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1.
Environ Monit Assess ; 196(4): 408, 2024 Apr 02.
Artigo em Inglês | MEDLINE | ID: mdl-38561517

RESUMO

Cyanobacteria inhabiting lotic environments have been poorly studied and characterized in Mexico, despite their potential risks from cyanotoxin production. This article aims to fill this knowledge gap by assessing the importance of benthic cyanobacteria as potential cyanotoxin producers in central Mexican rivers through: (i) the taxonomic identification of cyanobacteria found in these rivers, (ii) the environmental characterization of their habitats, and (iii) testing for the presence of toxin producing genes in the encountered taxa. Additionally, we introduce and discuss the use of the term "CyanoHAMs" for lotic water environments. Populations of cyanobacteria were collected from ten mountain rivers and identified using molecular techniques. Subsequently, these taxa were evaluated for genes producing anatoxins and microcystins via PCR. Through RDA analyses, the collected cyanobacteria were grouped into one of three categories based on their environmental preferences for the following: (1) waters with high ionic concentrations, (2) cold-temperate waters, or (3) waters with high nutrient enrichment. Populations from six locations were identified to genus level: Ancylothrix sp., Cyanoplacoma sp., and Oxynema sp. The latter was found to contain the gene that produces anatoxins and microcystins in siliceous rivers, while Oxynema tested positive for the gene that produces microcystins in calcareous rivers. Our results suggest that eutrophic environments are not necessarily required for toxin-producing cyanobacteria. Our records of Compactonostoc, Oxynema, and Ancylothrix represent the first for Mexico. Four taxa were identified to species level: Wilmottia aff. murrayi, Nostoc tlalocii, Nostoc montejanii, and Dichothrix aff. willei, with only the first testing positive using PCR for anatoxin and microcystin-producing genes in siliceous rivers. Due to the differences between benthic growths with respect to planktonic ones, we propose the adoption of the term Cyanobacterial Harmful Algal Mats (CyanoHAMs) as a more precise descriptor for future studies.


Assuntos
Toxinas Bacterianas , Cianobactérias , Tropanos , Microcistinas/análise , Proliferação Nociva de Algas , México , Toxinas Bacterianas/genética , Toxinas Bacterianas/análise , Monitoramento Ambiental , Cianobactérias/genética , Toxinas de Cianobactérias , Rios/microbiologia
2.
Anal Chem ; 96(15): 5887-5896, 2024 Apr 16.
Artigo em Inglês | MEDLINE | ID: mdl-38567874

RESUMO

Microcystin-LR (MC-LR) is a severe threat to human and animal health; thus, monitoring it in the environment is essential, especially in water quality protections. Herein, in this work, we synthesize PVDF/CNT/Ag molecular imprinted membranes (PCA-MIMs) via an innovative combination of surface-enhanced Raman spectroscopy (SERS) detection, membrane separation, and molecular-imprinted technique toward the analysis of MC-LR in water. In particular, a light-initiated imprint is employed to protect the chemical structure of the MC-LR molecules. Furthermore, in order to ensure the detection sensitivity, the SERS substrates are combined with the membrane via the assistance of magnetism. The effect of synthesis conditions on the SERS sensitivity was investigated in detail. It is demonstrated from the characteristic results that the PCA-MIMs present high sensitivity to the MC-LR molecules with excellent selectivity against the interfere molecules. Results clearly show that the as-prepared PCA-MIMs hold great potential applications to detect trace MC-LR for the protection of water quality.


Assuntos
Biomimética , Polímeros de Fluorcarboneto , Polivinil , Análise Espectral Raman , Humanos , Análise Espectral Raman/métodos , Microcistinas/análise , Toxinas Marinhas
3.
J Hazard Mater ; 470: 134170, 2024 May 15.
Artigo em Inglês | MEDLINE | ID: mdl-38613957

RESUMO

Cyanobacterial blooms, often dominated by Microcystis aeruginosa, are capable of producing estrogenic effects. It is important to identify specific estrogenic compounds produced by cyanobacteria, though this can prove challenging owing to the complexity of exudate mixtures. In this study, we used untargeted metabolomics to compare components of exudates from microcystin-producing and non-microcystin-producing M. aeruginosa strains that differed with respect to their ability to produce microcystins, and across two growth phases. We identified 416 chemicals and found that the two strains produced similar components, mainly organoheterocyclic compounds (20.2%), organic acids and derivatives (17.3%), phenylpropanoids and polyketides (12.7%), benzenoids (12.0%), lipids and lipid-like molecules (11.5%), and organic oxygen compounds (10.1%). We then predicted estrogenic compounds from this group using random forest machine learning. Six compounds (daidzin, biochanin A, phenylethylamine, rhein, o-Cresol, and arbutin) belonging to phenylpropanoids and polyketides (3), benzenoids (2), and organic oxygen compound (1) were tested and exhibited estrogenic potency based upon the E-screen assay. This study confirmed that both Microcystis strains produce exudates that contain compounds with estrogenic properties, a growing concern in cyanobacteria management.


Assuntos
Estrogênios , Aprendizado de Máquina , Metabolômica , Microcistinas , Microcystis , Microcystis/metabolismo , Microcystis/crescimento & desenvolvimento , Microcistinas/metabolismo , Microcistinas/análise , Microcistinas/química , Estrogênios/metabolismo , Estrogênios/química
4.
J Hazard Mater ; 470: 134281, 2024 May 15.
Artigo em Inglês | MEDLINE | ID: mdl-38626680

RESUMO

Eutrophication has led to the widespread occurrence of cyanobacterial blooms. Toxic cyanobacterial blooms with high concentrations of microcystins (MCs) have been identified in the Lalla Takerkoust reservoir in Morocco. The objective of this study was to evaluate the efficiency of the Multi-Soil-Layering (MSL) ecotechnology in removing natural cyanobacterial blooms from the lake. Two MSL pilots were used in rectangular glass tanks (60 × 10 × 70 cm). They consisted of permeable layers (PLs) made of pozzolan and a soil mixture layer (SML) containing local soil, ferrous metal, charcoal and sawdust. The main difference between the two systems was the type of local soil used: sandy soil for MSL1 and clayey soil for MSL2. Both MSL pilots effectively reduced cyanobacterial cell concentrations in the treated water to very low levels (0.09 and 0.001 cells/mL). MSL1 showed a gradual improvement in MC removal from 52 % to 99 %, while MSL2 started higher at 90 % but dropped to 54% before reaching 86%. Both MSL systems significantly reduced organic matter levels (97.2 % for MSL1 and 95.8 % for MSL2). Both MSLs were shown to be effective in removing cyanobacteria, MCs, and organic matter with comparable performance.


Assuntos
Cianobactérias , Eutrofização , Lagos , Microcistinas , Solo , Lagos/microbiologia , Cianobactérias/crescimento & desenvolvimento , Microcistinas/análise , Solo/química , Purificação da Água/métodos , Recuperação e Remediação Ambiental/métodos , Marrocos
5.
Methods Mol Biol ; 2788: 397-410, 2024.
Artigo em Inglês | MEDLINE | ID: mdl-38656527

RESUMO

Early monitoring of Microcystis, a cyanobacterium that produces microcystin, is paramount in order to confirm the presence of Microcystis spp. Both phenotypic and genotypic methods have been used. The phenotypic methods provide the presence of the microcystis but do not confirm its species type and toxin produced. Additionally, phenotypic methods cannot differentiate toxigenic from non-toxigenic Microcystis. Therefore, the current protocol also describes genetic methods based on PCR to detect toxigenic Microcystis spp. based on microcystin synthetase E (mcy E) gene and 16-23S RNA genes for species-specific identification, which can effectively comprehend distinct lineages and discrimination of potential complexity of microcystin populations. The presence of these microcystin toxins in blood, in most cases, indicates contamination of drinking water by cyanobacteria. The methods presented herein are used to identify microcystin toxins in drinking water and blood.


Assuntos
Cianobactérias , Lagos , Microcistinas , Lagos/microbiologia , Microcistinas/genética , Microcistinas/análise , Cianobactérias/genética , Cianobactérias/isolamento & purificação , Fenótipo , Genótipo , Reação em Cadeia da Polimerase/métodos , Microbiologia da Água , Microcystis/genética , Microcystis/isolamento & purificação , Microcystis/classificação , Técnicas de Genotipagem/métodos
6.
Environ Pollut ; 347: 123744, 2024 Apr 15.
Artigo em Inglês | MEDLINE | ID: mdl-38462202

RESUMO

The eutrophication of aquaculture water bodies seriously restricts the healthy development of the aquaculture industry. Among them, microcystins are particularly harmful. Therefore, the development of technologies for degrading microcystins is of great significance for maintaining the healthy development of the aquaculture industry. The feasibility and mechanism of removing microcystins-LR by dielectric barrier discharge (DBD) plasma were studied. DBD discharge power of 49.6 W and a treatment time of 40 min were selected as the more suitable DBD parameters, resulting in microcystin-LR removal efficiency of 90.4%. Meanwhile, the effects of initial microcystin-LR concentration, initial pH value, turbidity, anions on the degradation effect of microcystin-LR were investigated. The removal efficiency of microcystin-LR decreased with the increase of initial microcystin-LR concentration and turbidity. The degradation efficiency of microcystin-LR at pH 4.5 and 6.5 is significantly higher than that at pH 8.5 and 3.5. HCO3- can inhibit the removal efficiency of microcystin-LR. Furthermore, five intermediates products (m/z = 1029.5, 835.3, 829.3, 815.4, 642.1) were identified in this study, and the toxicity analysis of these degradation intermediates indicated that DBD treatment can reduce the toxicity of microcystin-LR. e-aq, •OH, H2O2, and O3 have been shown to play a major role in the degradation of microcystin-LR, and the contribution ranking of these active species is e-aq > â€¢OH > H2O2 > O3. The application of DBD plasma technology in microcystin-LR removal and detoxification has certain development potential.


Assuntos
Microcistinas , Água , Microcistinas/análise , Peróxido de Hidrogênio , Temperatura , Aquicultura
7.
Environ Sci Pollut Res Int ; 31(16): 24512-24524, 2024 Apr.
Artigo em Inglês | MEDLINE | ID: mdl-38443530

RESUMO

Cyanobacterial algal hepatotoxins, called microcystins (MCs), are a global health concern, necessitating research on effective removal methods from contaminated water bodies. In this study, we synthesized non-fluorine MIL-100(Fe) using an environmentally friendly room-temperature method and utilized it as an adsorbent to effectively remove microcystin-LR (MC-LR), which is the most toxic MC congener. MIL-100(Fe) was thoroughly characterized, and its adsorption process was investigated under various conditions. Results revealed rapid MC-LR adsorption, achieving 93% removal in just 5 min, with the pseudo-second-order kinetic model indicating chemisorption as the primary mechanism. The Langmuir isotherm model demonstrated a monolayer sorption capacity of 232.6 µg g-1 at room temperature, showing favorable adsorption. Furthermore, the adsorption capacity increased from 183 µg g-1 at 20 °C to 311 µg g-1 at 40 °C, indicating an endothermic process. Thermodynamic parameters supported MC-LR adsorption's spontaneous and feasible nature onto MIL-100(Fe). This study highlights MIL-100(Fe) as a promising method for effectively removing harmful biological pollutants, such as MC-LR, from contaminated water bodies in an environmentally friendly manner.


Assuntos
Poluentes Químicos da Água , Purificação da Água , Água , Microcistinas/análise , Toxinas Marinhas , Adsorção , Poluentes Químicos da Água/análise , Purificação da Água/métodos
8.
Toxicon ; 241: 107654, 2024 Apr.
Artigo em Inglês | MEDLINE | ID: mdl-38368956

RESUMO

The safety of drinking water source directly affects human health. Microcystin-LR (MC-LR), a toxic and common pollutant in drinking water source, is released by algae and can impede the in-situ remediation effect of aquatic plant. Finding out the effect mechanism of MC-LR on the purification of drinking water by aquatic plant is the key to its application. This study aims to explore the performance and mechanism of MC-LR on drinking water source purification by Hydrocharis dubia (Bl.) backer. The optimum removal efficiency of NH4+-N, TP and COD were 90.7%, 93.2% and 77.3% at MC-LR concentration of 0.5 µg L-1, respectively. With the increase of MC-LR concentration, the pollutants removal rate was obviously inhibited causing by concentration-dependent. Furthermore, the growth and development of the Hydrocharis dubia (Bl.) backer roots were significantly promoted at the concentration of 0.1 µg L-1. The length, tips, surface area, and average diameter of the root increased by 71.3%, 271.4%, 265.5%, and 113.0%, respectively. Chlorophyll contents under low-concentration MC-LR show a 14.5%-15.7% promoting effect compared with the control group. The activities of POD and CAT were also stimulated with the MC-LR increasing (<1.0 µg L-1). Notably, the MDA contents increased with increasing MC-LR concentration (p < 0.01). This study indicates the effect mechanism of MC-LR on Hydrocharis dubia (Bl.) backer purification performance relies on the increased growth and enzyme activity of Hydrocharis dubia (Bl.) backer.


Assuntos
Água Potável , Hydrocharitaceae , Poluentes Químicos da Água , Purificação da Água , Humanos , Água Potável/análise , Antioxidantes/farmacologia , Microcistinas/toxicidade , Microcistinas/análise , Toxinas Marinhas , Poluentes Químicos da Água/toxicidade , Poluentes Químicos da Água/análise
9.
Water Res ; 251: 121121, 2024 Mar 01.
Artigo em Inglês | MEDLINE | ID: mdl-38277829

RESUMO

Microcystins are highly toxic cyanotoxins and have been produced worldwide with the global expansion of harmful cyanobacterial blooms (HABs), posing serious threats to human health and ecosystem safety. Yet little knowledge is available on the underlying process occurring in the aquatic environment with microcystins. Microplastics as vectors for pollutants has received growing attention and are widely found co-existing with microcystins. On the one hand, microplastics could react with microcystins by adsorption, altering their environmental behavior and ecological risks. On the other hand, particular attention should be given to microplastics due to their implications on the outbreak of HABs and the generation and release of microcystins. However, limited reviews have been undertaken to link the co-existing microcystins and microplastics in natural water. This study aims to provide a comprehensive understanding on the environmental relevance of microcystins and microplastics and their potential interactions, with particular emphasis on the adsorption, transport, sources, ecotoxicity and environmental transformation of microcystins affected by microplastics. In addition, current knowledge gaps and future research directions on the microcystins and microplastics are presented. Overall, this review will provide novel insights into the ecological risk of microcystins associated with microplastics in real water environment and lay foundation for the effective management of HABs and microplastic pollution.


Assuntos
Microplásticos , Poluentes Químicos da Água , Humanos , Microplásticos/toxicidade , Microcistinas/análise , Plásticos , Ecossistema , Água , Poluentes Químicos da Água/análise , Monitoramento Ambiental
10.
Sci Total Environ ; 916: 170011, 2024 Mar 15.
Artigo em Inglês | MEDLINE | ID: mdl-38220005

RESUMO

Plastic products and nutrients are widely used in aquaculture facilities, resulting in copresence of nanoplastics (NPs) released from plastics and microcystins (MCs) from toxic cyanobacteria. The potential effects of NPs-MCs coexposure on aquatic products require investigation. This study investigated the toxic effects of polystyrene (PS) NPs and MC-LR on the gut-liver axis of silver carp Hypophthalmichthys molitrix, a representative commercial fish, and explored the effects of the coexposure on intestinal microorganism structure and liver metabolic function using traditional toxicology and multi-omics association analysis. The results showed that the PS-NPs and MC-LR coexposure significantly shortened villi length, and the higher the concentration of PS-NPs, the more obvious the villi shortening. The coexposure of high concentrations of PS-NPs and MC-LR increased the hepatocyte space in fish, and caused obvious loss of gill filaments. The diversity and richness of the fish gut microbes significantly increased after the PS-NPs exposure, and this trend was amplified in the copresence of MC-LR. In the coexposure, MC-LR contributed more to the alteration of fish liver metabolism, which affected the enrichment pathway in glycerophospholipid metabolism and folic acid biosynthesis, and there was a correlation between the differential glycerophospholipid metabolites and affected bacteria. These results suggested that the toxic mechanism of PS-NPs and MC-LR coexposure may be pathological changes of the liver, gut, and gill tissues, intestinal microbiota disturbance, and glycerophospholipid metabolism imbalance. The findings not only improve the understanding of environmental risks of NPs combined with other pollutants, but also provide potential microbiota and glycerophospholipid biomarkers in silver carp.


Assuntos
Carpas , Cianobactérias , Toxinas Marinhas , Animais , Carpas/metabolismo , Microcistinas/análise , Microplásticos/metabolismo , Fígado/química , Cianobactérias/metabolismo , Glicerofosfolipídeos/metabolismo , Glicerofosfolipídeos/farmacologia
11.
Harmful Algae ; 131: 102549, 2024 Jan.
Artigo em Inglês | MEDLINE | ID: mdl-38212082

RESUMO

Cyanobacterial blooms releasing harmful cyanotoxins, such as microcystin (MC) and cylindrospermopsin (CYN), are prominent threats to human and animal health. Constructed wetlands (CW) may be a nature-based solution for bioremediation of lake surface water containing cyanotoxins, due to its low-cost requirement of infrastructure and environmentally friendly operation. There is recent evidence that microcystin-LR (MC-LR) can efficiently be removed in CW microcosms where CYN degradation in CW is unknown. Likewise, the mechanistic background regarding cyanotoxins transformation in CW is not yet elucidated. In the present study, the objective was to compare MC-LR and CYN degradation efficiencies by two similar microbial communities obtained from CW mesocosms, by two different experiments setup: 1) in vitro batch experiment in serum bottles with an introduced CW community, and 2) degradation in CW mesocosms. In experiment 1) MC-LR and CYN were spiked at 100 µg L-1 and in experiment 2) 200 µg L-1 were spiked. Results showed that MC-LR was degraded to ≤1 µg L-1 within seven days in both experiments. However, with a markedly higher degradation rate constant in the CW mesocosms (0.18 day-1 and 0.75 day-1, respectively). No CYN removal was detected in the in vitro incubations, whereas around 50 % of the spiked CYN was removed in the CW mesocosms. The microbial community responded markedly to the cyanotoxin treatment, with the most prominent increase of bacteria affiliated with Methylophilaceae (order: Methylophilales, phylum: Proteobacteria). The results strongly indicate that CWs can develop an active microbial community capable of efficient removal of MC-LR and CYN. However, the CW operational conditions need to be optimized to achieve a full CYN degradation. To the best of our knowledge, this study is the first to report the ability of CW mesocosms to degrade CYN.


Assuntos
Alcaloides , Toxinas Bacterianas , Cianobactérias , Toxinas Marinhas , Animais , Humanos , Microcistinas/análise , Toxinas Bacterianas/metabolismo , Biodegradação Ambiental , Áreas Alagadas , Toxinas de Cianobactérias , Cianobactérias/metabolismo
12.
Environ Sci Technol ; 58(3): 1473-1483, 2024 Jan 23.
Artigo em Inglês | MEDLINE | ID: mdl-38205949

RESUMO

Though toxins produced during harmful blooms of cyanobacteria present diverse risks to public health and the environment, surface water quality surveillance of cyanobacterial toxins is inconsistent, spatiotemporally limited, and routinely relies on ELISA kits to estimate total microcystins (MCs) in surface waters. Here, we employed liquid chromatography tandem mass spectrometry to examine common cyanotoxins, including five microcystins, three anatoxins, nodularin, cylindrospermopsin, and saxitoxin in 20 subtropical reservoirs spatially distributed across a pronounced annual rainfall gradient. Probabilistic environmental hazard analyses identified whether water quality values for cyanotoxins were exceeded and if these exceedances varied spatiotemporally. MC-LR was the most common congener detected, but it was not consistently observed with other toxins, including MC-YR, which was detected at the highest concentrations during spring with many observations above the California human recreation guideline (800 ng/L). Cylindrospermopsin was also quantitated in 40% of eutrophic reservoirs; these detections did not exceed a US Environmental Protection Agency swimming/advisory level (15,000 ng/L). Our observations have implications for routine water quality monitoring practices, which traditionally use ELISA kits to estimate MC levels and often limit collection of surface samples during summer months near reservoir impoundments, and further indicate that spatiotemporal surveillance efforts are necessary to understand cyanotoxins risks when harmful cyanobacteria blooms occur throughout the year.


Assuntos
Toxinas Bacterianas , Cianobactérias , Humanos , Microcistinas/análise , Qualidade da Água , Toxinas Marinhas , Toxinas Bacterianas/análise , Água Doce/análise , Água Doce/química , Água Doce/microbiologia , Toxinas de Cianobactérias , Cianobactérias/química , Monitoramento Ambiental/métodos
13.
Anal Chem ; 96(2): 775-786, 2024 01 16.
Artigo em Inglês | MEDLINE | ID: mdl-38170221

RESUMO

Microcystins (MCs) are hepatotoxic cyclic heptapeptides produced by cyanobacteria, and their structural diversity has led to the discovery of more than 300 congeners to date. However, with known amino acid combinations, many more MC congeners are theoretically possible, suggesting many remain unidentified. Herein, two novel serine (Ser)-containing MCs were putatively identified in a Lake Erie cyanobacterial harmful algal bloom (cyanoHAB), using high-resolution UHPLC-MS as well as thiol and sulfoxide derivatization procedures. These MCs contain an α,ß-unsaturated carbonyl on methyl dehydroalanine (Mdha) residue that undergoes Michael addition to produce a thiol-derivatized MC. Derivatization reactions using various thiolation reagents were followed by MS/MS, and two Python codes were used for data analysis and structural elucidation of MCs. Two novel MCs containing Ser at position 1 (i.e., next to Mdha) were putatively identified as [Ser1]MC-RR and [Ser1]MC-YR. Using thiol- and sulfoxide-modified [Ser1]MCs, identifications were confirmed by the observation of specific neutral losses of the oxidized thiols or sulfoxides in CID-MS/MS spectra in both positive and negative electrospray ionization (ESI) modes. These novel neutral losses are unique for MCs with Mdha and an adjacent Ser residue. Data suggest that a gas-phase reaction occurs between oxygen from adjacent Ser residue and sulfur of the Mdha-bonded thiol or sulfoxide, which leads to the formation and detection of stable cyclic MC ions in MS/MS spectra at m/z values corresponding to the loss of oxidized thiols or oxidized sulfoxides from Ser1-containing MCs.


Assuntos
Cianobactérias , Safrol/análogos & derivados , Espectrometria de Massas em Tandem , Microcistinas/análise , Cromatografia Líquida de Alta Pressão , Serina , Cromatografia Líquida/métodos , Cianobactérias/química , Compostos de Sulfidrila/química
14.
J Chromatogr A ; 1717: 464666, 2024 Feb 22.
Artigo em Inglês | MEDLINE | ID: mdl-38266594

RESUMO

Cyanotoxins constitute a group of toxic secondary metabolites, the presence of which in any water body poses a major health risk. Moreover, advanced organisms such as edible plants exposed to these toxins, are a possible pathway for human exposure. Green analytical chemistry is demanding environmentally friendly analytical techniques. In this sense, we propose the use of capillary electrophoresis coupled to tandem mass spectrometry (CE-MS/MS) to determine a mixture of eight cyanotoxins belonging to three different classes: cyclic peptides (microcystin-LR, microcystin-RR and nodularin), alkaloids (cylindrospermopsin and anatoxin-a) and three isomeric non-protein amino acids (ß-methylamino-l-alanine, 2,4-diaminobutyric acid and N-(2-aminoethyl)glycine). Separation was achieved by using an acidic background electrolyte consisting of 2 M formic acid and 20% acetonitrile in water. Parameters affecting MS/MS detection and the sheath-liquid interface were also studied. Finally, a combination of pH-junction, field-amplified sample stacking (FASS) and acid barrage as online preconcentration strategies, was employed to improve sensitivity and efficiency. The online preconcentration applied, in combination with a dual cartridge solid-phase extraction (SPE) system, allows to obtain limits of detection in the very low range of µg·L-1 for these multiclass cyanotoxins in reservoir water samples (from 0.005 to 0.10 µg·L-1). Furthermore, for the first time cyanotoxins are analysed in spinach samples through CE-MS/MS using the same SPE procedure, following lyophilisation and solid-liquid extraction with 6 mL 80 % aqueous MeOH.


Assuntos
Spinacia oleracea , Espectrometria de Massas em Tandem , Humanos , Espectrometria de Massas em Tandem/métodos , Água , Cromatografia Líquida de Alta Pressão , Toxinas de Cianobactérias , Microcistinas/análise , Eletroforese Capilar
15.
Environ Res ; 242: 117623, 2024 Feb 01.
Artigo em Inglês | MEDLINE | ID: mdl-37956753

RESUMO

Lake Steinsfjorden, an important noble crayfish (Astacus astacus) habitat, is often affected by blooms of Planktothrix spp. that produce microcystins (MCs). A poor correlation between MCs by ELISA in the water and in crayfish tissue in a study in 2015 prompted further investigation by LC-HRMS. LC-HRMS analyses of filters from water samples and on selected crayfish tissue extracts from the 2015 study revealed the presence of known and previously unreported MCs. Crayfish samples from May and June 2015 were dominated by MCs from the Planktothrix bloom, whereas in September novel MCs that appeared to be metabolites of MC-LR were dominant, even though neither these nor MC-LR were detected in the water in 2015. A water sample from October 2016 also showed MCs typical of Planktothrix (i.e., [d-Asp3]- and [d-Asp3,Dhb7]MC-RR and -LR), but low levels of MC-RR and MC-LR were detected in the lake water for the first time. In late summer and autumn, the MC profiles of crayfish were dominated by the homonorvaline (Hnv) variant MC-LHnv, a putative metabolite of MC-LR. Taken together, ELISA, LC-HRMS and previous PCR analyses showed that although Planktothrix was part of the crayfish diet, it was not the sole source of MCs in the crayfish. Possibly, crayfish in Lake Steinsfjorden may be ingesting MCs from benthic cyanobacteria or from contaminated prey. Therefore, information on the cyanobacterial or MC content in the water column cannot safely be used to make predictions about MC concentrations in the crayfish in Lake Steinsfjorden. Interestingly, the results also show that targeted LC-MS analysis of the crayfish would at times have underestimated their MC content by nearly an order of magnitude, even if all previously reported MC variants had been included in the analysis.


Assuntos
Cianobactérias , Lagos , Animais , Lagos/microbiologia , Astacoidea , Água , Microcistinas/análise , Noruega
16.
Toxicon ; 237: 107551, 2024 Jan.
Artigo em Inglês | MEDLINE | ID: mdl-38070753

RESUMO

The presence of microcystins (MCs) is increasingly being reported in coastal areas worldwide. To provide reliable data regarding this emerging concern, reproducible and accurate methods are required to quantify MCs in salt-containing samples. Herein, we characterized methods of extraction and analysis by liquid chromatography coupled to tandem mass spectrometry (LC-MS/MS) for nine MCs and one nodularin (NOD) variants in both cyanobacteria (intracellular) and dissolved forms (extracellular). Different approaches have been used to cope with salinity for the extraction of dissolved MCs but none assessed solid phase extraction (SPE) so far. It was found that salt had negligible effect on the SPE recovery of dissolved MCs using the C18 cartridge while an overestimation up to 67% was noted for some variants with a polymeric sorbent. The limits of detection (LOD) and quantification (LOQ) were 1.0-22 and 5.5-124 pg on column for the intracellular toxins, while 0.05-0.81 and 0.13-2.4 ng/mL were obtained for dissolved toxins. Extraction recoveries were excellent for intracellular (89-121%) and good to excellent for extracellular cyanotoxins (73-102%) while matrix effects were considered neglectable (<12% for 16/20 toxin-matrix combinations), except for the two MC-RR variants. The strategy based on the application of a corrective factor to compensate for losses proved useful as the accuracy was satisfactory (73-117% for intra- and 81-139% for extracellular cyanotoxins, bias <10% for 46/60 conditions, with a few exceptions), with acceptable precisions (intra- and inter-days variabilities <11%). We then applied this method on natural colonies of Microcystis spp. subjected to a salt shock, mimicking their estuarine transfer, in order to assess their survival and to quantify their toxins. The colonies of Microcystis spp. had both their growth and photosynthetic activity impaired at salinities from 10, while toxins remained mainly intracellular (>76%) even at salinity 20, suggesting a potential health risk and contamination of estuarine organisms.


Assuntos
Cianobactérias , Microcystis , Microcistinas/análise , Cromatografia Líquida/métodos , Toxinas de Cianobactérias , Espectrometria de Massas em Tandem/métodos , Água Doce/química , Cromatografia Líquida de Alta Pressão , Extração em Fase Sólida
17.
Environ Pollut ; 342: 123123, 2024 Feb 01.
Artigo em Inglês | MEDLINE | ID: mdl-38081380

RESUMO

The death of aquatic and terrestrial organisms caused by cyanobacterial blooms has been a topic of considerable concern since the 19th century. Microcystin-LR (MC-LR) produced by cyanobacterial blooms threaten natural ecosystems and human health. Therefore, establishing an effective monitoring and early warning system to detect MC-LR in water bodies is crucial. However, rapidly and intuitively assessing the distribution traits of MC-LR in lakes is a challenging task due to the complexities and expenses associated with conventional detection methods. To overcome these technical limitations, we introduce a novel and effective method for evaluating the distribution of MC-LR in lakes. This method is achieved by using a fluorescence probe (BAD) technology, marking the first application of this technology in evaluating the distribution of MC-LR in natural lake environments. The probe BAD is endowed with unique functions through clever functionalization modification. Experimental results exhibit that BAD has different fluorescence signals at various lake sampling points. The correlation analysis of fluorescence data and physicochemical indicators determines that the fluorescence data of the probe exhibit good correlation with MC-LR, implying that BAD is capable of detecting MC-LR in lakes. Moreover, the introduction of fluorescence technology to achieve the intuitive distribution of MC-LR in the entire plateau lake. This study provides a new method for evaluating the distribution of MC-LR in plateau lakes. It opens a new avenue for exploring the relationship between cyanobacterial blooms and MC-LR in natural waters.


Assuntos
Cianobactérias , Ecossistema , Toxinas Marinhas , Humanos , Fluorescência , Microcistinas/análise , Tecnologia
18.
Sci Total Environ ; 912: 169249, 2024 Feb 20.
Artigo em Inglês | MEDLINE | ID: mdl-38081424

RESUMO

Harmful algal blooms (HABs) are a threat to freshwater systems over the world due to the production of hepatotoxins like microcystin (MC), and nuisance taste and odour (T&O) compounds like 2-methylisoborneol (MIB). While MCs are known to cause detrimental effects to both water quality and human health, MIB is only reported to cause aesthetical problems. In this study, we investigated a tropical, urban lake that was experiencing persistent MC and MIB events. Although it was dominated by Microcystis blooms, analysis revealed that the toxigenic Microcystis were not the only species driving the MC concentrations. Additionally, there was also a lack of causative species for the MIB events. Through isolation, we have identified three toxigenic Microcystis found to produce four different variants of MCs, and two novel non-toxigenic Microcystis that were capable of producing MIB. The ability to produce MIB had never been previously reported for this species. Compared to other major producers such as Planktothricoides sp. and Streptomyces sp., the MIB synthase genes of our Microcystis sp. strains were partial, illustrating the possibility of unique synthesis pathways. The Microcystis sp. strains were found to produce about 2.77-5.22 fg MIB cell-1, with a majority of the contents (70-80 %) existing in the extracellular phase. Correlation analysis of field study indicated that phosphorus limitation may have an indirect effect on non-toxigenic Microcystis abundance and proportion by influencing the toxigenic genotype, suggesting that current measures to control HABs may favour the proliferation of the non-toxigenic Microcystis. The potential for Microcystis sp. to produce MIB through unique synthesis pathway, coupled with the potential dominance of non-toxigenic genotypes in Microcystis blooms, signals the possibility that non-toxigenic Microcystis should be monitored as well.


Assuntos
Cianobactérias , Microcystis , Humanos , Microcystis/genética , Microcystis/metabolismo , Lagos/análise , Cianobactérias/genética , Microcistinas/análise , Proliferação Nociva de Algas , Genótipo
19.
J Microbiol Methods ; 217-218: 106886, 2024.
Artigo em Inglês | MEDLINE | ID: mdl-38159650

RESUMO

Research interest in ecological significance, toxicity, and potential applications of cyanobacterial metabolites has grown as a result of the current extensive cyanobacterial blooms in water bodies. Under favourable conditions, specific cyanobacterial species release cyanotoxins, hepatotoxins, dermatoxins, neurotoxins, and cytotoxins, creating a heightened threat to aquatic ecosystems and human health. Wastewater treatment plants (WWTPs) offer one of the best culture media for cyanobacterial development and synthesis of cyanotoxins by providing optimum environmental conditions, including temperature, light intensity, lengthy water residence time, and nutrient-rich habitat. To discover the intricate relationships between cyanobacterial populations and other living organisms, it is important to comprehend the cyanobacterial communities in the ecology of WWTPs. Monitoring strategies of these cyanotoxins typically involved combined assessments of biological, biochemical, and physicochemical methodologies. Microscopic observations and physicochemical factors analysis cannot be carried out for toxicity potential analysis of blooms. Due to their high sensitivity, molecular-based approaches allow for the early detection of toxic cyanobacteria, while biological analysis is carried out by using water bloom material and cell extracts to screen cyanotoxins build up in organisms. As each approach has benefits and drawbacks, the development of an integrated multi-method laboratory system is essential to obtain trustworthy results and accurate detection of cyanotoxin levels in WWTPs allowing us to take necessary proactive and preventative approaches for effective wastewater treatment.


Assuntos
Toxinas de Cianobactérias , Cianobactérias , Humanos , Ecossistema , Água , Microcistinas/análise
20.
Anal Biochem ; 687: 115429, 2024 04.
Artigo em Inglês | MEDLINE | ID: mdl-38113981

RESUMO

Microcystin-producing cyanobacterial blooms are a global issue threatening drinking water supplies and recreation on lakes and beaches. Direct measurement of microcystins is the only way to ensure waters have concentrations below guideline concentrations; however, analyzing water for microcystins takes several hours to days to obtain data. We tested LightDeck Diagnostics' bead beater cell lysis and two versions of the quantification system designed to give microcystin concentrations within 20 min and compared it to the standard freeze-thaw cycle lysis method and ELISA quantification. The bead beater lyser was only 30 % effective at extracting microcystins compared to freeze-thaw. When considering freeze-thaw samples analyzed in 2021, there was good agreement between ELISA and LightDeck version 2 (n = 152; R2 = 0.868), but the LightDeck slightly underestimated microcystins (slope of 0.862). However, we found poor relationships between LightDeck version 2 and ELISA in 2022 (n = 49, slopes 0.60 to 1.6; R2 < 0.6) and LightDeck version 1 (slope = 1.77 but also a high number of less than quantifiable concentrations). After the quantification issues are resolved, combining the LightDeck system with an already-proven rapid lysis method (such as microwaving) will allow beach managers and water treatment operators to make quicker, well-informed decisions.


Assuntos
Técnicas Biossensoriais , Cianobactérias , Microcistinas/análise , Microcistinas/metabolismo , Proliferação Nociva de Algas , Lagos/análise
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