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The authors would like to thank the Hydro Nation Scholar Programme funded by the Scottish Government through the Scottish Funding Council and managed by the Hydro Nation International Centre for funding this research. The authors would like to thank the Engineering and Physical Sciences Research Council (EPSRC) [EP/P029280/1]. Microplastic research has gained attention due to the increased detection of microplastics (

The potential of microplastics to act as a vector for micropollutants of natural or anthropogenic origin is of rising concern. Cyanobacterial toxins, including microcystins, are harmful to humans and wildlife. In this study, we demonstrate for the first time the potential of microplastics to act as vectors for two different microcystin analogues. A concentration of up to 28 times from water to plastic was observed for the combination of polystyrene and microcystin-LF achieving toxin concentrations on the plastic of 142 ± 7 μg g-1. Based on the experimental results, and assuming a worst-case scenario, potential toxin doses for daphnids are calculated based on published microplastic ingestion data. Progressing up through trophic levels, theoretically, the concentration of microcystins in organisms is discussed. The experimental results indicate that adsorption of microcystins onto microplastics is a multifactorial process, depending on the particle size, the variable amino acid composition of the microcystins, the type of plastic, and pH. Furthermore, the results of the current study stressed the limitations of exclusively investigating microcystin-LR (the most commonly studied microcystin congener) as a model compound representing a group of around 250 reported microcystin congeners.

Funding: We acknowledge the funding provided by the Engineering and Physical Sciences Research Council, UK (Global Challenge Research Fund: EP/P029280/1) towards carrying out this research. We also thank the support on electron microscopes from EPSRC Capital for Great Technologies (Grant EP/LP017008/1 and EP/R02375/1). Cyanobacteria and their toxins are a threat to drinking water safety as increasingly cyanobacterial blooms (mass occurrences) occur in lakes and reservoirs all over the world. Photocatalytic removal of cyanotoxins by solar light active catalysts is a promising way to purify water at relatively low cost compared to modifying existing infrastructure. We have established a facile and low-cost method to obtain TiO2 and g-C3N4 coated floating photocatalysts using recycled glass beads. g-C3N4 coated and TiO2+g-C3N4 co-coated beads were able to completely remove microcystin-LR in artificial fresh water under both natural and simulated solar light irradiation without agitation in less than 2 h. TiO2 coated beads achieved complete removal within 8 h of irradiation. TiO2+g-C3N4 beads were more effective than g-C3N4 beads as demonstrated by the increase reaction rate with reaction constants, 0.0485 min−1 compared to 0.0264 min−1 respectively, with TiO2 alone found to be considerably slower 0.0072 min−1. g-C3N4 based photocatalysts showed a similar degradation pathway to TiO2 based photocatalysts by attacking the C6–C7 double bond on the Adda side chain. Publisher PDF

Cyanobacteria and their toxic secondary metabolites present challenges for water treatment globally. In this study we have assessed TiO

The authors would like to thank the Scottish Goverment's Hydro Nation Scholars Programme for funding this research. The authors would like to thank the Engineering and Physical Sciences Research Council (EPSRC) [EP/P029280/1]. Plastics are utilised globally but are of environmental concern due to their persistence. The global presence of microplastics (particles

Cyanobacteria and their toxins are a threat to drinking water safety as increasingly cyanobacterial blooms (mass occurrences) occur in lakes and reservoirs all over the world. Photocatalytic removal of cyanotoxins by solar light active catalysts is a promising way to purify water at relatively low cost compared to modifying existing infrastructure. We have established a facile and low-cost method to obtain TiO

The authors would like to thank the Engineering and Physical Sciences Research Council (EPSRC) [EP/P029280/1], the Coordination for the Improvement of Higher Education Personnel - CAPES [PROEX 20/2016 and PrInt 88887.311806/2018–00], and the Brazilian National Research Council – CNPq [403116/2016–3 and 304164/2017–8] for funding this research. As per EPSRC requirement all data will be made publicly available via the Robert Gordon University's open access repository OpenAIR@RGU. Further, the first author also acknowledges the scholarship from the Brazilian National Research Council - CNPq. To date, the high cost of supplying UV irradiation has prevented the widespread application of UV photolysis and titanium dioxide based photocatalysis in removing undesirable organics in the water treatment sector. To overcome this problem, the use of UV-LEDs (365 nm) for photolysis and heterogeneous photocatalysis applying TiO2 coated glass beads under UV-LED illumination (365 nm) in a pilot scale reactor for the elimination of Microcystis aeruginosa PCC7813 and four microcystin analogues (MC-LR, -LY, -LW, -LF) with a view to deployment in drinking water reservoirs was investigated. UV-A (365 nm) photolysis was shown to be more effective than the UV/TiO2 photocatalytic system for the removal of Microcystis aeruginosa cells and microcystins. During photolysis, cell density significantly decreased over 5 days from an initial concentration of 5.8 × 106 cells mL−1 until few cells were left. Both intra- and extracellular microcystin concentrations were significantly reduced by 100 and 92 %, respectively, by day 5 of the UV treatment for all microcystin analogues. During UV/TiO2 treatment, there was great variability between replicates, making prediction of the effect on cyanobacterial cell and toxin behavior difficult. Postprint Postprint

Water radiolysis can serve as a useful tool to study the degradation of organic pollutants in water. Manipulation of the radiolytic system enables the selective production of reactive species (RS) with known yields. Our aim was to explore the effects of the radiolytically produced RS on commonly occuring water taste and odor compounds (T&O), 2-methylisoborneol (MIB) and geosmin (GSM). Observed degradation rate constants differ among experimental conditions/dominant RS and follow the order: HO•>H•>>eaq−>(O2−•/HO2•), ranging from 0.002 Gy−1 (O2−•/HO2•) to 0.083 Gy−1 (HO•) for MIB and from 0.006 Gy−1 (O2−•/HO2•) to 0.068 Gy−1 (HO•) for GSM. Degradation by HO• was very efficient, requiring 1.14 and 1.49 μmoles of HO• for each degraded μmole of MIB and GSM, respectively. The oxidative degradation of MIB by HO• proceeds with the production of carbonyl- and hydroxyl‑containing transformation products (TPs), leading to linear structures, while for GSM degradation proceeds with ring opening, followed by formation of carboxyl-groups. Fewer TPs are produced by HO2•, while degradation with H• led to numerous TPs, via dehydroxylation, dehydration and ring opening. Degradation with eaq−, yielded demethylated and rearranged TPs with formation of double bonds.

Many toxic and/or noxious cyanobacteria appear in nature with a filamentous, stacked cell arrangement called trichomes. Although water treatment can be optimized to keep cyanobacterial cells intact and avoid the release of toxic and/or noxious compounds, many physical and chemical stresses encountered during the treatment process may result in trichome truncation, decreasing treatment efficiency by allowing single cells or short trichomes to reach the product water. This makes it possible for harmful/noxious compounds as well as organic matter to enter the distribution system. Investigations in a pilot and three full-scale water treatment plants were carried out in order to elucidate the degree of trichome truncation across different unit processes. It was found that genera (Pseudanabaena, Planktolyngbya) with short trichomes (

In the past twenty years marine biotoxin analysis in routine regulatory monitoring has advanced significantly in Europe (EU) and other regions from the use of the mouse bioassay (MBA) towards the high-end analytical techniques such as high-performance liquid chromatography (HPLC) with tandem mass spectrometry (MS). Previously, acceptance of these advanced methods, in progressing away from the MBA, was hindered by a lack of commercial certified analytical standards for method development and validation. This has now been addressed whereby the availability of a wide range of analytical standards from several companies in the EU, North America and Asia has enhanced the development and validation of methods to the required regulatory standards. However, the cost of the high-end analytical equipment, lengthy procedures and the need for qualified personnel to perform analysis can still be a challenge for routine monitoring laboratories. In developing regions, aquaculture production is increasing and alternative inexpensive Sensitive, Measurable, Accurate and Real-Time (SMART) rapid point-of-site testing (POST) methods suitable for novice end users that can be validated and internationally accepted remain an objective for both regulators and the industry. The range of commercial testing kits on the market for marine toxin analysis remains limited and even more so those meeting the requirements for use in regulatory control. Individual assays include enzyme-linked immunosorbent assays (ELISA) and lateral flow membrane-based immunoassays (LFIA) for EU-regulated toxins, such as okadaic acid (OA) and dinophysistoxins (DTXs), saxitoxin (STX) and its analogues and domoic acid (DA) in the form of three separate tests offering varying costs and benefits for the industry. It can be observed from the literature that not only are developments and improvements ongoing for these assays, but there are also novel assays being developed using upcoming state-of-the-art biosensor technology. This review focuses on both currently available methods and recent advances in innovative methods for marine biotoxin testing and the end-user practicalities that need to be observed. Furthermore, it highlights trends that are influencing assay developments such as multiplexing capabilities and rapid POST, indicating potential detection methods that will shape the future market.

To date, the high cost of supplying UV irradiation has prevented the widespread application of UV photolysis and titanium dioxide based photocatalysis in removing undesirable organics in the water treatment sector. To overcome this problem, the use of UV-LEDs (365 nm) for photolysis and heterogeneous photocatalysis applying TiO

Funding: the Engineering and Physical Sciences Research Council, UK (Global Challenge Research Fund: EP/P029280/1) towards carrying out this research. We also thank the support on electron microscopes from EPSRC Capital for Great Technologies (Grant EP/LP017008/1 and EP/R02375/1). Many drinking water reservoirs can contain organic pollutants such as artificial synthesized dye and drugs. On the other hand, some naturally occurring microorganisms such as cyanobacteria, are capable of producing toxic secondary metabolites (cyanotoxins) causing detrimental health effects in humans and animals are also present in water reservoirs. Photocatalytic destruction of organic pollutants in-reservoir requires not only good photo-catalytically activity but also efficacy of distribution and recycling. We report here, a facile calcination method of coating graphitic carbon nitride (g-C3N4) onto porous glass beads. Influences of precursor and heating temperature on photocatalytic activity were evaluated by photocatalytic degradation of methyl orange. The yellow floating beads show comparable activity to P25 (TiO2) coated beads in the removal of two of the most frequently occurring cyanobacterial toxins, microcystin-LR and cylindrospermopsin, in artificial freshwater under UV light irradiation. Microcystin-LR was destroyed within 60 min and cylindrospermopsin was removed after 100 min UV irradiation. The coated g-C3N4 layer is very robust and shows negligible degradation on photocatalytic performance when recycled. The recycling of the photocatalyst is very simple because of the large size of the catalyst-coated beads. A large batch was successfully produced in a lab tube furnace. For further application, the ability of g-C3N4 absorbing visible light could pave the way to utilise sunlight for the destruction of toxins in the water. Postprint

International audience; Primary consumers in freshwater ecosystems, such as the zooplankton organism Daphnia magna, are highly affected by cyanobacteria, both as they may use it as a food source but also by cyanobacterial metabolites present in the water. Here, we investigate the impacts of cyanobacterial metabolites focussing on the environmental realistic scenario of the naturally released mixture without crushing cyanobacterial cells or their uptake as food. Therefore, D. magna were exposed to two concentrations of cell free cyanobacterial spent medium from Microcystis aeruginosa PCC 7806 to represent higher and lower ecologically-relevant concentrations of cyanobacterial metabolites. Including microcystin-LR, 11 metabolites have been detected of which 5 were quantified. Hypothesising concentration and time dependent negative impact, survival, gene expression marking digestion and metabolism, oxidative stress response, cell cycle and molting as well as activities of detoxification and antioxidant enzymes were followed for 7 days. D. magna suffered from oxidative stress as both catalase and glutathione S-transferase enzyme activities significantly decreased, suggesting enzyme exhaustibility after 3 and 7 days. Moreover, gene-expressions of the 4 stress markers (glutathione S-transferase, glutathione peroxidase, catalase and thioredoxin) were merely downregulated after 7 days of exposure. Energy allocation (expression of glyceraldehyde-3-phosphate dehydrogenase) was increased after 3 days but decreased as well after 7 days exposure. Cell cycle was impacted time dependently but differently by the two concentrations, along with an increasing downregulation of myosin heavy chain responsible for cell arrangement and muscular movements. Deregulation of nuclear hormone receptor genes indicate that D. magna hormonal steering including molting seemed impaired despite no detection of microviridin J in the extracts. As a consequence of all those responses and presumably of more than investigated molecular and physiological changes, D. magna survival was impaired over time, in a concentration dependent manner. Our results confirm that besides microcystin-LR, other secondary metabolites contribute to negative impact on D. magna survival and stress response.

Renewable energy, especially biofuels, has the potential to supplement a part of the existing fossil-based transportation fuels. Biofuels such as bioethanol can be produced from established glucose fermentation processes; however, cheap and efficient glucose production is a hindering factor. Cellulose, the world’s most abundant organic material, is a polymer of glucose and is locked within the lignocellulosic framework of plants. Pre-treatment is required to facilitate effective cellulose saccharification. Semiconductor photocatalysis, an advanced oxidation process, is a potential method for cellulose breakdown and the focus of this chapter will be on harnessing photocatalysis for cellulose-based renewable energy production.

Cyanobacterial blooms are increasingly reported worldwide, presenting a challenge to water treatment plants and concerning risks to human health and aquatic ecosystems. Advanced oxidative processes comprise efficient and safe methods for water treatment. Hydrogen peroxide (H2O2) has been proposed as a sustainable solution to mitigate bloom-forming cyanobacteria since this group presents a higher sensitivity compared to other phytoplankton, with no major risks to the environment at low concentrations. Here, we evaluated the effects of a single H2O2 addition (10 mg L−1) over 120 h in mesocosms introduced in a reservoir located in a semi-arid region presenting a Planktothrix-dominated cyanobacterial bloom. We followed changes in physical and chemical parameters and in the bacterioplankton composition. H2O2 efficiently suppressed cyanobacteria, green algae, and diatoms over 72 h, leading to an increase in transparency and dissolved organic carbon, and a decrease in dissolved oxygen and pH, while nutrient concentrations were not affected. After 120 h, cyanobacterial abundance remained low and green algae became dominant. 16S rRNA sequencing revealed that the original cyanobacterial bloom was composed by Planktothrix, Cyanobium and Microcystis. Only Cyanobium increased in relative abundance at 120 h, suggesting regrowth. A prominent change in the composition of heterotrophic bacteria was observed with Exiguobacterium, Paracoccus and Deinococcus becoming the most abundant genera after the H2O2 treatment. Our results indicate that this approach is efficient in suppressing cyanobacterial blooms and improving water quality in tropical environments. Monitoring changes in abiotic parameters and the relative abundance of specific bacterial taxa could be used to anticipate the regrowth of cyanobacteria after H2O2 degradation and to indicate where in the reservoir H2O2 should be applied so the effects are still felt in the water treatment plant intake.

The presence of harmful algal bloom in many reservoirs around the world, alongside the lack of sanitation law/ordinance regarding cyanotoxin monitoring (particularly in developing countries), create a scenario in which the local population could potentially chronically consume cyanotoxin-contaminated waters. Therefore, it is crucial to develop low cost tools to detect possible systems failures and consequent toxin release inferred by morphological changes of cyanobacteria in the raw water. This paper aimed to look for the best combination of convolutional neural network (CNN), optimizer and image segmentation technique to differentiate P. agardhii trichomes before and after chemical stress caused by the addition of hydrogen peroxide. This method takes a step towards accurate monitoring of cyanobacteria in the field without the need for a mobile lab. After testing three different network architectures (AlexNet, 3ConvLayer and 2ConvLayer), four different optimizers (Adam, Adagrad, RMSProp and SDG) and five different image segmentations methods (Canny Edge Detection, Morphological Filter, HP filter, GrabCut and Watershed), the combination 2ConvLayer with Adam optimizer and GrabCut segmentation, provided the highest median accuracy (93.33%) for identifying H2O2-induced morphological changes in P. agardhii. Our results emphasize the fact that the trichome classification problem can be adequately tackled with a limited number of learned features due to the lack of complexity in micrographs from before and after chemical stress. To the authors' knowledge, this is the first time that CNNs were applied to detect morphological changes in cyanobacteria caused by chemical stress. Thus, it is a significant step forward in developing low cost tools based on image recognition, to shield water consumers, especially in the poorest regions, against cyanotoxin-contaminated water.

Scotch Whisky is an important global commodity which generates extensive co-product known as pot ale or spent wash (> 10 L co-product per L whisky). Whilst this is often used as fertiliser or animal feed, a proportion requires disposal resulting in cost to the distillery along with the negative impact on the carbon footprint due to transportation. This study examined the composition of the soluble fraction of pot ale from twenty-two distilleries in Scotland in order to assess the potential for resource recovery and transition to a more circular economy. The results reinforced previous studies, demonstrating that pot ale is an excellent source of protein with a potential for recovery >150, 000 t per annum in Scotland based on Whisky production data. Lactic acid, an important industrial platform chemical, was the major organic acid produced with concentrations ranging from 0.3 to 6.6 g L−1, representing a potential opportunity for recovery for applications such as manufacture of biodegradable polylactic acid for plastics (> 15,000 t per annum based on mean values). Other important platform chemicals, succinic acid and lysine were also identified and considered in sufficient amounts for future use. Pot ale was also shown to contain significant amounts of critical raw materials, magnesium and phosphate, which could be reclaimed for use in fertiliser/feed supporting the development of a new circular economy whilst at the same time reducing the burden of mining and transportation on the environment. The data in this study demonstrated a potential 13.8 kt recoverable phosphate per annum representing more than half of the annual fertiliser consumption in Scotland. Whisky co-products can contribute to sustainable energy, food and platform chemicals with the added value that metal concentrations are not sufficiently high to prevent its utilisation.

It is proposed that microplastics discharged from wastewater treatment plants act as a vector of pharmaceuticals. In this study, adsorption of pharmaceuticals to polyethylene microplastics was investigated in municipal wastewater. Pharmaceuticals for study were selected to represent different speciation (anionic, cationic, and neutral) and a range of pH dependant octanol-water distribution coefficients (log DOW). Findings revealed adsorption favoured those in cationic form with the greatest hydrophobicity (e.g., fluoxetine log DOW 2.0 at pH 7.8). Adsorption of anionic pharmaceuticals was restricted due to repulsion with the microplastic's negatively charged surface. Only atorvastatin had any appreciable adsorption due to its comparatively high log DOW value (2.9). Those pharmaceuticals predominantly in neutral form (carbamazepine and ketamine) with log DOW values ≥2.4 had similar adsorption. Freundlich KF values were 3400, 386, 284, 259 and 218 (mg kg−1)(mg L−1)1/n for fluoxetine, propranolol, atorvastatin, ketamine, and carbamazepine, respectively. All pharmaceuticals with log DOW values

Reported here is the first study to investigate the adsorption of pharmaceutical drugs to microplastics in wastewater. Wastewater is an environmental source of microplastics and pharmaceuticals, which is discharged as treated effluent or combined sewer overflows. In this study, adsorption of cationic pharmaceuticals, with a range of octanol-water distribution coefficients, to polyamide (Nylon 12) microplastics was investigated in real wastewater samples. Significant adsorption was observed for the more hydrophobic pharmaceuticals studied, propranolol, amitriptyline, and fluoxetine, with equilibrium reached within 24 h. Microplastic-wastewater distribution coefficients for these three pharmaceuticals were 191, 749 and 1020 L kg−1, respectively. Favourable wastewater conditions for adsorption of pharmaceuticals to polyamide were at pH > 7, summer temperatures (20 °C), and no stormwater dilution. Adsorption of the more hydrophilic pharmaceuticals atenolol, pseudoephedrine, metoprolol, and tramadol was ≤7% under all conditions and considered insignificant. Limited desorption (7–17%) of propranolol, amitriptyline, and fluoxetine was observed in river water over 24 h. This suggests that microplastics may be able to transport adsorbed pharmaceuticals for considerable distances after discharge. In simulated gastric fluids their desorption increased to 24–27% and 40–58% in cold- and warm-blooded temperatures respectively. The findings demonstrate that wastewater microplastics could act as a vector of pharmaceutical drugs, from wastewater treatment plants to aquatic organisms. However, further research is needed to better appreciate the risks posed by pharmaceuticals adsorbed to microplastics in comparison to other organic particulates found in wastewater.

Cyanobacterial blooms are a serious threat to public health and water quality due to the production of cyanotoxins as a result of nutrient pollution from industry, agriculture, domestic waste as well as global warming. The microcystins (MCs) are the most abundant cyanotoxins consisting of >200 analogues causing both acute and chronic toxicity, sometimes resulting in death. In Asian countries, such as Sri Lanka, reports of kidney disease are constantly increasing. Although no direct link between metal and pesticide contamination in water and kidney disease has been found, high concentration of cyanobacteria cells in drinking water wells implies that the nephrotoxic effects of cyanotoxins might play a key factor in the reports of Chronic Kidney Disease of unknown aetiology (CKDu) in Sri Lanka. Therefore, we propose a nature-based approach for water treatment which will study the hypotheses that cyanotoxins can cause CKDu. Sri Lankan bacterial isolates (Alcaligens sp., Roseateles sp., Bacillus sp., and Micrococcus sp.) known to degrade microcystins, were used to form biofilm on biochar from Sri Lankan crop residues, such as coconut shells. The immobilisation of the microbes was assessed via a high-throughput colourimetric assay, followed by monitoring the biodegradation rate of microcystins when added to the immobilised cultures. Biodegradation products were analysed and identified through molecular networking and quantified via LC-MS/MS. Ultimately, this project will provide safe water in line with UN Sustainable Development Goal 6.1 as well contributing in sustainable goals 7 (Affordable and Clean Energy), 11 (Sustainable Cities and Communities) and 12 (Responsible Production and Consumption).

Cyanobacterial blooms are observed when high cell densities occur and are often dangerous to human and animal health due to the presence of cyanotoxins. Conventional drinking water treatment technology struggles to efficiently remove cyanobacterial cells and their metabolites during blooms, increasing costs and decreasing water quality. Although field applications of hydrogen peroxide have been shown to successfully suppress cyanobacterial growth, a rapid and accurate measure of the effect of oxidative stress on cyanobacterial cells is required. In the current study, H2O2 (5 and 20 mg L−1) was used to induce oxidative stress in Microcystis aeruginosa PCC 7813. Cell density, quantum yield of photosystem II, minimal fluorescence and microcystin (MC-LR, -LY, -LW, -LF) concentrations were compared when evaluating M. aeruginosa cellular stress. Chlorophyll content (determined by minimal fluorescence) decreased by 10% after 48 h while cell density was reduced by 97% after 24 h in samples treated with 20 mg L−1 H2O2. Photosystem II quantum yield (photosynthetic activity) indicated cyanobacteria cell stress within 6 h, which was considerably faster than the other methods. Intracellular microcystins (MC-LR, -LY, -LW and -LF) were reduced by at least 96% after 24 h of H2O2 treatment. No increase in extracellular microcystin concentration was detected, which suggests that the intracellular microcystins released into the surrounding water were completely removed by the hydrogen peroxide. Thus, photosynthetic activity was deemed the most suitable and rapid method for oxidative cell stress detection in cyanobacteria, however, an approach using combined methods is recomended for efficient water treatment management.

The increasing presence of freshwater toxins have brought new challenges to preserve water quality due to their potential impact on the environment and human health. Two commonly occurring cyanotoxins, microcystin-LR and cylindrospermopsin, with different physico-chemical properties were used to evaluate the efficiency of photocatalysis using a continuous-flow reactor with immobilized TiO

Cyanobacteria and their toxic secondary metabolites are a challenge in water treatment due to increased biomass and dissolved metabolites in the raw water. Retrofitting existing water treatment infrastructure is prohibitively expensive or unfeasible, hence 'in-reservoir' treatment options are being explored. In the current study, a treatment system was able to photocatalytically inhibit the growth of Microcystis aeruginosa and remove released microcystins by photocatalysis using titanium dioxide coated, porous foamed glass beads and UV-LEDs (365 nm). A 35% reduction of M. aeruginosa PCC7813 cell density compared to control samples was achieved in seven days. As a function of cell removal, intracellular microcystins (microcystin-LR, -LY, -LW, and -LF) were removed by 49% from 0.69 to 0.35 μg mL

Authors wish to thank EPSRC Global Challenges program for providing the funding for this project (Grant number EP/P029280/1). NS wishes to thank ‘Energy Pioneering Research Program (PRP)’ at QUB. JTSI and JH wish to acknowledge EPSRC Capital for Great Technologies (Grant EP/LP017008/1and EP/R02375/1). Blooms of blue-green algae (cyanobacteria) in water reservoirs frequently produce highly toxic secondary metabolites including microcystins which have resulted in both human and animal fatalities. To tackle this global problem, we present here a viable solution: utilising the photo-catalytic power of TiO2 immobilised on glass beads that are encased in ‘photo-reactor pods’, equipped with UV LEDs, for the photocatalytic destruction of cyanotoxins. These reactor pods are designed in such a way that they can be used continuously with the aid of a power supply to facilitate the photocatalytic process. This process could be used to address one of the Global Challenges: providing safe drinking water around the globe. Postprint

Photocatalysis has been shown to successfully remove microcystins (MC) in laboratory experiments. Most research to date has been performed under ideal conditions in pure or ultrapure water. In this investigation the efficiency of photocatalysis using titanium dioxide was examined in a complex matrix (waste stabilisation lagoon water). A flow-through photocatalytic reactor was used for the photocatalytic removal of four commonly occurring microcystin analogues (MC-YR, MC-RR, MC-LR, and MC-LA). Up to 51% removal for single MC analogues in waste lagoon water was observed. Similar removal rates were observed when a mixture of all four MC analogues was treated. Although treatment of MC-containing cyanobacterial cells of Microcystis aeruginosa resulted in no decline in cell numbers or viability with the current reactor design and treatment regime, the photocatalytic treatment did improve the overall quality of waste lagoon water. This study demonstrates that despite the presence of natural organic matter the microcystins could be successfully degraded in a complex environmental matrix.

International audience; Due to eutrophication, freshwater ecosystems frequently experience cyanobacterial blooms, many of which produce bioactive metabolites that can affect vertebrates and invertebrates life traits. Zooplankton are able to develop tolerance as a physiological response to cyanobacteria and their bioactive compounds, however, this comes with energetic cost that in turn influence Daphnia life traits and may impair populations. Vice versa, it has been suggested that Daphnia are able to reduce cyanobacterial dominance until a certain cyanobacterial density; it remains unclear whether Daphnia metabolites alone influence the physiological state and bioactive metabolites production of cyanobacteria. Hence, this study investigates mutual physiological reactions of toxic Microcystis aeruginosa PCC7806 and Daphnia magna. We hypothesize that a) the presence of D. magna will negatively affect growth, increase stress response and metabolites production in M. aeruginosa PCC7806 and b) the presence of M. aeruginosa PCC7806 will negatively affect physiological responses and life traits in D. magna. In order to test these hypotheses experiments were conducted in a specially designed co-culture chamber that allows exchange of the metabolites without direct contact. A clear mutual impact was evidenced. Cyanobacterial metabolites reduced survival of D. magna and decreased oxidative stress enzyme activity. Simultaneously, presence of D. magna did not affect photosynthetic activity. However, ROS increase and tendencies in cell density decrease were observed on the same day, suggesting possible energy allocation towards anti-oxidative stress enzymes, or other protection mechanisms against Daphnia infochemicals, as the strain managed to recover. Elevated concentration of intracellular and overall extracellular microcystin MC-LR, as well as intracellular concentrations of aerucyclamide A and D in the presence of Daphnia, indicating a potential protective or anti-grazing function. However, more research is needed to confirm these findings.

A simple, rapid UHPLC-MS/MS method has been developed and optimised for the quantitation of microcystins and nodularin in wide variety of sample matrices. Microcystin analogues targeted were MC-LR, MC-RR, MC-LA, MC-LY, MC-LF, LC-LW, MC-YR, MC-WR, [Asp3] MC-LR, [Dha7] MC-LR, MC-HilR and MC-HtyR. Optimisation studies were conducted to develop a simple, quick and efficient extraction protocol without the need for complex pre-analysis concentration procedures, together with a rapid sub 5min chromatographic separation of toxins in shellfish and algal supplement tablet powders, as well as water and cyanobacterial bloom samples. Validation studies were undertaken on each matrix-analyte combination to the full method performance characteristics following international guidelines. The method was found to be specific and linear over the full calibration range. Method sensitivity in terms of limits of detection, quantitation and reporting were found to be significantly improved in comparison to LC-UV methods and applicable to the analysis of each of the four matrices. Overall, acceptable recoveries were determined for each of the matrices studied, with associated precision and within-laboratory reproducibility well within expected guidance limits. Results from the formalised ruggedness analysis of all available cyanotoxins, showed that the method was robust for all parameters investigated. The results presented here show that the optimised LC-MS/MS method for cyanotoxins is fit for the purpose of detection and quantitation of a range of microcystins and nodularin in shellfish, algal supplement tablet powder, water and cyanobacteria. The method provides a valuable early warning tool for the rapid, routine extraction and analysis of natural waters, cyanobacterial blooms, algal powders, food supplements and shellfish tissues, enabling monitoring labs to supplement traditional microscopy techniques and report toxicity results within a short timeframe of sample receipt. The new method, now accredited to ISO17025 standard, is simple, quick, applicable to multiple matrices and is highly suitable for use as a routine, high-throughout, fast turnaround regulatory monitoring tool.

Cost-effective, efficient, and sustainable water treatment solutions utilising existing materials and technology will make it easier for low and middle-income countries to adopt them, improving public health. The ability of biochar to mediate and support microbial degradation of contaminants, combined with its carbon-sequestration potential, has attracted attention in recent years. Biochar is a possible candidate for use in cost-effective and sustainable biological water treatment, especially in agrarian economies with easy access to abundant biomass in the form of crop residues and organic wastes. This review evaluates the scope, potential benefits (economic and environmental) and challenges of sustainable biological water treatment using ‘Biologically-Enhanced Biochar’ or BEB. We discuss the various processes occurring in BEB systems and demonstrate the urgent need to investigate microbial degradation mechanisms. We highlight the need to correlate biochar properties to biofilm development, which can eventually determine process efficiency. We also demonstrate the various opportunities in adopting BEB as a cheaper and more viable alternative in Low and Middle Income Countries and compare it to the current benchmark, ‘Biological Activated Carbon’. We focus on the recent advances in the areas of data science, mathematical modelling and molecular biology to systematically and sustainably design BEB filters, unlike the largely empirical design approaches seen in water treatment. ‘Sequential biochar systems’ are introduced as specially designed end-of-life techniques to lower the environmental impact of BEB filters and examples of their integration into biological water treatment that can fulfil zero waste criteria for BEBs are given.

Although some studies have investigated the impact caused by chemicals used on water treatment (coagulants and oxidants) on cyanobacteria integrity, the isolated effect of shear stress during coagulation is still not fully understood. This study evaluated the impact of different velocity gradients, mixing times, and the addition of powdered activated carbon (PAC) on the integrity of Microcystis aeruginosa, Raphidiopsis raciborskii, and Dolichospermum circinale, known producers of toxin and taste and odor (T&O) compounds. No association was found between R. raciborskii cell lysis and velocity gradient, with or without PAC, demonstrating the high resilience of this taxon to shear stress. In contrast, an association was found for M. aeruginosa at the highest velocity gradient evaluated (1000 s−1) and for D. circinale above the lowest velocity gradient studied (600 s−1). After PAC addition, there was a reduction in the chances of finding M. aeruginosa intact cells above velocity gradient 800 s−1 at 45 s, while D. circinale show cell lysis in all the scenarios expect at 600 s−1 and 10 s of agitation. The additional impact of PAC on cell lysis may lead to more release of metabolites and shows the need to adjust the hydraulic conditions in the rapid mixing stage, especially when more “fragile” cyanobacteria are present. Neither cyanobacterial cell size nor morphology was shown to be relevant to shear stress sensitivity, indicating that cell wall composition might have been an important factor in controlling cell lysis.

Alternative renewable energy must emerge to sustainably meet the energy demands of the present and future. Current alternatives to fossil fuels are electricity from solar, wind and tidal energies and biofuels. Biofuels, especially bioethanol could be produced from lignocellulosic feedstock via pre-treatment and fermentation. The cellulose I content of most lignocellulosic feedstock is significant, yet its highly crystalline amphiphilic structure interlinked with the lignin network makes it difficult to process for bioethanol production. Processing lignocellulosic biomass via a range of physico-chemical, mechanical and biological pre-treatment methods have been well established, however a relatively new area on the use of cellulose II (a polymorph of native cellulose obtained via mercerisation or regeneration) for the production of bioethanol is still in its early stages. Hence, this review discusses in detail the advantages of using cellulose II over cellulose I as feedstock for bioethanol production. Furthermore, current green and sustainable methods for cellulose II production and the advantages and disadvantages of each method are discussed. In addition, examples from literature reporting higher fermentable sugar and bioethanol yields using cellulose II as feedstock are reviewed, thereby highlighting its importance in the field of bioethanol production. The conclusion from this review suggests that, in all the cases studied, fermentable sugar and/or bioethanol production was found to be higher when cellulose II was used as feedstock instead of native cellulose/lignocellulosic biomass. This higher yield could be attributed to the modified structural and lattice arrangement of cellulose II, its porous volume and degree of polymerisation. Postprint

A novel photocatalytic reactor based on a stirred tank configuration has been described. This reactor employs the use of photocatalytic impellers to aid the mass transport of gaseous organic compounds during photocatalytic reactions. Experiments involving toluene vapour photo-oxidation showed the reactor configuration is susceptible to catalyst deactivation even at low concentrations if treated for prolonged periods. For this reactor, the reactive time scale exceeds the diffusive time scale hence, toluene photo-oxidation was reaction limited. The dependency of photonic efficiency of the reaction on mass transfer and catalyst deactivation was observed when correlated with the Damkohler number and deactivation induced reduction reaction rates respectively. The results show an inverse variation with Damkohler number and proportionality to reaction rates.

Background: Microcystins are cyclic peptides containing seven amino acids with the condensation of two terminal amino acids of the linear peptide to form a cyclic compound. The cyclic nature of microcystins suggests that they are highly stable in water across a wide range of pH and temperatures. Microcystins are produced by several blue-green algae (cyanobacteria) including Microcystis, Anabaena, Planktothrix, Oscillatoria and Radiocystis commonly found in freshwater reservoirs in Ghana. Microcystins have very serious health implications on both humans and animals. Known symptoms associated with microcystin poisoning include skin irritation, allergic responses, mucosa blistering, muscular and joint pains, gastroenteritis, pulmonary consolidation, liver and kidney damage and other neurological effects. Methods: In this study, we present results of toxicological analysis conducted on water samples from the Brimsu and Kwanyarko Reservoirs used as sources of drinking water by some parts of the Central Region of Ghana in 2011. HPLC was used to measure microcystin and phytoplankton was identified using an inverted microscope. Results: HPLC analyses of samples gave four variants of microcystin, MC-LR, MC-YR, MC-RR and MC-LA with microcystins ranging from 0.79 μg/L during the intake of water at the Brimsu treatment plant to 0.1 μg/L in the final drinking water products of both reservoirs. Microcystin-LA is a microcystin variant identified in Ghana for the first time. Cyanobacteria diversity was low in both reservoirs. However, biomass was very high and constituted about 84% and 93% of the total algal counts of the water intake for Kwanyarko and Brimsu Reservoirs respectively. Dominant cyanobacteria species found in these reservoirs are Microcystis aeroginosa and Planktothrix agardhii. Conclusions: Due to the chronic effect of these toxins it is recommended that drinking reservoirs with low levels of microcystins must be regularly monitored to keep it free from microcystin to ensure safeguarding human health.

This work was supported by the Engineering and Physical Sciences Research Council (Project number EP/K036769/1), Robert Gordon University’s IDEAS PhD studentship and Queen’s University Belfast’s PhD studentship. To sustainably meet the global energy demand, unconventional methods to produce renewable energy must emerge. Biofuels from cellulose (via fermentable sugar production) mediated via photocatalysis provides an alternative to conventional fossil fuels. In order to effectively drive photocatalytic processes an effective reactor design is required, the design of which is influenced by a number of key factors such as the catalyst to reactant ratio and residence time, catalyst illumination time, light penetration and distribution for the system, mass transfer limitations (mixing) and product recovery. In this study we use COMSOL Multiphysics® to simulate and assess one of the mentioned parameters – mixing regime of cellulose particles in a Stacked Frame Photocatalysis Reactor (SFPR). In the reactor design, we compare two mixers: a ‘plus’ shaped magnetic stirrer bar and an 8 blade Rushton impeller. The simulations reveal that the Rushton impeller offers a radial mixing pattern with a higher fluid velocity of 1.2 m/s when compared to the stirrer bar that offers a fluid velocity of 0.9 m/s. Cellulose particle tracing simulations confirm that the particle dispersion is superior in the case of the Rushton impeller as the vorticity generated during the mixing push the particles to the reactor’s walls. Since the particles are forced towards the walls, there is a probability of more particles being illuminated than in the case of no or improper mixing. Postprint

Nodularia spumigena is one of the dominant toxic cyanobacteria which produce blooms in the Baltic Sea, a brackish water body, particularly in late summer. Nodularia spp. are known to produce hepatotoxic nodularins (NODs) and other bioactive peptides such as spumigins and nodulopeptins. In a recent study, three new nodulopeptins with a molecular weight of 899, 901 and 917 Da were characterized from N. spumigena KAC66. To gain further insight into the effects of environmental stress on growth and production of bioactive metabolites in N. spumigena KAC66, two parameters were investigated: temperature and salinity. It was found that growth conditions have a considerable effect on biomass and toxin levels of N. spumigena KAC66. Increasing temperature had a profound effect on NOD production with an increase from 22 to 25 °C resulting in a 50% decrease in intracellular NOD levels. At 30 °C, little or no NOD was detected. In contrast, while concentrations of nodulopeptin 901 decreased with increasing temperature, it was still detectable throughout the growth cycle at elevated temperatures. The light intensity of 13 μmol photons m−2 s−1, 22 °C and 11–20‰ salinity were optimal growth conditions to obtain maximum biomass, intra- and extracellular peptide productions. This is the first report to evaluate the effects of selected environmental parameters on NOD/nodulopeptin 901 productions which ultimately may be helpful to explain the distribution, control of natural blooms and toxin levels of N. spumigena in the Baltic Sea, as well as in laboratory based experiments.

This paper presents the scientific investigation of three Lemnian sphragides (terra sigillata, stamped earth), a famed medicinal clay in antiquity, dated to the sixteenth–seventeenth centuries, and presently in the Museum for the History of Pharmacy, University of Basel. The three specimens are compared with clays from the purported locality of its extraction, at Kotsinas, NE Lemnos, Greece. The study suggests a local origin for the Basel samples; it also demonstrates, for the first time, that the three Lemnian sphragides have a significant antibacterial effect against Staphylococcus aureus, a common Gram-positive pathogen, but have no such effect against Pseudomonas aeruginosa, a Gram-negative microorganism. Clay samples from the purported locality of extraction showed no antibacterial effect against S. aureus. Subsequent analysis with ultra-performance liquid-chromatography mass spectrometry (UPLC-MS) revealed the presence of organic constituents in one sphragis which were absent from a sample of modern clay. A fungal secondary metabolite is proposed here as the active ingredient but other factors may also play a role. The ongoing investigation into the bioactivity of some medicinal clays might aid in the re-evaluation of Belon's statement included at the start of this paper, namely, that the Lemnian earth worked only because people in the past wished it to work.

While the intracellular function of many toxic and bioactive cyanobacterial metabolites is not yet known, microcystins have been suggested to have a protective role in the cyanobacterial metabolism, giving advantage to toxic over nontoxic strains under stress conditions. The zooplankton grazer Daphnia reduce cyanobacterial dominance until a certain density, which may be supported by Daphnia exudates, affecting the cyanobacterial physiological state and metabolites&rsquo, production. Therefore, we hypothesized that D. magna spent medium will impact the production of cyanobacterial bioactive metabolites and affect cyanobacterial photosynthetic activity in the nontoxic, but not the toxic strain. Microcystin (MC-LR and des-MC-LR) producing M. aeruginosa PCC7806 and its non-microcystin producing mutant were exposed to spent media of different D. magna densities and culture durations. D. magna spent medium of the highest density (200/L) cultivated for the shortest time (24 h) provoked the strongest effect. D.magna spent medium negatively impacted the photosynthetic activity of M. aeruginosa PCC7806, as well as the dynamics of intracellular and extracellular cyanobacterial metabolites, while its mutant was unaffected. In the presence of Daphnia medium, microcystin does not appear to have a protective role for the strain. On the contrary, extracellular cyanopeptolin A increased in M. aeruginosa PCC7806 although the potential anti-grazing role of this compound would require further studies.

Mr Colby Chang would like to acknowledge the International Intern Aboard Program at Princeton University and Queens University Belfast (QUB) for funding his internship. Dr Sanjay Nagarajan would like to acknowledge QUB for funding his research while Dr Nathan Skillen would like to acknowledge the Pioneering Research Program at QUB for funding his research. Efficient energy production and waste valorisation are the most challenging fields in photocatalysis. Reported here is enhanced hydrogen production from cellulose, achieved through the conversion of cellulose I to II via a simple pretreatment step. Postprint Postprint

Photocatalysis has been shown to successfully remove microcystins (MC) in laboratory experiments. Most research to date has been performed under ideal conditions in pure or ultrapure water. In this investigation the efficiency of photocatalysis using titanium dioxide was examined in a complex matrix (waste stabilisation lagoon water). A flow-through photocatalytic reactor was used for the photocatalytic removal of four commonly occurring microcystin analogues (MC-YR, MC-RR, MC-LR, and MC-LA). Up to 51% removal for single MC analogues in waste lagoon water was observed. Similar removal rates were observed when a mixture of all four MC analogues was treated. Although treatment of MC-containing cyanobacterial cells of Microcystis aeruginosa resulted in no decline in cell numbers or viability with the current reactor design and treatment regime, the photocatalytic treatment did improve the overall quality of waste lagoon water. This study demonstrates that despite the presence of natural organic matter the microcystins could be successfully degraded in a complex environmental matrix.