Effects of calcium ions and polysaccharides type on transparent exopolymer particle formation and the related fouling mechanisms.

Organics and divalent cations are the primary barriers constraining the performance of membrane technology, while the interactions between them and the detailed mechanisms of their impacts are still lacking in-depth analysis. In this study, sodium alginate and xanthan gum were selected as polysaccharides models, and the formation of transparent extracellular polymer particles (TEP) was assessed to examine the effect of Ca2+ and polysaccharides type on membrane fouling from both qualitative and quantitative perspectives. The results revealed that higher Ca2+ concentrations led to a greater abundance of TEP, and the transformation of TEP microstructure is a key factor for the membrane fouling change indicated by specific filtration resistance (SFR). TEP formed by sodium alginate underwent a transformation from amorphous-TEP (a-TEP) form to particle-TEP (p-TEP), corresponding to a unimodal pattern of SFR variation. With increasing Ca2+ concentration, the molecular interactions of xanthan gum became stronger, resulting in larger fibrous a-TEP and a continuous SFR increase. According to the extended Derjaguin-Landau-Verwey-Overbeek (XDLVO) theory, TEP formed by xanthan gum exhibited higher adhesion energy, thus causing more severe membrane fouling. The SFR variation of the TEP system can be satisfactorily explained by the conception of chemical potential change in the filtration process depicted in Flory-Huggins theory. This study is the first work to introduce models regarding chemical potential and TEP microstructure, linking the system chemical potential and TEP microstructure with membrane fouling indicated by SFR. As all, this study provided a new perspective for analyzing the polysaccharide fouling behavior via TEP determination and further enhanced the understanding through thermodynamic analysis.

Life in the PFAS lane: The impact of perfluoroalkyl substances on photosynthesis, cellular exudates, nutrient cycling, and composition of a marine microbial community.

Perfluoroalkyl substances (PFAS) are of great ecological concern, however, exploration of their impact on bacteria-phytoplankton consortia is limited. This study employed a bioassay approach to investigate the effect of unary exposures of increasing concentrations of PFAS (perfluorooctane sulfonate (PFOS) and 6:2 fluorotelomer sulfonate (6:2 FTS)) on microbial communities from the northwestern Gulf of Mexico. Each community was examined for changes in growth and photophysiology, exudate production and shifts in community structure (16S and 18S rRNA genes). 6:2 FTS did not alter the growth or health of phytoplankton communities, as there were no changes relative to the controls (no PFOS added). On the other hand, PFOS elicited significant phototoxicity (p < 0.05), altering PSII antennae size, lowering PSII connectivity, and decreasing photosynthetic efficiency over the incubation (four days). PFOS induced a cellular protective response, indicated by significant increases (p < 0.001) in the release of transparent exopolymer particles (TEP) compared to the control. Eukaryotic communities (18S rRNA gene) changed substantially (p < 0.05) and to a greater extent than prokaryotic communities (16S rRNA gene) in PFOS treatments. Community shifts were concentration-dependent for eukaryotes, with the low treatment (5 mg/L PFOS) dominated by Coscinodiscophyceae (40 %), and the high treatment (30 mg/L PFOS) marked by a Trebouxiophyceae (50 %) dominance. Prokaryotic community shifts were not concentration dependent, as both treatment levels became depleted in Cyanobacteriia and were dominated by members of the Bacteroidia, Gammaproteobacteria, and Alphaproteobacteria classes. Further, PFOS significantly decreased (p < 0.05) the Shannon diversity and Pielou's evenness across treatments for eukaryotes, and in the low treatment (5 mg/L PFOS) for prokaryotes. These findings show that photophysiology was not impacted by 6:2 FTS but PFOS elicited toxicity that impacted photosynthesis, exudate release, and community composition. This research is crucial in understanding how PFOS impacts microbial communities.

Mechanistic insights into Ca-alginate gel-associated membrane fouling affected by ethylene diamine tetraacetic acid (EDTA).

While transparent exopolymer particles (TEP) is a major foulant, and ethylene diamine tetraacetic acid (EDTA) is a strong chelating agent frequently used for fouling mitigation in membrane-based water treatment processes, little has been known about TEP-associated membrane fouling affected by EDTA. This work was performed to investigate roles of EDTA addition in TEP (Ca-alginate gel was used as a TEP model) associated fouling. It was interestingly found that, TEP had rather high specific filtration resistance (SFR) of 2.49 × 1015 m-1·kg-1, and SFR of TEP solution firstly decreased and then increased rapidly with EDTA concentration increase (0-1 mM). A series of characterizations suggested that EDTA took roles in SFR of TEP solution by means of changing TEP microstructure. The rather high SFR of TEP layer can be attributed to the big chemical potential gap during filtration described by the extended Flory-Huggins lattice theory. Initial EDTA addition disintegrated TEP structure by EDTA chelating calcium in TEP, inducing reduced SFR. Continuous EDTA addition decreased solution pH, resulting into no effective chelating and accumulation of EDTA on membrane surface, increasing SFR. It was suggested that factors increasing homogeneity of TEP gel will increase SFR, and vice versa. This study revealed the thermodynamic mechanism of TEP fouling behaviors affected by EDTA, and also demonstrated the importance of EDTA dosage and pH adjustment for TEP-associated fouling control.

Fundamental thermodynamic mechanisms of membrane fouling caused by transparent exopolymer particles (TEP) in water treatment.

While transparent exopolymer particles (TEP) has high fouling potential, its underlying fouling mechanisms have not yet been well revealed. In current work, fouling characteristics of TEP under different Ca2+ concentrations (0 to 1.5 mM) were investigated. TEP quantification and filtration tests showed that TEP contents increased with Ca2+ concentration, while TEP's specific filtration resistance (SFR) under the influence of Ca2+ concentration presented a unimodal pattern. The peak of TEP's SFR reached at Ca2+ concentration of 1 mM when SA concentration was 0.3 g·L-1. A series of characterizations suggested that microstructure transformation of TEP particles was the main contributor to the resistance variations of TEP solution. The optical microscope observation showed that above and below the critical Ca2+ concentration (1 mM when SA concentration is 0.3 g·L-1 in this study), the formed TEP existed in the form of c-TEP (average particle size is 0.24 µm) and p-TEP (average particle size is 1.05 µm), respectively. Thermodynamic analysis showed that the adhesion ability of c-TEP (-249,989 and - 303,692 kT) was more than 19 times than that of p-TEP (-12,905 kT), which would accelerate foulant layer formation. In addition, below the critical value, the increased SFR with Ca2+ concentration could be explained by integrating Flory-Huggins lattice theory with the preferential intermolecular coordination. Above the critical value, the decreased SFR can be attributed to the formation of a "large-size crack structure" cake layer from the p-TEP. This study revealed fundamental mechanisms of membrane fouling caused by TEP, greatly deepening understanding of TEP fouling, and facilitating to development of effective fouling control strategies.

The Virioneuston: A Review on Viral⁻Bacterial Associations at Air⁻Water Interfaces.

Vast biofilm-like habitats at air⁻water interfaces of marine and freshwater ecosystems harbor surface-dwelling microorganisms, which are commonly referred to as neuston. Viruses in the microlayer, i.e., the virioneuston, remain the most enigmatic biological entities in boundary surface layers due to their potential ecological impact on the microbial loop and major air⁻water exchange processes. To provide a broad picture of the viral⁻bacterial dynamics in surface microlayers, this review compiles insights on the challenges that viruses likely encounter at air⁻water interfaces. By considering viral abundance and morphology in surface microlayers, as well as dispersal and infection mechanisms as inferred from the relevant literature, this work highlights why studying the virioneuston in addition to the bacterioneuston is a worthwhile task. In this regard, major knowledge gaps and possible future research directions are discussed.

Comparison of Alcian blue and total carbohydrate assays for quantitation of transparent exopolymer particles (TEP) in biofouling studies.

Transparent exopolymer particles (TEP) and their precursors are gel-like acidic polysaccharide particles. Both TEP precursors and TEP have been identified as causal factors in fouling of desalination and water treatment systems. For comparison between studies, it is important to accurately measure the amount and fouling capacity of both components. However, the accuracy and recovery of the currently used Alcian blue based TEP measurement of different surrogates and different size fractions are not well understood. In this study, we compared Alcian blue based TEP measurements with a total carbohydrate assay method. Three surrogates; xanthan gum, pectin and alginic acid; were evaluated at different salinities. Total carbohydrate concentrations of particulates (>0.4 µm) and their precursors (<0.4 µm, >10 kDa) varied depending on water salinity and method of recovery. As xanthan gum is the most frequently used surrogate in fouling studies, TEP concentration is expressed as xanthan gum equivalents (mg XGeq/L) in this study. At a salinity of 35 mg/L sea salt, total carbohydrate assays showed a much higher particulate TEP fraction for alginic acid (38%) compared to xanthan gum (9%) and pectin (12%). The concentrations of particulate TEP therefore may only represent ∼10% of the total mass; while precursor TEP represents ∼80% of the total TEP. This highlights the importance of reporting both particulate and precursor TEP for membrane biofouling studies. The calculated concentrations of TEP and their precursors in seawater samples are also highly dependent on type of surrogate and resulting calibration factor. A linear correlation between TEP recovery and calibration factor was demonstrated in this study for all three surrogates. The relative importance and accuracy of measurement method, particulate size, surrogate type, and recovery are described in detail in this study.

Improved method for measuring transparent exopolymer particles (TEP) and their precursors in fresh and saline water.

Transparent exopolymer particles (TEP) and their precursors produced by phyto-/bacterio-planktons in fresh and marine aquatic environments are increasingly considered as a major contributor to organic/particulate and biological fouling in micro-/ultra-filtration and reverse osmosis membrane (RO) systems. However, currently established methods which are based on Alcian blue (AB) staining and spectrophotometric techniques do not measure TEP-precursors and have the tendency to overestimate concentration in brackish/saline water samples due to interference of salinity on AB staining. Here we propose a new semi-quantitative method which allows measurement of both TEP and their colloidal precursors without the interference of salinity. TEP and their precursors are first retained on 10 kDa membrane, rinsed with ultra-pure water, and re-suspended in ultra-pure water by sonication and stained with AB, followed by exclusion of TEP-AB precipitates by filtration and absorbance measurement of residual AB. The concentration is then determined based on the reduction of AB absorbance due to reaction with acidic polysaccharides, blank correction and calibration with Xanthan gum standard. The extraction procedure allows concentration of TEP and their pre-cursors which makes it possible to analyse samples with a wide range of concentrations (down to <0.1 mg Xeq/L). This was demonstrated through application of the method for monitoring these compounds in algal cultures and a full-scale RO plant. The monitoring also revealed that concentrations of the colloidal precursors were substantially higher than the concentration of TEP themselves. In the RO plant, complete TEP removal was observed over the pre-treatment processes (coagulation-sedimentation-filtration and ultrafiltration) but the TEP precursors were not completely removed, emphasising the importance of measuring this colloidal component to better understand the role of TEP and acidic polysaccharides in RO membrane fouling.