive understanding of their potential applications in sustainable wastewater management.

An integrated approach for the phycoremediation of Pb(II) and the production of biofertilizer using nitrogen-fixing cyanobacteria.

In recent years, growing attention has been directed toward the phycoremediation of heavy metals from bodies of water; however, many challenges remain. The nitrogen requirements for algal growth in nutrient-poor waters can lead to substantial costs. Moreover, proper management of the metal-loaded biomass is a concern. This study assessed the performance of two nitrogen-fixing cyanobacteria, Anabaena sp. and Nostoc muscorum, in treating Pb(II)-contaminated water without nitrogen under batch and fed-batch modes, as well as the subsequent utilization of the produced biomass as a biofertilizer. After 12 days of the batch mode with initial Pb(II) concentrations of 10, 20, 35, and 60 mg/L, Pb(II) removal efficiencies were 98.90%, 98.95%, 97.20%, and 84.98% by Anabaena sp. and 88.00%, 73.10%, 54.54%, and 26.83% by N. muscorum, respectively. Anabaena sp. sustained growth and Pb(II) removal under the fed-batch mode by adjusting hydraulic retention time based on the influent Pb(II) concentration. Decontamination of the metal-loaded Anabaena sp. biomass was performed and resulted in a Pb(II) desorption of 93%. The desorbed Anabaena sp. extract provided the nutrient requirements for Chlorella vulgaris. The proposed strategy provides simultaneous Pb(II) bioremediation and biofertilizer production in a system driven by light energy, atmospheric N2, and CO2.

Pilot-scale feasibility study for the stabilization of coal tailings via microbially induced calcite precipitation.

Sustainable long-term solutions to managing tailings storage facilities (TSFs) are integral for mines to operate in a safe and environmentally responsible manner. The long-term storage of subaqueous tailings can pose significant safety, environmental, and economic risks; therefore, alternative containment strategies for maintaining geochemical stability of reactive materials must be explored. In this study, the physical and geochemical stabilization of coal tailings using microbially induced calcite precipitation (MICP) was evaluated at a laboratory pilot scale. Three application techniques simulated commonly used agricultural approaches and equipment that could be deployed for field-scale treatment: spraying on treatment solutions with irrigation sprinklers, mixing tailings and treatment solutions with a rototiller, and distributing treatment solutions via shallow trenches using an excavator ripper. Test cells containing 1.0 × 1.0 × 0.5 m of tailings were treated with ureolytic bacteria (Sporosarcina pasteurii) and cementation solutions composed of urea and calcium chloride for 28 days. Penetrometer tests were performed following incubation to evaluate the extent of cementation. The spray-on application method showed the greatest strength improvement, with in an increase in surface strength of more than 50% for the 28-day testing period. The distribution of treatment solution using trenches was found to be less effective and resulted in greater variability in particle size distribution of treated tailings and would not be recommended for use in the field. The use of rototilling equipment provided a homogenous distribution of treatment solution; however, the disruption to the tailings material was less effective for facilitating effective cementation. Bacterial plate counts of soil samples indicated that S. pasteurii cultures remained viable in a tailings environment for 28 days at 18 °C and near-neutral pH. The treatment was also found to stabilize the pH of tailings porewater sampled over the 28-day incubation period, suggesting the potential for the treatment to provide short-term geochemical stability under unsaturated conditions.

Understanding the influence of free nitrous acid on microalgal-bacterial consortium in wastewater treatment: A critical review.

Microalgal-bacterial consortium (MBC) constitutes a sustainable and efficient alternative to the conventional activated sludge process for wastewater treatment (WWT). Recently, integrating the MBC process with nitritation (i.e., shortcut MBC) has been proposed to achieve added benefits of reduced carbon and aeration requirements. In the shortcut MBC system, nitrite or free nitrous acid (FNA) accumulation exerts antimicrobial influences that disrupt the stable process performance. In this review, the formation and interactions that influence the performance of the MBC were firstly summarized. Then the influence of FNA on microalgal and bacterial monocultures and related mechanisms together with the knowledge gaps of FNA influence on the shortcut MBC were highlighted. Other challenges and future perspectives that impact the scale-up of the shortcut MBC for WWT were illustrated. A potential roadmap is proposed on how to maximize the stable operation of the shortcut MBC system for sustainable WWT and high-value biomass production.

Mathematical Description of the RAFT Copolymerization of Styrene and Glycidyl Methacrylate Using the Terminal Model.

A mathematical model for the kinetics, composition and molar mass development of the bulk reversible addition-fragmentation chain transfer (RAFT) copolymerization of glycidyl methacrylate (GMA) and styrene (St), at several GMA molar feed fractions at 103 °C, in the presence of 2-cyano isopropyl dodecyl trithiocarbonate as the RAFT agent and 1,1'-azobis(cyclohexane carbonitrile), as the initiator, is presented. The copolymerization proceeded in a controlled manner and dispersities of the copolymers remained narrow even at high conversions. Experimental data and calculated profiles of conversion versus time, composition versus conversion and molar mass development for the RAFT copolymerization of St and GMA agreed well for all conditions tested, including high-conversion regions. The kinetic rate constants associated with the RAFT- related reactions and diffusion-controlled parameters were properly estimated using a weighted nonlinear multivariable regression procedure. The mathematical model developed in this study may be used as an aid in the design and upscaling of industrial RAFT polymerization processes.

Optimization of biogas production during start-up with electrode-assisted anaerobic digestion.

To better understand anaerobic digestion (AD) conditions during start-up, a series of batch and bench-scale studies were conducted to investigate conditions affecting the performance of the anaerobic reactors, including pH fluctuations, ammonia inhibition, and bioaugmentation. Capacitive soil moisture sensors were placed inside the AD reactors to provide near real-time microbial monitoring under experimental batch conditions and to create a microbial electrolysis cell (MEC) environment. After an eight-day digestion process at 40 °C, the capacitive soil moisture sensors performed as a rudimentary microbial activity tracking device. However, the electrodes had a statistically significant impact on biogas production with a small potential 0.8 V having a stabilizing effect on AD at 40 °C during start-up. Furthermore, electrode-assisted AD noted a biogas output 63.7% higher than the conventional AD without electrodes. Conversely, the bioaugmented electrode-assisted AD showed a 7% increase in biogas volume when compared to the non-bioaugmented batch.

A comprehensive review on current technologies for removal of endocrine disrupting chemicals from wastewaters.

In the recent years, endocrine disrupting compounds (EDCs) has received increasing attention due to their significant toxic effects on human beings and wildlife by affecting their endocrine systems. As an important group of emerging pollutant, EDCs have been detected in various aquatic environments, including surface waters, groundwater, wastewater, runoff, and landfill leachates. Their removal from water resources has also been an emerging concern considering growing population as well as reducing access to fresh water resources. EDC removal from wastewaters is highly dependent on physicochemical properties of the given EDCs present in each wastewater types as well as various aquatic environments. Due to chemical, physical and physicochemical diversities in these parameters, variety of technologies consisting of physical, biological, electrochemical, and chemical processes have been developed for their removal. This review highlights that the effectiveness of EDC removal is highly dependent of selecting the appropriate technology; which decision is made upon a full wastewater chemical characterization. This review aims to provide a comprehensive perspective about all the current technologies used for EDCs removal from various aquatic matrices along with rising challenges such as the antimicrobial resistance gene transfer during EDC treatment.

Polysaccharide-Based Nanoparticles as Pickering Emulsifiers in Emulsion Formulations and Heterogenous Polymerization Systems.

Bio-based Pickering emulsifiers are a nontoxic alternative to surfactants in emulsion formulations and heterogenous polymerizations. Recent demand for biocompatible and sustainable formulations has accelerated academic interest in polysaccharide-based nanoparticles as Pickering emulsifiers. Despite the environmental advantages, the inherent hydrophilicity of polysaccharides and their nanoparticles limits efficiency and application range. Modification of the polysaccharide surface is often required in the development of ultrastable, functional, and water-in-oil (W/O) systems. Complex surface modification calls into question the sustainability of polysaccharide-based nanoparticles and is identified as a significant barrier to commercialization. This review summarizes the use of nanocelluloses, -starches, and -chitins as Pickering emulsifiers, highlights trends and best practices in surface modification, and provides recommendations to expedite commercialization.

Time series relationships between chlorophyll-a, physicochemical parameters, and nutrients in the Eastern Harbour of Alexandria, Egypt.

The Eastern Harbour of Alexandria, on the Egyptian Mediterranean coast, is characterized by environmental complications due to different types of anthropogenic stressors associated with water dynamics inside the harbor as well as the rapid water exchange with the open sea. These conditions caused chronic eutrophication conditions, with variable levels in the long term. The present study followed daily some physicochemical parameters, nutrients, and phytoplankton biomass, for a complete year. The results indicate coincidence on the short-time scale between the nutrients, phytoplankton biomass, pH, and dissolved oxygen. Spearman's correlation illustrated strong positive correlations between algal blooms and both pH and dissolved oxygen. The present study recorded twelve separate algal blooms, with an average of chlorophyll-a > 16.7 µg/L, confirming the continuity of high eutrophication in the Eastern Harbour. The seasonal Mann-Kendall tests showed that summer attained significant increasing trends for chlorophyll-a, silicate, nitrite, and nitrate, while winter has a significant decreasing trend for chlorophyll-a and pH.

The role of antibiotics and heavy metals on the development, promotion, and dissemination of antimicrobial resistance in drinking water biofilms.

Antimicrobial resistance (AMR), as well as the development of biofilms in drinking water distribution systems (DWDSs), have become an increasing concern for public health and management. As bulk water travels from source to tap, it may accumulate contaminants of emerging concern (CECs) such as antibiotics and heavy metals. When these CECs and other selective pressures, such as disinfection, pipe material, temperature, pH, and nutrient availability interact with planktonic cells and, consequently, DWDS biofilms, AMR is promoted. The purpose of this review is to highlight the mechanisms by which AMR develops and is disseminated within DWDS biofilms. First, this review will lay a foundation by describing how DWDS biofilms form, as well as their basic intrinsic and acquired resistance mechanisms. Next, the selective pressures that further induce AMR in DWDS biofilms will be elaborated. Then, the pressures by which antibiotic and heavy metal CECs accumulate in DWDS biofilms, their individual resistance mechanisms, and co-selection are described and discussed. Finally, the known human health risks and current management strategies to mitigate AMR in DWDSs will be presented. Overall, this review provides critical connections between several biotic and abiotic factors that influence and induce AMR in DWDS biofilms. Implications are made regarding the importance of monitoring and managing the development, promotion, and dissemination of AMR in DWDS biofilms.

Improving Recycled Poly(lactic Acid) Biopolymer Properties by Chain Extension Using Block Copolymers Synthesized by Nitroxide-Mediated Polymerization (NMP).

The aim of this contribution is to assess the use poly(styrene-co-glycidyl methacrylate-b-styrene) copolymers synthesized by nitroxide mediated polymerization (NMP) as chain extenders in the recycling of poly(lactic acid) biopolyester. Concisely, the addition of such block copolymers during the melt processing of recycled poly(lactic acid) (rPLA) leads to important increases in the viscosity average molecular weight of modified polymeric materials. Molar masses increase from 31,000 g/mol for rPLA to 48,000 g mol-1 for the resulting rPLA/copolymer blends (bPLA). Fortuitously, this last value is nearly the same as the one for pristine PLA, which constitutes a first piece of evidence of the molar mass increase of the recycled biopolymer. Thermograms of chain extended rPLA show significant decreases in cold crystallization temperature and higher crystallinity degrees due to the chain extension process using NMP-synthesized copolymers. It was found that increasing epoxide content in the NMP-synthesized copolymers leads to increased degrees of crystallinity and lower cold crystallization temperatures. The rheological appraisal has shown that the addition of NMP synthesized copolymers markedly increases complex viscosity and elastic modulus of rPLA. Our results indicate that P(S-co-GMA)-b-S) copolymers act as efficient chain extenders of rPLA, likely due to the reaction between the epoxy groups present in P(S-co-GMA)-b-PS and the carboxyl acid groups present in rPLA. This reaction positively affects viscometric molar mass of PLA and its performance.

A review of biopolymer (Poly-ß-hydroxybutyrate) synthesis in microbes cultivated on wastewater.

The large quantities of non-degradable single use plastics, production and disposal, in addition to increasing amounts of municipal and industrial wastewaters are among the major global issues known today. Biodegradable plastics from biopolymers such as Poly-ß-hydroxybutyrates (PHB) produced by microorganisms are potential substitutes for non-degradable petroleum-based plastics. This paper reviews the current status of wastewater-cultivated microbes utilized in PHB production, including the various types of wastewaters suitable for either pure or mixed culture PHB production. PHB-producing strains that have the potential for commercialization are also highlighted with proposed selection criteria for choosing the appropriate PHB microbe for optimization of processes. The biosynthetic pathways involved in producing microbial PHB are also discussed to highlight the advancements in genetic engineering techniques. Additionally, the paper outlines the factors influencing PHB production while exploring other metabolic pathways and metabolites simultaneously produced along with PHB in a bio-refinery context. Furthermore, the paper explores the effects of extraction methods on PHB yield and quality to ultimately facilitate the commercial production of biodegradable plastics. This review uniquely discusses the developments in research on microbial biopolymers, specifically PHB and also gives an overview of current commercial PHB companies making strides in cutting down plastic pollution and greenhouse gases.

Surface Modification of Cellulose Nanocrystals via RAFT Polymerization of CO2-Responsive Monomer-Tuning Hydrophobicity.

Cellulose nanocrystals (CNCs) were converted into a CO2-responsive composite nanomaterial by grafting poly(dimethylaminoethyl methacrylate) (PDMAEMA), poly(diethylaminoethyl methacrylate) (PDEAEMA), and poly(diisopropylaminoethyl methacrylate) (PDPAEMA) onto its surface using both grafting-to and grafting-from approaches. The zeta potential (ζ) of the graft-modified CNC could be reversibly switched by protonation/deprotonation of the tertiary amine groups simply by sparging with CO2 and N2, respectively. Depending on the grafting density and the molecular weight of the polymer grafts, CNC can form stable aqueous dispersions at either mildly acidic pH (under CO2) or mildly basic (under N2) conditions. Moreover, it was also determined that the CNC hydrophobicity, assessed using phase-shuttling experiments at different pH values, was also dependent on both the grafting density and molecular weight of the polymer grafts, thereby making it possible to easily tune CNC dispersibility and/or hydrophobicity.

Activated persulfate by iron-based materials used for refractory organics degradation: a review.

Recently, the advanced oxidation processes (AOPs) based on sulfate radicals (SRs) for organics degradation have become the focus of water treatment research as the oxidation ability of SRs are higher than that of hydroxyl radicals (HRs). Since the AOP-SRs can effectively mineralize organics into carbon dioxide and water under the optimized operating conditions, they are used in the degradation of refractory organics such as dyes, pesticides, pharmaceuticals, and industrial additives. SRs can be produced by activating persulfate (PS) with ultraviolet, heat, ultrasound, microwave, transition metals, and carbon. The activation of PS in iron-based transition metals is widely studied because iron is an environmentally friendly and inexpensive material. This article reviews the mechanism and application of several iron-based materials, including ferrous iron (Fe2+), ferric iron (Fe3+), zero-valent iron (Fe0), nano-sized zero-valent iron (nFe0), materials-supported nFe0, and iron-containing compounds for PS activation to degrade refractory organics. In addition, the current challenges and perspectives of the practical application of PS activated by iron-based systems in wastewater treatment are analyzed and prospected.

Nitrogen removal bacterial strains, MSNA-1 and MSD4, with wide ranges of salinity and pH resistances.

Nitrogenous wastewater is difficult to treat using conventional microorganisms in high salinity and acidic/alkaline environments. Two halotolerant bacteria, heterotrophic nitrifying Stenotrophomonas sp. MSNA-1 and aerobic denitrifying Pseudomonas sp. MSD4, were isolated, and the amplification of functional genes provided the evidences of nitrogen removal performance. The results regarding salinity and pH resistance showed that strain MSNA-1 is robust at salinities of 0-15% and pH of 3-10. It can remove 51.2% of NH4+-N (180 mg/L) at salinity of 10% (pH: 7) and 49.2% of NH4+-N under pH 4 (salinity: 3%). For strain MSD4, it is robust at salinities of 0-10% and pH of 5-11. It can remove 62.4% of TN (100 mg/L) at salinity of 7% (pH: 7) and 72.2% of TN under pH 9 (salinity: 3%). Their excellent salinity and pH resistances make them promising candidates for treating nitrogenous wastewaters under extreme conditions with low operational cost.

Microsuspension Polymerization of Styrene Using Cellulose Nanocrystals as Pickering Emulsifiers: On the Evolution of Latex Particles.

We report a mechanistic study of the microsuspension polymerization of styrene stabilized by cellulose nanocrystals (CNCs) in its native form as well as graft-modified with copolymers of styrene and N-3-(dimethylamino)propyl methacrylamide (DMAPMAm) or N,N-(diethylamino)ethyl methacrylate (DEAEMA). Native CNCs and graft-modified CNCs were shown to form stable styrene emulsions with an average droplet diameter of 18-20 and 5-9 µm, respectively. Initiators of widely varying water solubilities [2,2'-azobisisobutyronitrile (AIBN), 2-2'-azobis(2,4-dimethylvaleronitrile) (Vazo-52), and lauroyl peroxide (LPO)] were employed for the polymerizations. The type of initiator and the type of CNC were shown to directly affect the microsuspension polymerization kinetics, particle size, and molecular weight distribution. Using AIBN and Vazo-52, submicron latex particles were observed in the final latex in addition to the desired 3-20 µm CNC-armored microsuspension particles. The resulting latex and microsuspension polystyrene particles were studied for their CNC coverage and surface charge. We found that the presence of CNCs in the aqueous phase did not lead to Pickering emulsion polymerization by heterogeneous nucleation.

Crosslinkable-Chitosan-Enabled Moisture-Resistant Multilayer Gas Barrier Thin Film.

Chitosan-based films exhibit good oxygen barrier that degrades when exposed to high humidity. In an effort to overcome this drawback, a multilayer nanocoating consisting of crosslinkable chitosan (CHQ) and poly(acrylic acid) [PAA] is deposited on polyethylene terephthalate (PET) using layer-by-layer assembly. Chitosan is functionalized with glycidyl methacrylate to introduce acrylic functionalities within the film. The deposited films are crosslinked using a free radical initiator and this crosslinking is confirmed by FTIR and reduced film thickness. A 10-bilayer (BL) crosslinked CHQ/PAA film, which is only 165 nm thick, results in a 36× reduction of the oxygen transmission rate of PET at 90% relative humidity. To achieve these same results without crosslinking, a 15-BL unmodified chitosan (CH)/PAA film, which is almost 5× thicker, must be deposited on PET. This environmentally friendly, transparent nanocoating is promising for food packaging or protection of flexible electronics, especially in high-humidity environments.

Wastewater treatment for nutrient removal with Ecuadorian native microalgae.

The aim of this project was to study the feasibility of utilizing native microalgae for the removal of nitrogen and phosphorus, as a potential secondary wastewater treatment process in Ecuador. Agitation and aeration batch experiments were conducted using synthetic secondary wastewater effluent, to determine nitrogen and phosphorus removal efficiencies by a native Ecuadorian microalgal strain. Experimental results indicated that microalgal cultures could successfully remove nitrogen and phosphorus. NH4+-N and PO43--P removal efficiencies of 52.6 and 55.6%, and 67.0 and 20.4%, as well as NO3--N production efficiencies of 87.0 and 93.1% were reported in agitation and aeration photobioreactors, respectively. Aeration was not found to increase the nutrient removal efficiency of NH4+-N . Moreover, in the case of PO43--P , a negative impact was observed, where removal efficiencies decreased by a factor of 3.3 at higher aeration rates. To the best of our knowledge, this is the first report of the removal of nutrients by native Ecuadorian Chlorella sp., hence the results of this study would indicate that this native microalgal strain could be successfully incorporated in a potential treatment process for nutrient removal in Ecuador.

Pilot-scale evaluation of semi-passive treatment technologies for the treatment of septage under temperate climate conditions.

Population growth in rural Canada has resulted in an increase in municipal septage generation, which could overload existing treatment facilities that rely on biological treatment approaches. To address concerns associated with potential shock loading of these systems, three semi-passive wastewater treatment technologies were compared at the pilot-scale to identify a suitable approach to augment the capacity of an existing wastewater stabilization pond facility in rural Ontario. Two of these technologies, the BioDome and BioCord systems, were commercially available systems that make use of biofilm technology to improve treatment performance and enhance the robustness to temperature and hydraulic loading fluctuations. The third approach involved the use of the natural filtration capacity of zebra mussels to improve effluent quality. The three technologies were assessed against a control for reductions in regulated wastewater parameters with an emphasis on nutrient (ammonia/ammonium, orthophosphate) reductions, air cycling, energy consumption, and performance following exposure to anoxic conditions. The BioCord system was the only technology that was found to significantly outperform the control, exhibiting reductions of 69%, 47%, 77% and 81% for NH3/NH4+, TN, COD and TSS, respectively. The BioCord system also had the lowest maintenance and energy requirements, likely due to its design, which provided the biofilm with optimal oxygen and substrate contact. Consequently, the BioCord system could develop a more stable, heterogeneous microbial population and maintain high levels of activity in its biofilm, even during periods of extended anaerobic conditions. This also suggested that the BioCord system would require less aeration, and hence a lower energy expenditure, than the other systems. Furthermore, the BioCord system showed the fastest rates of recovery, reaching significant levels of parameter reductions within one week of system re-initiation.