Selective separation of nutrients and volatile fatty acids from food wastes using electrodialysis and membrane contactor for resource valorization.

Transport and selectivity parameters describe the quantity and purity of nutrients and volatile fatty acids (VFAs) separated from fermentation media. However, the complexity of fermentation media and low nutrient concentrations hinder the optimal conditions of such parameters. Exploring technologies to overcome such limitations is crucial for selectively separating VFAs from nutrients in fermented media. The objectives of this study were to investigate the: (1) flux, (2) recovery, (3) concentration factor, and (4) specific energy consumption of nutrients (NH4+, K+, NO3-, and PO43-) and VFAs (acetic, propionic, and butyric acid) via electrodialysis (ED), and (5) selectively separate the VFAs from the nutrients in the ED concentrate using a hydrophobic membrane contactor (HMC). Synthetic feed and real industrial fermented food wastes were used for ED and HMC experiments. The ED consumed 0.395 kWh/kg, recovering 64-95% of the nutrients and VFAs, corresponding to 4.1-9.4 and 0.6-22.1 g/L nutrients and VFAs, respectively. The HMC selectively separated over 94% of VFAs after ED, with <2% nutrients contamination in the final VFA stream. The results suggest that applying HMC after ED can concentrate and selectively separate VFAs from nutrients in fermented food wastes, which can be valorized for bio-based fertilizers and chemical platforms.

Citrate-Coated Silver Nanoparticles Interactions with Effluent Organic Matter: Influence of Capping Agent and Solution Conditions.

Fate and transport studies of silver nanoparticles (AgNPs) discharged from urban wastewaters containing effluent organic matter (EfOM) into natural waters represent a key knowledge gap. In this study, EfOM interfacial interactions with AgNPs, and their aggregation kinetics were investigated by atomic force microscopy (AFM) and time-resolved dynamic light scattering (TR-DLS), respectively. Two well-characterized EfOM isolates, i.e., wastewater humic (WW humic) and wastewater colloids (WW colloids, a complex mixture of polysaccharides-proteins-lipids), and a River humic isolate of different characteristics were selected. Citrate-coated AgNPs were selected as representative capped-AgNPs. Citrate-coated AgNPs showed a considerable stability in Na(+) solutions. However, Ca(2+) ions induced aggregation by cation bridging between carboxyl groups on citrate. Although the presence of River humic increased the stability of citrate-coated AgNPs in Na(+) solutions due to electrosteric effects, they aggregated in WW humic-containing solutions, indicating the importance of humics characteristics during interactions. Ca(2+) ions increased citrate-coated AgNPs aggregation rates in both humic solutions, suggesting cation bridging between carboxyl groups on their structures as a dominant interacting mechanism. Aggregation of citrate-coated AgNPs in WW colloids solutions was significantly faster than those in both humic solutions. Control experiments in urea solution indicated hydrogen bonding as the main interacting mechanism. During AFM experiments, citrate-coated AgNPs showed higher adhesion to WW humic than to River humic, evidencing a consistency between TR-DLS and AFM results. Ca(2+) ions increased citrate-coated AgNPs adhesion to both humic isolates. Interestingly, strong WW colloids interactions with citrate caused AFM probe contamination (nanoparticles adsorption) even at low Na(+) concentrations, indicating the impact of hydrogen bonding on adhesion. These results suggest the importance of solution conditions and capping agents on the stability of AgNPs in solution. However, the characteristics of organics would play a crucial role in the fate and transport of these nano contaminants in urban wastewaters and natural water systems.

Interactions between rotavirus and natural organic matter isolates with different physicochemical characteristics.

Interaction forces between rotavirus and Suwanee River natural organic matter (SRNOM) or Colorado River NOM (CRNOM) were studied by atomic force microscopy (AFM) in NaCl solutions and at unadjusted pH (5.7-5.9). Compared to CRNOM, SRNOM has more aromatic carbon and phenolic/carboxylic functional groups. CRNOM is characterized with aliphatic structure and considerable presence of polysaccharide moieties rich in hydroxyl functional groups. Strong repulsive forces were observed between rotavirus and silica or mica or SRNOM. The interaction decay length derived from the approaching curves for these systems involving rotavirus in high ionic strength solution was significantly higher than the theoretical Debye length. While no adhesion was observed for rotavirus and SRNOM, attraction was observed between CRNOM and rotavirus during approach and adhesion during retraction. Moreover, these adhesion forces decreased with increasing ionic strength. Interactions due to ionic hydrogen bonding between deprotonated carboxyl groups on rotavirus and hydroxyl functional groups on CRNOM were suggested as the dominant interaction mechanisms between rotavirus and CRNOM.

Kinetic study of seawater reverse osmosis membrane fouling.

Reverse osmosis (RO) membrane fouling is not a static state but a dynamic phenomenon. The investigation of fouling kinetics and dynamics of change in the composition of the foulant mass is essential to elucidate the mechanism of fouling and foulant-foulant interactions. The aim of this work was to study at a lab scale the fouling process with an emphasis on the changes in the relative composition of foulant material as a function of operating time. Fouled membrane samples were collected at 8 h, and 1, 2, and 4 weeks on a lab-scale RO unit operated in recirculation mode. Foulant characterization was performed by CLSM, AFM, ATR-FTIR, pyrolysis GC-MS, and ICP-MS techniques. Moreover, measurement of active biomass and analysis of microbial diversity were performed by ATP analysis and DNA extraction, followed by pyro-sequencing, respectively. A progressive increase in the abundance of almost all the foulant species was observed, but their relative proportion changed over the age of the fouling layer. Microbial population in all the membrane samples was dominated by specific groups/species belonging to Proteobacteria and Actinobacteria phyla; however, similar to abiotic foulant, their relative abundance also changed with the biofilm age.

Comparison of MBR and MBBR followed by UV or electrochemical disinfection for decentralized greywater treatment.

Greywater is an attractive source for water reuse at the household or building level, particularly for non-potable applications. Two greywater treatment approaches are membrane bioreactors (MBR) and moving bed biofilm reactors (MBBR), yet, their performance has not been compared so far within their respective treatment flowsheets, including post-disinfection. Two lab-scale treatment trains were operated on synthetic greywater: a) MBR with either polymeric (chlorinated polyethylene, C-PE, 165 days) or ceramic (silicon carbide, SiC, 199 days) membranes coupled with UV disinfection; and b) single-stage (66 days) or two-stage (124 days) MBBR coupled with an electrochemical cell (EC) for in-situ disinfectant generation. Water quality was constantly monitored, and Escherichia coli log removals were assessed through spike tests. Under low-flux operation of the MBR (<8 L·m - 2·h - 1), the SiC membranes delayed the onset of membrane fouling and needed less frequent cleaning compared to C-PE membranes. Both treatment systems met most water quality requirements for unrestricted greywater reuse, at a 10-fold lower reactor volume for the MBR than the MBBR. However, neither the MBR nor the two-staged MBBR allowed adequate nitrogen removal, and the MBBR did not consistently meet effluent chemical oxygen demand and turbidity requirements. Both EC and UV provided non-detectable E. coli concentrations in the effluent. Although the EC provided residual disinfection, scaling and fouling decreased its energetic and disinfection performance over time, making it less efficient than UV disinfection. Several outlines to improve the performance of both treatment trains and disinfection processes are proposed, thus, allowing a fit-for-use approach that leverages the advantages of the respective treatment trains. Results from this investigation will assist in elucidating the most efficient, robust, and low-maintenance technology and configurations for small-scale greywater treatment for reuse.

Fate of organic micropollutants during brackish water desalination for drinking water production in decentralized capacitive electrodialysis.

Capacitive electrodialysis (CED) is an emerging and promising desalination technology for decentralized drinking water production. Brackish water, often used as a drinking water source, may contain organic micropollutants (OMPs), thus raising environmental and health concerns. This study investigated the transport of OMPs in a fully-functional decentralized CED system for drinking water production under realistic operational conditions. Eighteen environmentally-relevant OMPs (20 µg L-1) with different physicochemical properties (charge, size, hydrophobicity) were selected and added to the feed water. The removal of OMPs was significantly lower than that of salts (∼94%), mainly due to their lower electrical mobility and higher steric hindrance. The removal of negatively-charged OMPs reached 50% and was generally higher than that of positively-charged OMPs (31%), whereas non-charged OMPs were barely transported. Marginal adsorption of OMPs was found under moderate water recovery (50%), in contrast to significant adsorption of charged OMPs under high water recovery (80%). The five-month operation demonstrated that the CED system could reliably produce water with low salt ions and TOC concentrations, meeting the respective WHO requirements. The specific energy consumption of the CED stack under 80% water recovery was 0.54 kWh m-3, which is competitive to state-of-the-art RO, ED, and emerging MCDI in brackish water desalination. Under this condition, the total OPEX was 2.43 € m-3, of which the cost of membrane replacement contributed significantly. Although the CED system proved to be a robust, highly adaptive, and fully automated technology for decentralized drinking water production, it was not highly efficient in removing OMPs, especially non-charged OMPs.

Abundance and distribution of cigarette butts on the sand of five touristic beaches in Latin America during the COVID-19 pandemic.

Cigarette butts (CB) and cigarette butt fibers (CBF) are highly abundant and frequent residues on beach sand. Also, they are hazardous waste due to their significant toxicity and potential risk to the ecosystems' biota and the health of beach tourists. This study aimed to determine the abundance and density of CB and CBF found on the active, rest, and service zones of five pilot beaches in Argentina, Colombia, Brazil, Ecuador, and Mexico. The methodology involved collecting CB and CBF in 500 m2 transects of urban tourist beaches using a citizen science-adapted methodology between June 2021 and May 2022, during the COVID-19 pandemic. The abundance and density of CB and CBF, and the Cigarette Butt Pollution Index (CBPI) were calculated. The highest proportion of CB was found in service and rest areas. Bocagrande (CO) reported the highest generation of CB and CBF and a severe CBPI.

Interactions between rotavirus and Suwannee River organic matter: aggregation, deposition, and adhesion force measurement.

Interactions between rotavirus and Suwannee River natural organic matter (NOM) were studied by time-resolved dynamic light scattering, quartz crystal microbalance, and atomic force microscopy. In NOM-containing NaCl solutions of up to 600 mM, rotavirus suspension remained stable for over 4 h. Atomic force microscopy (AFM) measurement for interaction force decay length at different ionic strengths showed that nonelectrostatic repulsive forces were mainly responsible for eliminating aggregation in NaCl solutions. Aggregation rates of rotavirus in solutions containing 20 mg C/L increased with divalent cation concentration until reaching a critical coagulation concentration of 30 mM CaCl(2) or 70 mM MgCl(2). Deposition kinetics of rotavirus on NOM-coated silica surface was studied using quartz crystal microbalance. Experimental attachment efficiencies for rotavirus adsorption to NOM-coated surface in MgCl(2) solution were lower than in CaCl(2) solution at a given divalent cation concentration. Stronger adhesion force was measured for virus-virus and virus-NOM interactions in CaCl(2) solution compared to those in MgCl(2) or NaCl solutions at the same ionic strength. This study suggested that divalent cation complexation with carboxylate groups in NOM and on virus surface was an important mechanism in the deposition and aggregation kinetics of rotavirus.

Removal of pharmaceutical and personal care products (PPCPs) from wastewater using microalgae: A review.

Pharmaceuticals and personal care products (PPCPs) are a group of emerging micro-pollutants causing detrimental effects on living organisms even at low doses. Previous investigations have confirmed the presence of PPCPs in the environment at hazardous levels, mainly due to the inefficiency of conventional wastewater treatment plants (CWWTPs). Their stable structure induces longer persistence in the environment. Microalgae are currently used to bioremediate numerous pollutants of different characteristics and properties released from the domestic, industrial, agricultural, and farm sectors. CO2 mitigation during culture and the use of biomass as feedstock for biodiesel or biofuel production are, briefly, other benefits of microalgae-mediated treatment over CWWTPs. This review provides a comprehensive summary of recent literature, an overview of approaches and treatment systems, and breakthrough in the field of algal-mediated removal of PPCPs in wastewater treatment processes. The mechanisms involved in phycoremediation, along with their experimental approaches, have been discussed in detail. Factors influencing the removal of PPCPs from aqueous media are comprehensively described and assessed. A comparative study on microalgal strains is analyzed for a more efficient implementation of future processes. The role of microalgae to mitigate the most severe environmental impacts of PPCPs and the generation of antibiotic-resistant bacteria is discussed. Also, a detailed assessment of recent research on potential toxic effects of PPCPs on microalgae was conducted. The current review highlights microalgae as a promising and sustainable approach to efficiently bio-transform or bio-adsorb PPCPs.

Transport of organic solutes in ion-exchange membranes: Mechanisms and influence of solvent ionic composition.

Ion-exchange membrane (IEM)-based processes are used in the industry or in the drinking water production to achieve selective separation. The transport mechanisms of organic solutes/micropollutants (i.e., paracetamol, clofibric acid, and atenolol) at a single-membrane level in diffusion cells were similar to that of salts (i.e., diffusion, convection, and electromigration). The presence of an equal concentration of salts at both sides of the membrane slightly decreased the transport of organics due to lower diffusion coefficients of organics in salts and the increase of hindrance and/or decrease of partitioning in the membrane phase. In the presence of a salt gradient, diffusion was the main transport mechanism for non-charged organics, while the counter-transport of salts promoted the transport of charged organics through electromigration (electroneutrality). Conversely, the co-transport of salts hindered the transport of charged organics, where diffusion was the main transport mechanism of the latter. Although convection played a role in the transport of non-charged organics, its influence on the charged solutes was minimal due to the dominant electromigration. Positron annihilation lifetime spectroscopy showed a bimodal size distribution of free-volume elements of IEMs, with both classes of free-volume elements contributing to salt transport, while larger organics can only transport through the larger class.

Internet of Things for Mental Health: Open Issues in Data Acquisition, Self-Organization, Service Level Agreement, and Identity Management.

The increase of mental illness cases around the world can be described as an urgent and serious global health threat. Around 500 million people suffer from mental disorders, among which depression, schizophrenia, and dementia are the most prevalent. Revolutionary technological paradigms such as the Internet of Things (IoT) provide us with new capabilities to detect, assess, and care for patients early. This paper comprehensively survey works done at the intersection between IoT and mental health disorders. We evaluate multiple computational platforms, methods and devices, as well as study results and potential open issues for the effective use of IoT systems in mental health. We particularly elaborate on relevant open challenges in the use of existing IoT solutions for mental health care, which can be relevant given the potential impairments in some mental health patients such as data acquisition issues, lack of self-organization of devices and service level agreement, and security, privacy and consent issues, among others. We aim at opening the conversation for future research in this rather emerging area by outlining possible new paths based on the results and conclusions of this work.

Non-steady diffusion and adsorption of organic micropollutants in ion-exchange membranes: effect of the membrane thickness.

There is no efficient wastewater treatment solution for removing organic micropollutants (OMPs), which, therefore, are continuously introduced to the Earth's surface waters. This creates a severe risk to aquatic ecosystems and human health. In emerging water treatment processes based on ion-exchange membranes (IEM), transport of OMPs through membranes remains unknown. We performed a comprehensive investigation of the OMP transport through a single IEM under non-steady-state conditions. For the first time, positron annihilation lifetime spectroscopy was used to study differences in the free volume element radius between anion- and cation-exchange membranes, and between their thicknesses. The dynamic diffusion-adsorption model was used to calculate the adsorption and diffusion coefficients of OMPs. Remarkably, diffusion coefficients increased with the membrane thickness, where its surface resistance was more evident in thinner membranes. Presented results will contribute to the improved design of next-generation IEMs with higher selectivity toward multiple types of organic compounds.

Influence of salts and natural organic matter on the stability of bacteriophage MS2.

The stability of functionalized nanoparticles generally results from both steric and electrostatic interactions. Viruses like bacteriophage MS2 have adopted similar strategies for stability against aggregation, including a net negative charge under natural water conditions and using polypeptides that form loops extending from the surface of the protein capsid for stabilization. In natural systems, dissolved organic matter can adsorb to and effectively functionalize nanoparticle surfaces, affecting the fate and transport of these nanoparticles. We used time-resolved dynamic light scattering to measure the aggregation kinetics of a model virus, bacteriophage MS2, across a range of solution chemistries to determine what factors might destabilize viruses in aquatic systems. In monovalent electrolytes (LiCl, NaCl, and KCl), aggregation of MS2 could not be induced within a reasonable kinetic time frame, and MS2 was stable even at salt concentrations greater than 1.0 M. Aggregation of MS2 could be induced in divalent electrolytes when we employed Ca(2+). This trend was also observed in solutions containing 10 mg/L Suwannee River organic matter (SROM) reference material. Even at Ca(2+) concentrations as high 200 mM, diffusion-controlled aggregation was never achieved, demonstrating an additional barrier to aggregation. These results were confirmed by small-angle X-ray scattering experiments, which indicate a transition from repulsive to attractive interactions between MS2 virus particles as monovalent salts are replaced by divalent salts.

CT and MR in non-neonatal hypoxic-ischemic encephalopathy: radiological findings with pathophysiological correlations.

Non-neonatal hypoxic-ischemic encephalopathy is a clinical condition often related to cardiopulmonary arrest that demands critical management and treatment decisions. Management depends mainly on the degree of neurological impairment and prognostic considerations. Computed tomography (CT) is often used to exclude associated or mimicking pathology. If any, only nonspecific signs such as cerebral edema, sulci effacement, and decreased gray matter (GM)/white matter (WM) differentiation are evident. Pseudosubarachnoid hemorrhage, a GM/WM attenuation ratio <1.18, and inverted GM attenuation are associated with a poor prognosis. Magnetic resonance (MR) imaging is more sensitive than CT in assessing brain damage in hypoxic-ischemic encephalopathy. Some MR findings have similarities to those seen pathologically, based on spatial distribution and time scale, such as lesions distributed in watershed regions and selective injury to GM structures. In the acute phase, lesions are better depicted using diffusion-weighted imaging (DWI) because of the presence of cytotoxic edema, which, on T2-weighted images, only become apparent later in the early subacute phase. In the late subacute phase, postanoxic leukoencephalopathy and contrast enhancement could be observed. In the chronic phase, atrophic changes predominate over tissue signal changes. MR can be useful for estimating prognosis when other tests are inconclusive. Some findings, such as the extent of lesions on DWI and presence of a lactate peak and depleted N-acetyl aspartate peak on MR spectroscopy, seem to have prognostic value.

Hydroxyl and sulfate radical-based oxidation of RhB dye in UV/H2O2 and UV/persulfate systems: Kinetics, mechanisms, and comparison.

The degradation kinetics and mechanisms of Rhodamine B (RhB) dye by •OH and SO4•- based advanced oxidation processes were investigated. The •OH and SO4•- radicals were generated by UV photolysis of hydrogen peroxide and persulfate (i.e., UV/H2O2 and UV/PS), respectively. The effects of initial solution pH, RhB concentration, oxidant dosage, Fe2+ concentration, and water matrices were examined. The results showed that the degradation of RhB followed pseudo-first-order kinetics in both processes, with the UV/H2O2 process exhibiting better performance than that of the UV/PS process. Acidic conditions were favorable to the degradation of RhB in both systems. Increasing the oxidant dosage or decreasing the contaminant concentration could enhance the degradation of RhB. Photo-Fenton-like processes accelerated the performance when Fe2+ was added into both systems. The removal efficiency of RhB was inhibited upon the addition of humic substances. The addition of Cl- displayed no significant effect and promoted RhB degradation in UV/H2O2 and UV/PS systems, respectively. The presence of NO3- promoted RhB degradation, while H2PO4- and C2O42- showed an inhibitory effect on both UV/H2O2 and UV/PS processes. Radical scavenging tests revealed the dominant role of SO4•- radicals in the UV/PS system. Furthermore, the evolution of low molecular weight organic acids and NH4+ during the degradation of RhB in these two processes were compared. Both UV/H2O2 and UV/PS systems led to similar formation trends of NH4+ and some ring-opening products (e.g., formic acid, acetic acid, and oxalic acid), suggesting some analogies in the decay pathways of RhB by •OH and SO4•--induced oxidation processes.

Impact of DOM source and character on the degradation of primidone by UV/chlorine: Reaction kinetics and disinfection by-product formation.

The presence of Dissolved Organic Matter (DOM) can exert a strong influence on the effectiveness of the UV/chlorine process. This study examined the impact of five DOM isolates with different characteristics on the degradation kinetics of model contaminant primidone (PM) during UV/chlorine treatment. The formation of Disinfection By-Products (DBPs) from DOM after 15-min UV/chlorine treatment followed by 24 h chlorination was investigated and compared with chlorination alone. The use of chemical probes and radical scavengers revealed that •OH and ClO• were the main radical species responsible for the loss of PM at acidic and alkaline conditions, respectively. All tested DOM isolates significantly inhibited the decay of PM. A strong negative correlation (>0.93) was observed between the decay rate constants of PM and SUVA of DOM isolates, except for EfOM isolate, which induced the strongest inhibitory effect due to its higher abundance in sulfur-containing functional groups (i.e., sink of •OH/Cl• radicals). Compared with chlorination, the formation of Adsorbable Organic Chlorine (AOCl) and Trichloromethane (TCM) during the UV/Chlorine process was enhanced and hindered for low SUVA isolates and high SUVA DOM, respectively. However, Dichloroacetonitrile (DCAN) formation was generally lower for all isolates except for Ribou Reservoir DOM at pH 8.4 because of its high reactive nitrogenous DBP precursors at caustic conditions. However, when normalized to the chlorine consumed, the UV/Chlorine process always led to a lower DBPs formation compared with chlorination alone.

Reactivity of chromophoric dissolved organic matter (CDOM) to sulfate radicals: Reaction kinetics and structural transformation.

Sulfate radical (SO4•-) has been extensively studied as a promising alternative in advanced oxidation processes (AOPs) for water treatment. However, little is known about its reactivity to the ubiquitous dissolved organic matter (DOM) in water bodies. SO4•- would selectively react with electron rich moieties in DOM, known as chromophoric DOM (CDOM), due to its light absorbing property. In this study, the reactivity and typical structural transformation of CDOM with SO4•- was investigated. Four well characterized hydrophobic DOM fractions extracted from different surface water sources were selected as model CDOM. SO4•- was produced through the activation of peroxymonosulfate (PMS) by Co(II) ions at pH 8 in borate buffer. The reactivity of CDOM was studied based on the decrease in its ultraviolet absorbance at 254 nm (UVA254) as a function of time. The reactivity of CDOM changed with time where fast and slow reacting CDOMs (i.e., CDOMfast and CDOMslow) were clearly distinguished. A second-order rate constant of CDOMfast with SO4•- was calculated by plotting UVA254 decrease versus PMS exposure; where a Rct value (i.e., ratio of sulfate radical exposure to PMS exposure) was calculated using pCBA as a probe compound. The transformation of CDOM was studied through the analysis of the changes in UVA254, electron donating capacity, fluorescence intensity, and total organic carbon. A transformation pathway leading to a significant carbon removal was proposed. This new knowledge on the kinetics and transformation of CDOM would ultimately assist in the development and operation of SO4•--based water treatment processes.

The characteristics of organic matter influence its interfacial interactions with MnO2 and catalytic oxidation processes.

The influence of dissolved organic matter (DOM) properties on its interfacial interactions with MnO2 and on catalytic oxidation processes was studied by Time-Resolved Dynamic Light Scattering (TR-DLS) and Atomic Force Microscopy (AFM) under varied solution conditions. Four DOM fractions of different characteristics (e.g., SUVA, hydrophobic character, structural properties) were selected. Bared-MnO2 nanoparticles readily aggregated in NaCl and CaCl2 solutions. Classic DLVO Theory successfully described critical coagulation concentrations and aggregation behaviors. In NaCl solution, DOM adsorbed on MnO2 nanoparticles and provided electrosteric stabilization. The two DOM fractions of higher hydrophobic (HPO) character were more efficient in decreasing the aggregation rates. Enhanced MnO2 aggregation was observed at high Ca2+ concentrations due to charge screening and cation bridging between carboxyl groups in DOM structures. The addition of oxidant (H2O2) induced a high aggregation of bared-MnO2 nanoparticles, possibly due to the release of Mn2+ (i.e., complexation mechanisms) and generation of reactive species (O2-, HO2-, and H). Contrasted with their hydrophilic (HPI) counterparts, HPO isolates adsorbed on MnO2 significantly decreased the catalytic oxidation processes between H2O2/MnO2; suggesting a more efficient and stronger DOM coating. Interfacial forces measured by AFM, showed weaker interactions between HPI isolates and MnO2; suggesting unfavorable polar interactions. Conversely, the high adhesion forces between MnO2/HPO isolate would indicate stronger bonds and hydrophobic interactions. This study provided a nanoscale understanding of the impact of DOM characteristics on: a) performance of the MnO2 coated ceramic membranes in water treatment, and b) biogeochemical cycle of Mn-oxides in the environmental.

Interfacial interactions between Skeletonema costatum extracellular organic matter and metal oxides: Implications for ceramic membrane filtration.

In the current study, the interfacial interactions between the high molecular weight (HMW) compounds of Skeletonema costatum (SKC) extracellular organic matter (EOM) and ZrO2 or Al2O3, were investigated by atomic force microscopy (AFM). HMW SKC-EOM was rigorously characterized and described as a hydrophilic organic compound mainly comprised of polysaccharide-like structures. Lipids and proteins were also observed, although in lower abundance. HMW SKC-EOM displayed attractive forces during approaching (i.e., leading to jump-to-contact events) and adhesion forces during retracting regime to both metal oxides at all solution conditions tested, where electrostatics and hydrogen bonding were suggested as dominant interacting mechanisms. However, the magnitude of these forces was significantly higher on ZrO2 surfaces, irrespective of cation type (Na+ or Ca2+) or concentration. Interestingly, while HMW SKC-EOM interacting forces to Al2O3 were practically insensitive to solution chemistry, the interactions between ZrO2 and HMW SKC-EOM increased with increasing cation concentration in solution. The structure, and lower charge, hydrophilicity, and density of hydroxyl groups on ZrO2 surface would play a key role on favoring zirconia associations with HMW SKC-EOM. The current results contribute to advance our fundamental understanding of Algogenic Organic Matter (AOM) interfacial interactions with metal oxides (i.e., AOM membrane fouling), and would highly assist in the proper selection of membrane material during episodic algal blooms.

Organic matter interactions with natural manganese oxide and synthetic birnessite.

Redox reactions of inorganic and organic contaminants on manganese oxides have been widely studied. However, these reactions are strongly affected by the presence of natural organic matter (NOM) at the surface of the manganese oxide. Interestingly, the mechanism behind NOM adsorption onto manganese oxides remains unclear. Therefore, in this study, the adsorption kinetics and equilibrium of different NOM isolates to synthetic manganese oxide (birnessite) and natural manganese oxide (Mn sand) were investigated. Natural manganese oxide is composed of both amorphous and well-crystallised Mn phases (i.e., lithiophorite, birnessite, and cryptomelane). NOM adsorption on both manganese oxides increased with decreasing pH (from pH7 to 5), in agreement with surface complexation and ligand exchange mechanisms. The presence of calcium enhanced the rate of NOM adsorption by decreasing the electrostatic repulsion between NOM and Mn sand. Also, the adsorption was limited by the diffusion of NOM macromolecules through the Mn sand pores. At equilibrium, a preferential adsorption of high molecular weight molecules enriched in aromatic moieties was observed for both the synthetic and natural manganese oxide. Hydrophobic interactions may explain the adsorption of organic matter on manganese oxides. The formation of low molecular weight UV absorbing molecules was detected with the synthetic birnessite, suggesting oxidation and reduction processes occurring during NOM adsorption. This study provides a deep insight for both environmental and engineered systems to better understand the impact of NOM adsorption on the biogeochemical cycle of manganese.