The impact of the COVID-19 pandemic on the seawater quality of Ha Long Bay, Vietnam.

Ha Long Bay is a UNESCO World Heritage Site in Vietnam with unique natural scenery. Development and socio-economic activity impact its water quality. In the context of the Vietnam National Standards, historical follow-up data taken over a five-year period (2016 to 2020), for twenty-eight widely dispersed sampling sites, has been used to carry out a temporal assessment of seawater quality utilizing a Water Quality Index (WQI) method. The analysis shows that the seawater quality is generally acceptable over this period. However, the calculated WQI values for the "pandemic year" of 2020 compared to the data for 2016 to 2019, demonstrate a significantly lesser impact for the bay overall and, more specifically, for seventeen individual sites. Ten sites remain unaffected, and one site shows a significantly higher impact. This study demonstrates how the occurrence of the pandemic in 2020 may be exploited for the interrogation of anthropogenic impacts around the bay.

W254 in furin functions as a molecular gate promoting anti-viral drug binding: Elucidation of putative drug tunneling and docking by non-equilibrium molecular dynamics.

Furins are serine endoproteases that process precursor proteins into their biologically active forms, and they play essential roles in normal metabolism and disease presentation, including promoting expression of bacterial virulence factors and viral pathogenesis. Thus, furins represent vital targets for development of antimicrobial and antiviral therapeutics. Recent experimental evidence indicated that dichlorophenyl (DCP)-pyridine "BOS" drugs (e.g., BOS-318) competitively inhibit human furin by an induced-fit mechanism in which tryptophan W254 in the furin catalytic cleft (FCC) functions as a molecular gate, rotating nearly 180o through a steep energy barrier about its chi-1 dihedral to an "open" orientation, exposing a buried (i.e., cryptic) hydrophobic pocket 1. Once exposed, the non-polar DCP group of BOS-318, and similar halo-phenyl groups of analogs, enter the cryptic pocket, stabilizing drug binding. Here, we demonstrate flexible-receptor docking of BOS-318 (and various analogs) was unable to emulate the induced-fit motif, even when tryptophan was replaced with less bulky phenylalanine or glycine. While either substitution allowed access to the hydrophobic pocket for most ligands tested, optimal binding was observed only for W254, inferring a stabilizing effect of the indole sidechain. Furthermore, non-equilibrium steered molecular dynamics (sMD) in which the bound drugs (or their fragments) were extracted from the FCC did not cause closure of the open W254 gate, consistent with the thermodynamic stability of the open or closed W254 orientations. Finally, interactive molecular dynamics (iMD) revealed two putative conduits of drug entry and binding into the FCC, each coupled with W254 dihedral rotation and opening of the cryptic pocket. The iMD simulations further revealed ligand entry and binding in the FCC is likely driven in part by energy fluxes stemming from disruption and re-formation of ligand and protein solvation shells during drug migration from the solution phase into the FCC.

Transformation of endocrine disrupting chemicals, pharmaceutical and personal care products during drinking water disinfection.

Pharmaceuticals and personal care products (PPCPs) and endocrine disrupting compounds (EDCs) are frequently detected in drinking water sources. This raises concerns about the formation of potentially more toxic transformation products (TPs) after drinking water disinfection. This study applied a combination of computational and experimental methods to investigate the biological activity of eight EDCs and PPCPs commonly detected in source waters (acetaminophen, bisphenol A, carbamazepine, estrone, 17α-ethinylestradiol, gemfibrozil, naproxen and triclosan) before and after disinfection. Using a Stepped Forced Molecular Dynamics (SFMD) method, we detected 911 unique TPs, 36% of which have been previously reported in the scientific literature. We calculated the likelihood that TPs would cause damage to biomolecules or DNA relative to the parent compound based on lipophilicity and the occurrence of structural alerts, and applied two Quantitative Structure-Activity Relationship (QSAR) tools to predict toxicity via receptor-mediated effects. In parallel, batch experiments were performed with three disinfectants, chlorine, chlorine dioxide and chloramine. After solid-phase extraction, the resulting TP mixtures were analyzed by chemical analysis and a battery of eleven in vitro bioassays covering a variety of endpoints. The laboratory results were in good agreement with the predictions. Overall, the combination of computational and experimental chemistry and toxicity methods used in this study suggest that disinfection of the studied EDCs and PPCPs will produce a large number of TPs, which are unlikely to increase specific toxicity (e.g., endocrine activity), but may result in increased reactive and non-specific toxicity.

Influence of acid hydrolysis, saponification and sample clean-up on the measurement of phytosterols in dairy cattle feed using GC-MS and GC with flame ionization detection.

The fortification of processed foods including dairy products is increasingly commonplace with phytosterols among many compounds used to improve the nutritional value of food products. It is also increasingly common practice for some dairy cattle feeds to be fortified for their potential to increase phytosterol levels in milk. In this study, a combined, streamlined protocol using acid hydrolysis, saponification and sample clean-up was developed to enable the rapid and reliable measurement of phytosterols. The method was developed with focus on streamlining the overall technique to make it suitable for commercial laboratories, to reduce labor and consumable costs, while maintaining accuracy. A total of 12 different feed types commonly used in the dairy industry were analyzed with the highest and lowest sterol contents found in cotton seed oil and tannin with average phytosterol contents of 256 and <30 mg per 100 g, respectively. With a limit of reporting of 30 mg/kg for individual sterols and a correlation coefficient > 0.99, the method was validated for milk to enable feed comparison studies with respect to the total phytosterol content in raw milk.

Effects of dissolution conditions on the properties of PVDF ultrafiltration membranes.

Poly (vinylidene fluoride) (PVDF) is an important membrane forming material for water treatment. Earlier works have shown that major morphological changes can be achieved when PVDF is dissolved under different conditions with practical applications in membrane distillation and protein attachment. However, no previous report has discussed the effects of dissolution conditions on the performance of PVDF under ultrafiltration, which is one of the most important applications of the polymer. In this work, four different PVDF ultrafiltration membranes were produced from dopes dissolved either by stirring at 24°C, 90°C, 120°C or by sonication. It is shown that dope sonication results in membrane with enhanced thermal and mechanical stability, improved permeate flux during oil emulsion filtration and high flux recovery of ∼63% after cleaning. As a comparison, flux recovery of only ∼26% was obtained for the membrane produced from dope dissolved at 24°C. The outstanding performance of the dope-sonicated membrane was linked to its slightly lower porosity, narrow distribution of small pores and relatively smooth skin layer. Performance parameters for all membranes showed good correlation to porosity suggesting a tool for membrane design achievable by simple variation in the mode of polymer dissolution. The polymer dissolution effect was related to the degree of unfolding of the polymer molecular chains and their entanglements.

Charge tunable thin-film composite membranes by gamma-ray triggered surface polymerization.

Thin-film composite poly(amide) (PA) membranes have greatly diversified water supplies and food products. However, users would benefit from a control of the electrostatic interactions between the liquid and the net surface charge interface in order to benefit wider application. The ionic selectivity of the 100 nm PA semi-permeable layer is significantly affected by the pH of the solution. In this work, for the first time, a convenient route is presented to configure the surface charge of PA membranes by gamma ray induced surface grafting. This rapid and up-scalable method offers a versatile route for surface grafting by adjusting the irradiation total dose and the monomer concentration. Specifically, thin coatings obtained at low irradiation doses between 1 and 10 kGy and at low monomer concentration of 1 v/v% in methanol/water (1:1) solutions, dramatically altered the net surface charge of the pristine membranes from -25 mV to +45 mV, whilst the isoelectric point of the materials shifted from pH 3 to pH 7. This modification resulted in an improved water flux by over 55%, from 45.9 to up 70 L.m-2.h-1, whilst NaCl rejection was found to drop by only 1% compared to pristine membranes.

Towards a quantitative indicator of feather disruption following the cleansing of oiled birds.

A computer-based imaging method for determining feather microstructure coherency following a cleansing treatment, was developed, calibrated and trialled on Mallard Duck (Anas platyrhyhchos) feathers. The feathers were initially contaminated with a light crude oil and then cleansed by either detergent (Deacon 90) treatment or, alternatively, by magnetic particle technology (MPT) using iron powder. The imaging method provides a single quantitative parameter for the coherence of feather microstructure and the results confirm that MPT treatment imparts less disruption to the feather microstructure than detergent treatment. It is proposed that this imaging method can be developed and implemented for the assessment of feather disruption and possibly damage, either for the trialling of different treatment protocols, or as a tool during the rehabilitation process, along with other such indicators, to give a more comprehensive assessment of feather condition than is currently available.

A structural basis for the amphiphilic character of alginates - Implications for membrane fouling.

Ostensibly hydrophilic alginates are known to foul hydrophobic membranes, under various conditions. Here, controlled experiments have been conducted at high and low pH on the fouling of a polypropylene membrane by alginate and the results suggest that the observed fouling is due to an intrinsic property of the alginate. Thus quantum chemical calculations on the M and G monomers of alginate reveal that M adopts an equilibrium geometry that is hydrophilic on one face and hydrophobic on the other, i.e. is potentially amphiphilic. Molecular dynamics simulations on short alginate chains of different sequences interacting with a modelled polypropylene surface, show that this characteristic is carried over to the polymer and results in hydrophobic patches along the chain that facilitate attractive interactions with the polypropylene surface. This concept is buttressed by an analysis of the binding characteristics of a previously reported X-ray structure of the mannuronan C-5 epimerase AlgE4 enzyme.

Metals and metalloids in Little Penguin (Eudyptula minor) prey, blood and faeces.

Piscivorous species like the Little Penguin (Eudyptula minor) are particularly at risk of being negatively impacted by pollution due to their heightened exposure through aquatic food chains. Therefore, determining the concentration of heavy metals in the fish prey of seabirds is an essential component of assessing such risk. In this study, we report on arsenic, cadmium, mercury, lead and selenium concentrations in three fish species, which are known to comprise a substantial part of the diet of Little Penguins at the urban colony of St Kilda, Melbourne, Australia. Metal concentrations in the fish sampled were generally within the expected limits, however, arsenic and mercury were higher than reported elsewhere. Anchovy (Engraulis australis) and sandy sprat (Hyperlophus vittatus) contained higher Hg concentrations than pilchard (Sardinops sagax), while sandy sprat and pilchard contained more selenium. We present these findings together with metal concentrations in Little Penguin blood and faeces, sampled within weeks of the fish collection. Mercury concentrations were highest in the blood, while faeces and fish prey species contained similar concentrations of arsenic and lead, suggesting faeces as a primary route of detoxification for these elements. We also investigated paired blood - faecal samples and found a correlation for selenium only. Preliminary data from stable isotope ratios in penguin blood indicate that changes in penguin blood mercury concentrations cannot be explained by trophic changes in their diet alone, suggesting a variation of bioavailable Hg within this semi-enclosed bay.

Towards Enhanced Performance Thin-film Composite Membranes via Surface Plasma Modification.

Advancing the design of thin-film composite membrane surfaces is one of the most promising pathways to deal with treating varying water qualities and increase their long-term stability and permeability. Although plasma technologies have been explored for surface modification of bulk micro and ultrafiltration membrane materials, the modification of thin film composite membranes is yet to be systematically investigated. Here, the performance of commercial thin-film composite desalination membranes has been significantly enhanced by rapid and facile, low pressure, argon plasma activation. Pressure driven water desalination tests showed that at low power density, flux was improved by 22% without compromising salt rejection. Various plasma durations and excitation powers have been systematically evaluated to assess the impact of plasma glow reactions on the physico-chemical properties of these materials associated with permeability. With increasing power density, plasma treatment enhanced the hydrophilicity of the surfaces, where water contact angles decreasing by 70% were strongly correlated with increased negative charge and smooth uniform surface morphology. These results highlight a versatile chemical modification technique for post-treatment of commercial membrane products that provides uniform morphology and chemically altered surface properties.

Seasonal variation and annual trends of metals and metalloids in the blood of the Little Penguin (Eudyptula minor).

Little Penguins (Eudyptula minor) are high-trophic coastal feeders and are effective indicators of bioavailable pollutants in their foraging zones. Here, we present concentrations of metals and metalloids in blood of 157 Little Penguins, collected over three years and during three distinct seasons (breeding, moulting and non-breeding) at two locations: the urban St Kilda colony and the semi-rural colony at Phillip Island, Victoria, Australia. Penguin metal concentrations were foremostly influenced by location (St Kilda>Phillip Island for non-essential elements) and differed among years and seasons at both locations, reflecting differences in seasonal metal bioaccumulation or seasonal exposure through prey. Mean blood mercury concentrations showed an increasing annual trend and a negative correlation with flipper length at St Kilda. Notably, this study is the first to report on blood metal concentrations during the different stages of moult, showing the mechanism of non-essential metal mobilisation and detoxification.

The effect of electromagnetic fields, from two commercially available water treatment devices, on bacterial culturability.

Commercially available pulsed-electromagnetic field (PEMF) devices are currently being marketed and employed to ostensibly manage biofouling. The reliable application and industry acceptance of such technologies require thorough scientific validation - and this is currently lacking. We have initiated proof-of-principle research in an effort to investigate whether such commercially available PEMF devices can influence the viability (culturability) of planktonic bacteria in an aqueous environment. Thus two different commercial PEMF devices were investigated via a static (i.e. non-flowing) treatment system. 'Healthy' Escherichia coli cells, as well as cultures that were physiologically compromised by silver nano-particles, were exposed to the PEMFs from both devices under controlled conditions. Although relatively minor, the observed effects were nevertheless statistically significant and consistent with the hypothesis that PEMF exposure under controlled conditions may result in a decrease in cellular viability and culturability. It has also been observed that under certain conditions bacterial growth is actually stimulated.

The Little Penguin (Eudyptula minor) as an indicator of coastal trace metal pollution.

Monitoring trace metal and metalloid concentrations in marine animals is important for their conservation and could also reliably reflect pollution levels in their marine ecosystems. Concentrations vary across tissue types, with implications for reliable monitoring. We sampled blood and moulted feathers of the Little Penguin (Eudyptula minor) from three distinct colonies, which are subject to varying levels of anthropogenic impact. Non-essential trace metal and metalloid concentrations in Little Penguins were clearly linked to the level of industrialisation adjacent to the respective foraging zones. This trend was more distinct in blood than in moulted feathers, although we found a clear correlation between blood and feathers for mercury, lead and iron. This study represents the first reported examination of trace metals and metalloids in the blood of any penguin species and demonstrates that this high trophic feeder is an effective bioindicator of coastal pollution.

Amine Enrichment of Thin-Film Composite Membranes via Low Pressure Plasma Polymerization for Antimicrobial Adhesion.

Thin-film composite membranes, primarily based on poly(amide) (PA) semipermeable materials, are nowadays the dominant technology used in pressure driven water desalination systems. Despite offering superior water permeation and salt selectivity, their surface properties, such as their charge and roughness, cannot be extensively tuned due to the intrinsic fabrication process of the membranes by interfacial polymerization. The alteration of these properties would lead to a better control of the materials surface zeta potential, which is critical to finely tune selectivity and enhance the membrane materials stability when exposed to complex industrial waste streams. Low pressure plasma was employed to introduce amine functionalities onto the PA surface of commercially available thin-film composite (TFC) membranes. Morphological changes after plasma polymerization were analyzed by SEM and AFM, and average surface roughness decreased by 29%. Amine enrichment provided isoelectric point changes from pH 3.7 to 5.2 for 5 to 15 min of plasma polymerization time. Synchrotron FTIR mappings of the amine-modified surface indicated the addition of a discrete 60 nm film to the PA layer. Furthermore, metal affinity was confirmed by the enhanced binding of silver to the modified surface, supported by an increased antimicrobial functionality with demonstrable elimination of E. coli growth. Essential salt rejection was shown minimally compromised for faster polymerization processes. Plasma polymerization is therefore a viable route to producing functional amine enriched thin-film composite PA membrane surfaces.

The role of poly-M and poly-GM sequences in the metal-mediated assembly of alginate gels.

Whilst the involvement of poly-G sequences in the formation of metal-mediated alginate gels has been previously studied in some detail, investigations into the role of poly-M and poly-GM sequences has been relatively neglected. In this regard, the binding of sodium and calcium ions to poly-M and poly-GM decamers, and their influence on chain aggregation, has been modelled by conducting a series of molecular dynamics simulations. This work complements a previous analogous study carried out for the poly-G decamer, whereby up to three strands are systematically introduced into each simulation. As in the previous study, this method allows intrinsic binding modes and interchain structural motifs to be revealed, that are consistent with those observed in available AFM images of consolidated 3-D networks. It is apparent from these studies that different sequences have different structural implications for metal-mediated chain association.

Exploring the molecular basis for the metal-mediated assembly of alginate gels.

The binding of sodium and calcium ions to single and multiple poly-G decamer strands has been modelled by conducting a series of molecular dynamics simulations. Implications for metal mediated inter-strand interactions and gel assembly have been explored by systematically introducing up to three strands into each of these simulations. A particular emphasis has been placed on revealing intrinsic binding modes by an unbiased initial positioning of the metal ions. The results have revealed binding modes that provide a rationale for the observed gelling of alginate by calcium rather than sodium ions. A number of junction zones involving calcium ions have been identified that result in chain aggregation. This includes a distinctive perpendicular motif that appears to be ubiquitous in previously reported AFM images of open 3-D alginate networks. The coordination geometries of the metal ions have been characterised and the metal-mediated junctions between associated strands are described in detail.

Experimental and computational investigations of the interactions between model organic compounds and subsequent membrane fouling.

The formation of aggregates of sodium alginate and bovine serum albumin (BSA) (as representative biopolymers) with humic acid were detected by Liquid Chromatography (LC) UV254 response in the biopolymer region for mixture solutions. BSA interaction with humic acid showed that aggregation occurred both in the presence and absence of calcium, suggesting that multivalent ions did not play a part in the aggregation process. Similar analyses of the alginate interaction with humic acid also showed a positive interaction, but only in the presence of calcium ions. The fouling characteristics for the BSA-humic acid mixture appeared to be significantly greater than the fouling characteristics of the individual solutions, while for the sodium alginate-humic acid mixture, the fouling rate was similar to that of the sodium alginate alone. The effectiveness of hydraulic backwashing, 10-15% reversibility, was observed for the BSA-humic acid mixture, while the % reversibility was 20-40% for the sodium alginate-humic acid mixture. Increased humic acid and DOC rejection were observed for both BSA-humic acid and sodium alginate-humic acid solutions compared to the individual solutions, indicating that the biopolymer filter cakes were able to retain humic acids. When compared with BSA-humic acid mixture solution, greater removal of humic acid was observed for alginate-humic mixture, suggesting that sodium alginate may have a greater capacity for associations with humic acid when in the presence of calcium than BSA. Complementary molecular dynamics simulations were designed to provide insights into the specific mechanisms of interaction between BSA and humic acid, as well as between alginate and humic acid. For the BSA-humic acid system; electrostatic, hydrophobic and hydrogen bonding were the dominant types of interactions predicted, whilst divalent ion-mediated bonding was not identified in the simulations, which supported the LC-results. Similarly for the alginate-humic acid system, the interactions predicted were divalent ion-mediated interactions only and this was also supported the LC results. This work suggests that LC-UV254 might be used to identify aggregated biopolymers, and that combined with current characterisation techniques, be used to better explain performance variations between water sources.

Effect of IX dosing on polypropylene and PVDF membrane fouling control.

The performance of ion exchange (IX) resin for organics removal from wastewater was assessed using advanced characterisation techniques for varying doses of IX. Organic characterisation using liquid chromatography with a photodiode array (PDA) and fluorescence spectroscopy (Method A), and UV254, organic carbon and organic nitrogen detectors (Method B), was undertaken on wastewater before and after magnetic IX treatment. Results showed partial removal of the biopolymer fraction at high IX doses. With increasing concentration of IX, evidence for nitrogen-containing compounds such as proteins and amino acids disappeared from the LC-OND chromatogram, complementary to the fluorescence response. A greater fluorescence response of tryptophan-like proteins (278 nm/343 nm) for low IX concentrations was consistent with aggregation of tryptophan-like compounds into larger aggregates, either by self-aggregation or with polysaccharides. Recycling of IX resin through multiple adsorption steps without regeneration maintained the high level of humics removal but there was no continued removal of biopolymer. Subsequent membrane filtration of the IX treated waters resulted in complex fouling trends. Filtration tests with either polypropylene (PP) or polyvinylidene fluoride (PVDF) membranes showed higher rates of initial fouling following treatment with high IX doses (10 mL/L) compared to filtration of untreated water, while treatment with lower IX doses resulted in decreased fouling rates relative to the untreated water. However, at longer filtration times the rate of fouling of IX treated waters was lower than untreated water and the relative fouling rates corresponded to the amount of biopolymer material in the feed. It was proposed that the mode of fouling changed from pore constriction during the initial filtration period to filter cake build up at longer filtration times. The organic composition strongly influenced the rate of fouling during the initial filtration period due to competitive adsorption processes, while at longer filtration times the rate of fouling appeared to depend upon the amount of biopolymer material in the feed water.

Comparative studies on the antioxidant properties and polyphenolic content of wine from different growing regions and vintages, a pilot study to investigate chemical markers for climate change.

Many health benefits of wine result from specific polyphenolic compounds. Factors such as climate, CO2 levels and region are known to affect polyphenolic compounds in wine; therefore a pilot study was conducted to focus on the Australian climate which has shifted from El Niño to La Niña. This research paper presents the influence of climate conditions and growing regions on the in vitro and ex vivo antioxidant capacity of red and white wine and the profile and concentration of polyphenols in these wines from the 2008 and 2009 vintages. The ORAC and polyphenolic data show that warmer climate wines had lower in vitro antioxidant capacity values but retained good bioavailability based on data from the RBC ex vivo assay compared to cool climate wines. Based on this pilot study, further research is being conducted at the National Measurement Institute, Australia (NMIA) with the goal of determining more polyphenolic compounds which appear to be affected by climate conditions.

An approach to industrial water conservation--a case study involving two large manufacturing companies based in Australia.

This study presents the application of an integrated water management strategy at two large Australian manufacturing companies that are contrasting in terms of their respective products. The integrated strategy, consisting of water audit, pinch analysis and membrane process application, was deployed in series to systematically identify water conservation opportunities. Initially, a water audit was deployed to completely characterize all water streams found at each production site. This led to the development of a water balance diagram which, together with water test results, served as a basis for subsequent enquiry. After the water audit, commercially available water pinch software was utilized to identify possible water reuse opportunities, some of which were subsequently implemented on site. Finally, utilizing a laboratory-scale test rig, membrane processes such as UF, NF and RO were evaluated for their suitability to treat the various wastewater streams. The membranes tested generally showed good contaminant rejection rates, slow flux decline rates, low energy usage and were well suited for treatment of specific wastewater streams. The synergy between the various components of this strategy has the potential to reduce substantial amounts of Citywater consumption and wastewater discharge across a diverse range of large manufacturing companies.