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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.

Cyanotoxins (CTs) produced by cyanobacteria in surface freshwater are a major threat for public health and aquatic ecosystems. Cyanobacteria can also produce a wide variety of other understudied bioactive metabolites such as oligopeptides microginins (MGs), aeruginosins (AERs), aeruginosamides (AEGs) and anabaenopeptins (APs). This study reports on the co-occurrence of CTs and cyanopeptides (CPs) in Lake Vegoritis, Greece and presents their variant-specific profiles obtained during 3-years of monitoring (2018–2020). Fifteen CTs (cylindrospermopsin (CYN), anatoxin (ATX), nodularin (NOD), and 12 microcystins (MCs)) and ten CPs (3 APs, 4 MGs, 2 AERs and aeruginosamide (AEG A)) were targeted using an extended and validated LC-MS/MS protocol for the simultaneous determination of multi-class CTs and CPs. Results showed the presence of MCs (MC-LR, MC-RR, MC-YR, dmMC-LR, dmMC-RR, MC-HtyR, and MC-HilR) and CYN at concentrations of &lt, 1 μg/L, with MC-LR (79%) and CYN (71%) being the most frequently occurring. Anabaenopeptins B (AP B) and F (AP F) were detected in almost all samples and microginin T1 (MG T1) was the most abundant CP, reaching 47.0 μg/L. This is the first report of the co-occurrence of CTs and CPs in Lake Vegoritis, which is used for irrigation, fishing and recreational activities. The findings support the need for further investigations of the occurrence of CTs and the less studied cyanobacterial metabolites in lakes, to promote risk assessment with relevance to human exposure.

Cyanobacteria are photosynthetic microorganisms distributed globally in aquatic and terrestrial environments. They are also industrially cultivated to be used as dietary supplements, as they have a high nutritional value; however, they are also known to produce a wide range of toxic secondary metabolites, called cyanotoxins. BMAA (β-methylamino-l-alanine) and its most common structural isomers, DAB (2,4-diaminobutyric acid) and AEG (N-2-aminoethylglycine) produced by cyanobacteria, are non-proteinogenic amino acids that have been associated with neurodegenerative diseases. A possible route of exposure to those amino acids is through consumption of food supplements based on cyanobacteria. The review critically discusses existing reports regarding the occurrence of BMAA, DAB and AEG in cyanobacteria and cyanobacteria-based food supplements. It is shown that inconsistencies in reported results could be attributed to performance of different methods of extraction and analysis applied and in ambiguities regarding determination of soluble and bound fractions of the compounds. The critical aspect of this review aims to grow awareness of human intake of neurotoxic amino acids, while results presented in literature concerning dietary supplements aim to promote further research, quality control as well as development of guidelines for cyanotoxins in food products.

The authors acknowledge COST Action ES 1105 "CYANOCOST Cyanobacterial blooms and toxins in water resources: Occurrence impacts and management" and COST Action Global Change Biology ES 1201 NETLAKE -Networking Lake Observatories in Europe" for contributing to this study through networking and knowledge sharing with European experts in the field. We acknowledge the members of the Global Lake Ecological Observatory Network (GLEON) for their collaborative spirit and enthusiasm that inspired the grassroots effort of the EMLS. E.M. was supported by a grant from the Swiss State Secretariat for Education, Research and Innovation to Bas Ibelings and by supplementary funding from University of Geneva. We thank Wendy Beekman for the nutrient analysis. We thank Pieter Slot for assisting with the pigment analysis. We thank Dr. Ian Jones for valuable feedback on an earlier version of the manuscript. We thank the Leibniz Institute of Freshwater Ecology and the Aquatic Microbial Ecology Group for logistic and technical support of J. Fonvielle and H.-P. Grossart, and the Leibniz Association for financial support. H.P. was supported by the US National Science Foundation (1840715, 1831096). A.C.'s work was funded by the Spanish Agencia Estatal de Investigacion and EU funds through the project CLIMAWET (CGL2015-69557-R). The collection of data for Lough Erne and Lough Neagh were funded by the Department of Agriculture, Environment and Rural Affairs, Northern Ireland. We are grateful to Kristiina Vuorio from the Freshwater Centre of the Finnish Environment institute for her help in organizing, collecting and analysing samples by the University of Jyvaskyla and to Gerald Dorflinger from the Water Development Department of Cyprus for his assistance with the sampling in Cyprus and for granting the CUT team permission to use WDD's equipment. Finally, we would like to thank the numerous other assistants that helped realizing each local survey. Open access funding provided by Universite de Geneve., To determine the drivers of phytoplankton biomass, we collected standardized morphometric, physical, and biological data in 230 lakes across the Mediterranean, Continental, and Boreal climatic zones of the European continent. Multilinear regression models tested on this snapshot of mostly eutrophic lakes (median total phosphorus [TP] = 0.06 and total nitrogen [TN] = 0.7 mg L-1), and its subsets (2 depth types and 3 climatic zones), show that light climate and stratification strength were the most significant explanatory variables for chlorophyll a (Chl a) variance. TN was a significant predictor for phytoplankton biomass for shallow and continental lakes, while TP never appeared as an explanatory variable, suggesting that under high TP, light, which partially controls stratification strength, becomes limiting for phytoplankton development. Mediterranean lakes were the warmest yet most weakly stratified and had significantly less Chl a than Boreal lakes, where the temperature anomaly from the long-term average, during a summer heatwave was the highest (+4 degrees C) and showed a significant, exponential relationship with stratification strength. This European survey represents a summer snapshot of phytoplankton biomass and its drivers, and lends support that light and stratification metrics, which are both affected by climate change, are better predictors for phytoplankton biomass in nutrient-rich lakes than nutrient concentrations and surface temperature., European Cooperation in Science and Technology (COST) ES 1105 ES 1201, Swiss State Secretariat for Education, Research and Innovation, University of Geneva, Leibniz Association, National Science Foundation (NSF) 1840715 1831096, Spanish Agencia Estatal de Investigacion, European Commission CGL2015-69557-R, Department of Agriculture, Environment and Rural Affairs, Northern Ireland

Biological and advanced chemical treatment of cyanotoxins and other cyanobacteria-related contaminants such as taste and odor compounds, results in the formation of myriad transformation products (TPs) prior to their mineralization to simpler compounds such as H2O and CO2. This chapter gives an overview of the TPs formed for the major groups of cyanotoxins, with both biological and chemical treatment processes. In addition, it provides detailed explanations on the mechanistic steps followed that lead up to the formation of stable TPs for each oxidant used. It becomes apparent that besides the oxidizing ability of each oxidant, TP formation can be affected by the experimental conditions used, including oxidant and catalyst dose, solution pH, and presence of scavengers. Finally, the toxic potential of TPs is discussed.

The production of β-Ν-methylamino-L-alanine (BMAA) in cyanobacteria is triggered by nitrogen-starvation conditions and its biological role, albeit unknown, is associated with nitrogen assimilation. In the present study, the effect of BMAA (773 μg L−1) on nitrogen metabolism and physiology of the non-diazotrophic cyanobacterium and non-BMAA producer, Synechococcus sp. TAU-MAC 0499, was investigated. In order to study the combined effect of nitrogen availability and BMAA, nitrogen-starvation conditions were induced by transferring cells in nitrogen-free medium and subsequently exposing the cultures to BMAA. After short-term treatment (180 min) and in the presence of nitrogen, BMAA inhibited glutamine synthetase, which resulted in low concentration of glutamine. In the absence of nitrogen, although there was no effect on glutamine synthetase, a possible perturbation in nitrogen assimilation is reflected on the significant decrease in glutamate levels. During the long-term exposure (24–96 h), growth, photosynthetic pigments and total protein were not affected by BMAA exposure, except for an increase in protein and phycocyanin levels at 48 h in nitrogen replete conditions. Results suggest that BMAA interferes with nitrogen assimilation, in a different way, depending on the presence or absence of combined nitrogen, providing novel data on the potential biological role of BMAA.

Heterogeneous photocatalysis can be a suitable add-on process to conventional wastewater treatment methods aiming to the full degradation of emerging contaminants contributing to water pollution. This work examines the photo-degradation of two frequently detected emerging contaminants (caffeine and salicylic acid) using titanium dioxide nanotubular films (TNTs) so as commercial TiO 2 nanoparticulate films (Evonik P25) for comparison. The TNT films were prepared by electrochemical anodization of titanium metal and reached lengths of 20 μm, with a high growth rate (10 μm/h). They present an open porous structure with large specific surface area suitable for efficient adsorption of the contaminants and formation of a large number of photocatalytic active sites. After calcination at 450 °C, TNT films obtain the anatase crystal structure, absorb well in the UV range and present significant photocatalytic activity with high degradation rates for both examined emerging pollutants. Furthermore, they present small variability of their photocatalytic efficiency in a big range of the solutions pH values and under consecutive photocatalytic cycles, rendering them suitable at various wastewater treatment conditions.

Cyanobacteria are a diverse group of photosynthetic Gram-negative bacteria that produce an array of secondary compounds with selective bioactivity against a broad spectrum of organisms and cell lines. In this study, 29 strains isolated from freshwaters in Greece were classified using a polyphasic approach and assigned to Chroococcales, Synechococcales, and Nostocales, representing 11 genera and 17 taxa. There were good agreements between 16S ribosomal RNA (rRNA)&ndash, cpcBA&ndash, internal genetic spacer (IGS) characterization and morphological features, except for the Jaaginema&ndash, Limnothrix group which appears intermixed and needs further elucidation. Methanol extracts of the strains were analyzed for cyanotoxin production and tested against pathogenic bacteria species and several cancer cell lines. We report for the first time a Nostoc oryzae strain isolated from rice fields capable of producing microcystins (MCs) and a Chlorogloeopsis fritschii strain isolated from the plankton of a lake, suggesting that this species may also occur in freshwater temperate habitats. Strains with very high or identical 16S rRNA gene sequences displayed different antibacterial and cytotoxic activities. Extracts from Synechococcus cf. nidulans showed the most potent antibacterial activity against Staphylococcus aureus, whereas Jaaginema sp. strains exhibited potent cytotoxic activities against human colorectal adenocarcinoma and hepatocellular carcinoma cells. Jaaginema Thessaloniki Aristotle University Microalgae and Cyanobacteria (TAU-MAC) 0110 and 0210 strains caused pronounced changes in the actin network and triggered the formation of numerous lipid droplets in hepatocellular carcinoma and green monkey kidney cells, suggesting oxidative stress and/or mitochondrial damage leading to apoptosis.

Visible light (VIS) photocatalysis has large potential as a sustainable water treatment process, however the reaction pathways and degradation processes of organic pollutants are not yet clearly defined. The presence of cyanobacteria cause water quality problems since several genera can produce potent cyanotoxins, harmful to human health. In addition, cyanobacteria produce taste and odor compounds, which pose serious aesthetic problems in drinking water. Although photocatalytic degradation of cyanotoxins and taste and odor compounds have been reported under UV-A light in the presence of TiO2, limited studies have been reported on their degradation pathways by VIS photocatalysis of these problematic compounds. The main objectives of this work were to study the VIS photocatalytic degradation process, define the reactive oxygen species (ROS) involved and elucidate the reaction mechanisms. We report carbon doped TiO2 (C-TiO2) under VIS leads to the slow degradation of cyanotoxins, microcystin-LR (MC-LR) and cylindrospermopsin (CYN), while taste and odor compounds, geosmin and 2-methylisoborneol, were not appreciably degraded. Further studies were carried-out employing several specific radical scavengers (potassium bromide, isopropyl alcohol, sodium azide, superoxide dismutase and catalase) and probes (coumarin) to assess the role of different ROS (hydroxyl radical OH, singlet oxygen (1)O2, superoxide radical anion [Formula: see text] ) in the degradation processes. Reaction pathways of MC-LR and CYN were defined through identification and monitoring of intermediates using liquid chromatography tandem mass spectrometry (LC-MS/MS) for VIS in comparison with UV-A photocatalytic treatment. The effects of scavengers and probes on the degradation process under VIS, as well as the differences in product distributions under VIS and UV-A, suggested that the main species in VIS photocatalysis is [Formula: see text] , with OH and (1)O2 playing minor roles in the degradation.

The present study was launched as a continuation of global efforts to tackle problems associated with two important aesthetic characteristics, taste and odor (T&O), of drinking water. The UV-A/Chlorine process, a promising advanced oxidation process (AOP), was evaluated for the first time for the removal of 2-isopropyl-3-methoxy pyrazine (IPMP), a widely reported compound in the literature that causes unpleasant taste and odor when present in water at or below the ng L-1 level. It was found that the studied process was efficient for the removal of IPMP in both ultrapure and drinking water. The initial chlorine dosage influenced significantly the degradation efficiency under initial neutral pH values. Degradation efficiency of IPMP was slightly inhibited by using drinking water as matrix. Scavenging experiments highlighted the significant role of various reactive species (e.g. HO, ClO, Cl, Cl2-) generated during the process that have not been studied comprehensively until now. In addition, the significant role of HO was further verified by Electron paramagnetic resonance spectroscopy (EPR) experiments. Overall, the formation of diverse radicals during the UV-A/Chlorine treatment enhanced the degradation of IPMP, promoting mainly the formation of hydroxy, hydroperoxy and dealkylated derivatives. In contrast, chlorinated by-products were only identified in traces.

Insight into how environmental change determines the production and distribution of cyanobacterial toxins is necessary for risk assessment. Management guidelines currently focus on hepatotoxins (microcystins). Increasing attention is given to other classes, such as neurotoxins (e.g., anatoxin-a) and cytotoxins (e.g., cylindrospermopsin) due to their potency. Most studies examine the relationship between individual toxin variants and environmental factors, such as nutrients, temperature and light. In summer 2015, we collected samples across Europe to investigate the effect of nutrient and temperature gradients on the variability of toxin production at a continental scale. Direct and indirect effects of temperature were the main drivers of the spatial distribution in the toxins produced by the cyanobacterial community, the toxin concentrations and toxin quota. Generalized linear models showed that a Toxin Diversity Index (TDI) increased with latitude, while it decreased with water stability. Increases in TDI were explained through a significant increase in toxin variants such as MC-YR, anatoxin and cylindrospermopsin, accompanied by a decreasing presence of MC-LR. While global warming continues, the direct and indirect effects of increased lake temperatures will drive changes in the distribution of cyanobacterial toxins in Europe, potentially promoting selection of a few highly toxic species or strains. © 2018 by the authors. Licensee MDPI, Basel, Switzerland., The authors acknowledge COST Action ES 1105 “CYANOCOST—Cyanobacterial blooms and toxins in water resources: Occurrence impacts and management” and COST Action ES 1201 “NETLAKE—Networking Lake Observatories in Europe” for contributing to this study through networking and knowledge sharing with European experts in the field. Evanthia Mantzouki was supported by a grant from the Swiss State Secretariat for Education, Research and Innovation (SERI) to Bas Ibelings and by supplementary funding from the University of Geneva. We thank Clare Ahnlund, Ena Suarez and Irene Gallego for helping out with the Swiss survey. We thank Wendy Beekman and Els J. Faassen for the nutrient and toxin analysis.

Under ongoing climate change and increasing anthropogenic activity, which continuously challenge ecosystem resilience, an in-depth understanding of ecological processes is urgently needed. Lakes, as providers of numerous ecosystem services, face multiple stressors that threaten their functioning. Harmful cyanobacterial blooms are a persistent problem resulting from nutrient pollution and climate-change induced stressors, like poor transparency, increased water temperature and enhanced stratification. Consistency in data collection and analysis methods is necessary to achieve fully comparable datasets and for statistical validity, avoiding issues linked to disparate data sources. The European Multi Lake Survey (EMLS) in summer 2015 was an initiative among scientists from 27 countries to collect and analyse lake physical, chemical and biological variables in a fully standardized manner. This database includes in-situ lake variables along with nutrient, pigment and cyanotoxin data of 369 lakes in Europe, which were centrally analysed in dedicated laboratories. Publishing the EMLS methods and dataset might inspire similar initiatives to study across large geographic areas that will contribute to better understanding lake responses in a changing environment., The authors acknowledge COST Action ES 1105 “CYANOCOST – Cyanobacterial blooms and toxins in water resources: Occurrence impacts and management” and COST Action ES 1201 “NETLAKE – Networking Lake Observatories in Europe” for contributing to this study through networking and knowledge sharing with European experts in the field. Evanthia Mantzouki was supported by a grant from the Swiss State Secretariat for Education, Research and Innovation (SERI) to Bas Ibelings and by supplementary funding from University of Geneva. We thank Wendy Beekman for the nutrient analysis and the University of Wageningen for covering the costs of this analysis from the personal funding of dr. Miquel Lürling. We thank Pieter Slot for assisting with the pigment analysis and the University of Amsterdam for covering the costs of the analysis through funding from the group of Prof. Jef Huisman and dr. Petra Visser (IBED). We would like to thank the Environmental Data Initiative for covering the cost of archiving the EMLS dataset. We would like to thank the Leibniz Institute of Freshwater Ecology and Inland Fisheries, Dept. of Experimental Limnology and the Aquatic Microbial Ecology Group for logistic and technical support of J. Fonvielle and H.-P. Grossart; and the Leibniz Association for financial support. The collection of data for Lough Erne and Lough Neagh were funded by the Department of Agriculture, Environment and Rural Affairs, Northern Ireland.

Research on the development of new TiO2 based photocatalysts has been receiving increased attention due to the ability of TiO2 to degrade a great variety of organic compounds upon UV-A irradiation. In order to evaluate the photocatalytic performance of the new synthesized materials, it is essential to follow specific procedures during the photocatalytic process. Special care should be given on light intensity, presence of oxygen, catalyst loading, initial concentration of substrate, adsorption, pH, different irradiation wavelength, mineralization, intermediate products and toxicity. In this study, catalysts such as commercially available materials (Degussa P25, Kronos vlp-7000) and home prepared materials (N-TiO2, GO–TiO2 and Ref-TiO2) have been tested for their photocatalytic ability on the degradation and mineralization of the cyanobacterial toxin microcystin-LR and off-odor causing compounds (geosmin, 2-methylisoborneol) under UV-A, solar and visible light irradiation. Also, the identification of intermediate products and their toxicity under different experimental conditions for microcystin-LR was studied. Our results showed that in all cases of the compounds Degussa P25 was the better performing catalyst under UV-A light irradiation. Under solar light, all compounds were effectively degraded with the doped materials (N-TiO2, GO–TiO2, Kronos vlp-7000) showing better photocatalytic performance than theirs undoped material (Ref-TiO2). As far as concerning visible light irradiation, only the visible light activated materials showed some photocatalytic activity (N-TiO2, Kronos vlp-7000). It was also showed in order to have reproducible evaluation results on the photocatalytic performance of several catalysts (intra and inter-laboratory), a careful selection of experimental parameters is required.

Lake Karla (Central Greece) is a unique example - at European scale - of a shallow lake ecosystem that was dried in the 1960s and in 2009 started to be restored. The lake is listed in the network of the Greek protected areas as it is considered a vital aquatic ecosystem, in terms of biodiversity. It has, however, already been adversely affected by both agricultural and industrial land uses in the surrounding area, leading to eutrophication and shifting algal community towards bloom-forming toxic cyanobacterial species. After repeated heavy-blooms, cyanotoxin occurrence and mass fish kills, the local ecosystem management authority has implemented a water quality monitoring program (July 2013 - July 2015) to assess environmental pressures and the response of aquatic biota in the lake. Microscopic, immunological, and molecular techniques combined with physico-chemical parameters, complemented by liquid chromatography tandem mass spectrometry (LC-MS/MS), were used to monitor cyanobacteria blooms and the associated cyanotoxin production from three different sites in Lake Karla and from the adjacent Kalamaki Reservoir. Water quality was also assessed by the structure of benthic invertebrate community on the sediment. Cyanobacteria were the main phytoplankton component, representing more than 70% of the total phytoplankton abundance; dominant taxa belonged toCylindrospermopsis raciborskii,Limnothrix redekei,Anabaenopsis elenkinii, andMicrocystisspp. Euglenophytes (Euglena), diatoms (Nitzschia), and chlorophytes (Scenedesmus) were also important phytoplankton constituents. LC-MS/MS confirmed the co-occurrence of microcystins, cylindrospermopsin, saxitoxin, neo-saxitoxin and anatoxin-a. The occurrence of cyanotoxins in relation to the persistent and dominant cyanobacteria and the impact of cyanobacterial harmful algal blooms on the newly constructed lake along with the land uses and the emergent mitigation measures are discussed.&nbsp

International audience; This review aims to summarise the outcomes of some recent European research concerning toxic cyanobacteria and cyanotoxins, with an emphasis on developments within the framework of the CYANOCOST Action (COST Action ES1105, Cyanobacterial Blooms and Toxins in Water Resources: Occurrence, Impacts and Management). State of the art research and management capabilities in Europe on cyanobacteria have benefitted from input from the pure and applied life sciences, the human and animal health sectors, water engineers, economists and planners. Many of these professional groups have been brought together and they interacted favourably within the framework of CYANOCOST. Highlights of the Action include phycological and ecological studies, development of advanced techniques for cyanotoxin analysis, elucidation of cyanotoxin modes of action, management techniques to reduce cyanobacterial mass development, and research on methods and practices for cyanotoxin removal during drinking water treatment. The CYANOCOST Action has had an active outreach policy throughout its lifetime, resulting in e.g. three handbooks, two special issues in scientific journals and activities in the social media. The many contact channels to end-users, including environmental and drinking water supply authorities, health professionals and the general public are described in this review. Furthermore, the authors have identified a number of gaps in knowledge. Proposed directions for future research in the field of toxic cyanobacteria and cyanotoxins are also discussed

Geosmin (GSM) and 2-methylisoborneol (MIB) are produced by several species of cyanobacteria and actinomycetes. These compounds can taint water and fish causing undesirable taste and odours. Studies have shown that GSM/MIB are resistant in standard water treatments. Polyoxometalates (POM) are efficient photocatalysts in the degradation and mineralization of a great variety of organic pollutants, presenting similar behaviour with the widely published titanium dioxide (TiO 2 ). Photocatalytic degradation of GSM and MIB under UV-A light in the presence of a characteristic POM photocatalyst, SiW 12 O 40 4− , in aqueous solution has been studied and compared with the photodegradation by TiO 2 suspensions. GSM and MIB are effectively degraded in the presence of both photocatalysts. Addition of OH radical scavengers (KBr and tertiary butyl alcohol, TBA) retards the photodegradation rates of both compounds, suggesting that photodegradation mechanism takes place via OH radicals. Intermediates identified using GC–MS in the case of GSM and MIB, are mainly identical in the presence of both photocatalysts, also suggesting a common reaction mechanism. Possible photocatalytic degradation pathway for both GSM and MIB is proposed.

Microcystin-LR (MC-LR) is the most common and toxic variant of the group of microcystins (MCs) produced during the formation of harmful cyanobacterial blooms. Geosmin (GSM) and 2-methylisoborneol (...

In this study, the simultaneous adsorption of methyl orange (MO) and humic acid (HA), which are frequently encountered together in waste waters, onto a low-cost adsorbent (acid-activated bentonite) was described and compared to a single adsorbate situations. Acidification appreciably increased the specific surface area of the bentonite. The effect of activation on montmorillonite was determined by identifying changes in the characteristic absorption bands of the FTIR spectra. Non-competitive Langmuir and Freundlich isotherm models were used to analyze the equilibrium data from single adsorbate situations. In binary mixtures, competition for binding sites and interactions between the MO and HA molecules were identified. The equilibrium MO uptake decreased with an increased initial HA concentration, whereas the existence of MO in the solution enhanced the HA removal. The inadequacy of multi-component isotherm models to describe this situation demonstrated the complex behavior of this adsorption process. An empirical extension of a competitive Langmuir model was proposed to predict the simultaneous adsorption behavior of MO and HA. Pseudo-first-order and pseudo-second-order equations were fitted to the kinetic data, and the rate constants were evaluated. The effect of pH and ionic strength on the simultaneous adsorption efficiency was also studied.

Cyanobacterial and algal toxins comprise a large group of harmful metabolites, belonging to different chemical classes, with a variety of chemical structures, physicochemical properties and toxic activities. In this study, a fast, simple and sensitive analytical method was developed for the simultaneous determination of multi-class cyanobacterial and algal toxins in water. The target compounds were: Cylindrospermopsin, Anatoxin-a, Nodularin, 12 Microcystins ([D-Asp3]MC-RR, MC-RR, MC-YR, MC-HtyR, [D-Asp3]MC-LR, MC-LR, MC-HilR, MC-WR, MC-LA, MC-LY, MC-LW and MC-LF), Okadaic acid and Domoic acid. Analytes were determined using liquid chromatography-tandem mass spectrometry (LC-MS/MS). A dual Solid Phase Extraction (SPE) cartridge assembly was applied for the extraction of target compounds from water. Optimized SPE parameters included cartridge material, initial sample pH, sequence of the cartridges in the SPE assembly as well as composition and volume of the elution solvent. The method was validated, providing acceptable mean recoveries and reproducibility for most analytes. Limits of detection were at the ngL-1 level. The method was successfully applied in real lake water samples from Greece, where a wide range of Microcystins were detected for the first time, at concentrations ranging from 0.034 to 63μgL-1.

This chapter discusses thoroughly the outcomes of the TiO2 photocatalytic degradation of organic contaminants of emerging concern, including manmade (insecticides, organochlorinated compounds, and antibiotics) and naturally occurring compounds (cyanotoxins and taste and odor compounds). Specifically, information is provided on the degradation of various organic contaminants in actual water samples, their corresponding reaction kinetics, the individual effects of water quality parameters (including pH, natural organic matter, and alkalinity) and nano-interfacial adsorption phenomena. Emphasis is given to the mechanisms of photocatalytic degradation of organic contaminants based on their structural differences and the corresponding transformation products formed.

Cyanobacteria blooms pose an environmental hazard because of the release of water soluble toxic compounds, called cyanotoxins. Microcystins (MCs), hepatotoxic cyclic peptide toxins, are the most widespread cyanotoxins with microcystin-LR (MC-LR) the most common and toxic variant. Health effects of MCs have resulted in the need of using efficient treatment methods for the removal of this class of toxins in water supplies. While physical treatment methods can remove MCs at full or some extent from contaminated water, their function is primary separation of the whole toxins as intact molecules and further processing is required. On the other hand, chemical oxidation processes are a promising alternative treatment option due to the potential of complete destruction of the MCs, transformation to less toxic by-products, and even complete mineralization. MCs reactivity towards different conventional oxidants is strongly affected by water quality parameters like pH, DOC and oxidant dose. Although there is a general trend for MCs oxidation (ozone > permanganate > chlorine >>> chlorine-based oxidants), the selection of the appropriate oxidant for toxin elimination during water treatment should be assessed for each particular source of water. Although advanced oxidation processes are generally more effective on MCs degradation than conventional oxidation processes, scale-up studies are needed before these methods are considered as economically-feasible and practical sustainable alternatives in water treatment facilities. In this review, recent literature concerning treatment of MCs in water by conventional and advanced oxidation processes are reviewed and discussed in terms of the degree of degradation, reaction kinetics, identity and toxicity of oxidation by-products and possible degradation pathways.

The destruction of the commonly found cyanobacterial toxin, microcystin-LR (MC-LR), in surface waters by UV-C/H2O2 advanced oxidation process (AOP) was studied. Experiments were carried out in a bench scale photochemical apparatus with low pressure mercury vapor germicidal lamps emitting at 253.7 nm. The degradation of MC-LR was a function of UV fluence. A 93.9% removal with an initial MC-LR concentration of 1 μM was achieved with a UV fluence of 80 mJ/cm2 and an initial H2O2 concentration of 882 μM. When increasing the concentration of MC-LR only, the UV fluence-based pseudo-first order reaction rate constant generally decreased, which was probably due to the competition between by-products and MC-LR for hydroxyl radicals. An increase in H2O2 concentration led to higher removal efficiency; however, the effect of HO scavenging by H2O2 became significant for high H2O2 concentrations. The impact of water quality parameters, such as pH, alkalinity and the presence of natural organic matter (NOM), was also studied. Field water samples from Lake Erie, Michigan and St. Johns River, Florida were employed to evaluate the potential application of this process for the degradation of MC-LR. Results showed that the presence of both alkalinity (as 89.6–117.8 mg CaCO3/L) and NOM (as ∼2 to ∼9.5 mg/L TOC) contributed to a significant decrease in the destruction rate of MC-LR. However, a final concentration of MC-LR bellow the guideline value of 1 μg/L was still achievable under current experimental conditions when an initial MC-LR concentration of 2.5 μg/L was spiked into those real water samples.

The photocatalytic degradation of lindane (γ-1,2,3,4,5,6-hexachlorocyclohexane) has been studied in the presence of the polyoxometalate PW12O403− in aqueous solutions. Lindane is fully decomposed to CO2, Cl− and H2O, while a great variety of intermediates has been detected using GC–MS, including aromatic compounds (dichlorophenol, trichlorophenols, tetrachlorophenol, hexachlorobenzene, di- and trichloro-benzenodiol), non-aromatic cyclic compounds (penta-, tetrachlorocyclohexene, heptachlorocyclohexane), aliphatic compounds (tetrachloroethane) and condensation products (polychlorinated biphenyls). The number and nature of the intermediates implies that the mechanism of decomposition of lindane is based on both oxidative and reductive processes. Common intermediates have been reported during photolysis of lindane in the presence of titanium dioxide. A similar overall mechanism of polyoxometalates and TiO2 photocatalysis through the formation of common reactive species is suggested.

Selenium nanoparticles are formed upon photolysis of solutions of (propan-2-ol/POM/Se(IV)), where polyoxometalate (POM) is either PW 12 O 40 3− or SiW 12 O 40 4− . Propan-2-ol serves as sacrificial reagent for the photoformation of 1-equivalent reduced blue polyoxometalate, POM(e), which further reacts with Se(IV) to produce selenium nanoparticles. POM serves both as relay for the transfer of electrons from propan-2-ol to Se(IV) and stabilizer for the nanoparticles. Changing the ionic strength from 0 to 0.025 and 0.05 M, results in the formation of gradually larger nanoparticles 40, 60 and 90 nm, respectively. Increase of the initial concentration of SiW 12 O 40 4− , from 2 to 4 and 10 × 10 −3 M, results in the formation of gradually smaller nanoparticles, 110, 80 and 60 nm, respectively.

Uniform silver nanoparticles were obtained upon the reduction of silver ions by reduced polyoxometalates (POMs) by simple mixing at room temperature. Control of the size and the dispersity of silver nanoparticles was achieved by rate control. Faster reduction of Ag+ led to smaller and more uniform silver nanoparticles, suggesting that the rate of Ag+ reduction strongly affects the initial nucleation of silver particles. A faster rate is achieved by either (i) increasing the concentration of the reducing reagent (reduced POM) or, more interestingly (ii) selecting POMs having appropriate (more negative) redox potentials: different POMs with increasing negative reduction potential or the same POM with more electrons accumulated on it. The rates of Ag+ reduction parallel the more negative reduction potential for POMs according to the series H2W12O407– > SiW12O405– > P2W18O628– > P2W18O627– > P2Mo18O6210– > P2Mo18O628– = 0. This precise redox-control is summarized in a log k (E0) electrochemical-like behavior, in alliance to a “soluble cathode” behavior of POMs, which leads to more uniform particles than those obtained with conventional electrochemistry. Alternatively, the concentration of silver ions influences the size of the particles obtained: increasing the amount of Ag+ leads to larger nanoparticles.(© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2008)

A new method for the simultaneous determination of 1,4-dichlorobenzene (p-DCB), naphthalene and 1,2-dibromoethane (1,2-DBE) residues in honey has been developed. Analysis is carried out using gas chromatography-mass spectrometry (GC/MS) in selected ion monitoring mode (SIM), after extraction and preconcentration of target analytes by headspace solid-phase microextraction (HS-SPME), with a 100 microm film thickness polydimethylsiloxane (PDMS) fiber. Several parameters affecting the extension of the adsorption process (i.e., addition of salt, extraction time, extraction temperature) were studied. The optimal conditions for the determination of these analytes were established. The proposed HS-SPME method showed good sensitivity, without carryover between the samples. Linearity was studied from 5 to 2500 microg kg(-1) for p-DCB, 0.5 to 500 microg kg(-1) for naphthalene and 5 to 500 microg kg(-1) honey for 1,2-DBE with correlation coefficients (r(2)) ranging from 0.9901 to 0.9999. Precision was assessed and both intra and inter-day R.S.D.s (%) were below 6.3%. The detection limits were found to be 1, 0.1 and 2 microg kg(-1) honey for p-DCB, naphthalene and 1,2-DBE, respectively. The percentage recoveries that were evaluated with the proposed HS-SPME method and the standard addition calibration technique gave values among 72.8 and 104.3% for measurements in samples spiked with one target analyte or mixtures of the three. This method has been applied for the analysis of unknown honey samples. The results showed an excellent applicability of the proposed method for the determination of the target compounds in honey samples.

Polyoxometallates (POMs) as a homogeneous photocatalyst and TiO2 as a heterogeneous photocatalyst seem to exhibit overall similar photocatalytic behavior. Both systems cause photodecomposition of a variety of organic pollutants via the formation and decay of several similar intermediates formed by OH addition (hydroxylation), dehalogenation, deamination, decarboxylation, etc. The final degradation products, for most organic substrates for both systems are CO2, H2O and inorganic anions. The similarity of behavior has been attributed to the formation of the common powerful oxidizing reagent, OH radical, from the reaction of the excited catalyst and water molecules. On the other hand, lately, various laboratories have pointed out differences in reactivity and degradation mechanism between the two photocatalysts. The results are interesting and to a great extent contradictory. This study compares the photodegradation of four substrates with diversified structures, namely, atrazine, fenitrothion, 4-chlorophenol (4-ClPh), and 2,4-dichlorophenoxyacetic acid (2,4-D) by both PW12O403− and TiO2 and how their photodegradation is affected by the presence of strong OH radical scavengers, i.e., Br− and isopropyl alcohol (i-prOH). The results provide substantial evidence that the literature data on the apparent photooxidation mechanism of these two categories of photocatalysts is circumstantial, depending on substrate and the mode of investigation. Overall, though, the action of OH radicals relative to h+ appears to be more pronounced with PW12O403− than TiO2. With respect to thermal (dark) reaction of photoreduced catalysts, both systems can deliver their electrons to a variety of oxidants including metal ions. The advantages of POM relative to TiO2 relates to the selective reduction precipitation of metal ions and to their unique ability to form metal nanoparticles in which POM serve both as reducing reagents and stabilizers.

Various polyoxometallates (POM) PW12O403−, SiW12O404−, P2W18O626− and P2Mo18O626− have been used as photocatalysts for the reductive destruction of the azo dye naphthol blue black (NB). In the process POM absorb light and mediate the electron transfer from a sacrificial donor, propan-2-ol, to the azo dye. NB is rapidly destructed in the presence of POM, while toxic intermediate products, such as aromatic amine derivatives (aniline, p-nitro-aniline and p-phenylene-diamine) are observed in a multi-electron process. Increase of catalyst and/or propan-2-ol concentration accelerates the photodegradation of dye till a saturation value, while an optimum concentration of the added dye is required. The nature of the POM catalyst dictates the efficiency of the reductive decoloration of NB, following the order PW12O403− > SiW12O404− > P2W18O626− according to their photooxidizing ability. No reaction is noticed with the 2-e-reduced molybdate, P2Mo18O628−, which exhibits a more positive redox potential.