Freshwater Toxins Research Articles

A short-term exposure to saxitoxin triggers a multitude of deleterious effects in Daphnia magna at levels deemed safe for human health

Harmful algal blooms and the toxins produced during these events are a human and environmental health concern worldwide. Saxitoxin and its derivatives are potent natural aquatic neurotoxins produced by certain freshwater cyanobacteria and marine algae species during these bloom events. Saxitoxins effects on human health are well studied, however its effects on aquatic biota are still largely unexplored. This work aims at evaluating the effects of a pulse acute exposure (24 h) of the model cladoceran Daphnia magna to 30 μg saxitoxin L−1, which corresponds to the safety guideline established by the World Health Organization (WHO) for these toxins in recreational freshwaters. Saxitoxin effects were assessed through a comprehensive array of biochemical (antioxidant enzymes activity and lipid peroxidation), genotoxicity (alkaline comet assay), neurotoxicity (total cholinesterases activity), behavioral (swimming patterns), physiological (feeding rate and heart rate), and epigenetic (total 5-mC DNA methylation) biomarkers. Exposure resulted in decreased feeding rate, heart rate, total cholinesterases activity and catalase activity. Contrarily, other antioxidant enzymes, namely glutathione-S-transferases and selenium-dependent Glutathione peroxidase had their activity increased, together with lipid peroxidation levels. The enhancement of the antioxidant enzymes was not sufficient to prevent oxidative damage, as underpinned by lipid peroxidation enhancement. Accordingly, average DNA damage level was significantly increased in STX-exposed daphnids. Total DNA 5-mC level was significantly decreased in exposed organisms. Results showed that even a short-term exposure to saxitoxin causes significant effects on critical molecular and cellular pathways and modulates swimming patterns in D. magna individuals. This study highlights sub-lethal effects caused by saxitoxin in D. magna, suggesting that these toxins may represent a marked challenge to their thriving even at a concentration deemed safe for humans by the WHO.

Underway measurement of cyanobacterial microcystins using a surface plasmon resonance sensor on an autonomous underwater vehicle

AbstractFreshwater cyanobacterial harmful algal blooms (CHABs) are a well‐known global public health threat. Monitoring and early detection of CHAB toxins are currently accomplished using labor‐intensive sampling techniques and subsequent shore‐based analyses, with results typically reported 24–48 h after sample collection. We have developed and implemented an uncrewed, autonomous mobile sampler‐analytical system capable of conducting targeted in situ toxin measurements in < 2 h. A surface plasmon resonance (SPR) instrument was combined with the environmental sample processor (ESP) to fully automate detection and quantification of particle‐associated cyanobacterial microcystins (pMC). This sensor‐sampler system was integrated with a long‐range autonomous underwater vehicle (LRAUV) and deployed in western Lake Erie for field trials in the summer of 2021. The LRAUV was remotely piloted to acquire samples at selected locations within and adjacent to a CHAB. Sixteen pMC measurements ranging from 0.09 to 0.55 μg/L lake water were obtained over a 14‐day period without recovery of the LRAUV. The SPR/ESP/LRAUV system complements existing satellite, aerial, and manual sampling CHAB survey techniques, and could be used to enhance predictive models that underpin bloom and toxicity forecasts. This system is also extensible to detection of other algal toxins in freshwater and marine environments, with its near real‐time assessment of bloom toxin levels potentially offering additional socioeconomic benefits and public health protection in a variety of settings.

Optimization and validation of a protein phosphatase inhibition assay for accessible microcystin detection

The presence of cyanobacterial toxins in freshwater constitutes an increasing public health concern, especially affecting developing countries where the high cost of available methods makes monitoring programs difficult. The phosphatase inhibition assay (PPIA) is a sensitive method with low instrument requirements that allows the quantification of the most frequent cyanotoxins, microcystins (MCs). In this work, we implemented a PPIA, starting from Protein Phosphatase 1 (PP1) expression up to the validation with samples of algal blooms from Argentina. To do this, we optimized the expression and lyophilization of PP1, and the assay conditions. Also, we included robustness and possible interference analysis. We evaluated the most widely used cyanobacterial lysis methods and determined that heating for 15 min at 95 °C is simple and adequate for this assay. Then, we performed MC spikes recovery assays on water samples from three dams from Argentina, resulting in a recovery ranging from 77 to 115%. The limit of detection (LOD) was 0.4 μg/L and the linear range is 0.4 μg/L - 5 μg/L. Finally, we evaluated 65 environmental samples where MCs was measured by ELISA test containing from 0 μg/L to 625 μg/L. The PPIA showed excellent correlation (Pearson correlation coefficient = 0.967), no false negative and no false positives above the 1 μg/L WHO guideline (0.11 false positive rate). In conclusion, we optimized and validated a PPIA to be an effective and accessible alternative to available commercial tests.

Microcystin-LR in Primary Liver Cancers: An Overview.

The cyanobacterial blooms produced by eutrophic water bodies have become a serious environmental issue around the world. After cellular lysing or algaecide treatment, microcystins (MCs), which are regarded as the most frequently encountered cyanobacterial toxins in fresh water, are released into water. Among all the variants of MCs, MC-LR has been widely studied due to its severe hepatotoxicity. Since 1992, various studies have identified the important roles of MC-LR in the origin and progression of primary liver cancers (PLCs), although few reviews have focused on it. Therefore, this review aims to summarize the major achievements and shortcomings observed in the past few years. Based on the available literature, the mechanisms of how MC-LR induces or promotes PLCs are elucidated in this review. This review aims to enhance our understanding of the role that MC-LR plays in PLCs and provides a rational approach for future applications.

Occurrence of cylindrospermopsin, anatoxin-a and their homologs in the southern Czech Republic – Taxonomical, analytical, and molecular approaches

Water bloom-forming cyanobacteria have a severe impact on freshwater quality. Although some cyanobacterial toxins such as microcystins have been studied extensively, other toxins like anatoxin-a (ATX) and their structural analogs - as well as cyanobacterial taxa producing these toxins remain to be explored in detail. The present study investigated levels of ATX, CYN and their homologs along with the occurrence of anaC and cyrJ genes in water blooms in 16 sites in the Czech Republic that were pre-selected concerning the presence of potential toxin producers. Besides, we also studied toxins and genes in a series of strains available in our laboratories. ATX and its congener HATX were detected in 5 natural biomass samples from the Czech Republic (maximum concentration 2.8 micrograms per gram d.w.). Interestingly, the anaC gene coding for ATX production was not detected in any of these toxin-positive biomass samples. The concentrations of ATX congeners in cyanobacterial laboratory strains were about 10-times higher than those of the original ATX, which calls for further research addressing levels and hazards of ATX analogs. Regarding the CYN and 7-deoxyCYN (other CYN congeners were not analyzed in this study) - these toxins were identified in a single small pond in the Czech Republic at concentrations 4.3 and 2.7 micrograms per gram of biomass d.w., respectively (corresponded to dissolved concentrations higher than 1 microgram per liter). The CYN-positive sample was dominated by CYN-producing taxa Raphidiopsis (basionym Cylindrospermopsis) and Cuspidothrix. We also confirmed the presence of a specific cyrJ gene in this natural bloom sample. To our knowledge, this is the first study pointing to Raphidiopsis (Cylindrospermopsis) and Cuspidothrix as producers of CYN in Europe. This observation calls for further research because of their increasing occurrence in (Central) Europe along with the global change. The present study demonstrates the importance of using combined (taxonomical, analytical, and molecular) approaches in the assessment of hazardous cyanobacteria and their toxins in freshwaters.

Cucurbituril Ameliorates Liver Damage Induced by Microcystis aeruginosa in a Mouse Model.

Microcystis aeruginosa is a cyanobacterium that produces a variety of cyclic heptapeptide toxins in freshwater. The protective effects of the macromolecular container cucurbit[7]uril (CB7) were evaluated using mouse models of cyanotoxin-induced liver damage. Biochemical analysis of liver function was performed to gauge the extent of liver damage after exposure to cyanobacterial crude extract [CCE; LD50 = 35 mg/kg body weight; intraperitoneal (i.p.)] in the absence or presence of CB7 (35 mg/kg body weight, i.p.). CCE injection resulted in liver enlargement, potentiated the activities of alanine aminotransferase (ALT) and glutathione S-transferase (GST), increased lipid peroxidation (LPO), and reduced protein phosphatase 1 (PP1) activity. CCE-induced liver enlargement, ALT and GST activities, and LPO were significantly reduced when CB7 was coadministered. Moreover, the CCE-induced decline of PP1 activity was also ameliorated in the presence of CB7. Treatment with CB7 alone did not affect liver function, which exhibited a dose tolerance of 100 mg/kg body wt. Overall, our results illustrated that the addition of CB7 significantly reduced CCE-induced hepatotoxicity (P < 0.05).

Degradation of microcystin-LR and cylindrospermopsin by continuous flow UV-A photocatalysis over immobilised TiO2

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 TiO2 on glass tubes and UV-A light. The effect of flow rate and hydrogen peroxide addition on the efficiency of cyanotoxin removal were evaluated. An analysis of the effects on microcystin-LR removal efficiency showed that low flow rates (1 mL/min) and high H2O2 concentrations (120 mg/L) were needed to provide effective degradation. Up to 27.9% and 39.1% removal of MC-LR and CYN, respectively were achieved by UV-A/TiO2 after a single pass through the reactor. A slight increase of the removal of both cyanotoxins was observed when they were in a mixture (35.5% of MC-LR and 51.3% of CYN). The addition of H2O2 to the UV/TiO2 system led to an average removal enhancement of 92.6% of MC-LR and of 29.5% of CYN compared to the UV/TiO2 system. Photolysis assisted by H2O2 degraded MC-LR by up to 77.7%. No significant removal (<10%) was observed by photolysis alone or physical adsorption.This study presents a proof-of-principle that demonstrates the feasibility for this technology to be integrated in large-scale applications.

First Report of the Co-occurrence of Cylindrospermopsin, Nodularin and Microcystins in the Freshwaters of Lake Victoria, Tanzania

There is a global concern regarding the increase of cyanotoxins in freshwater and their potential effects on human health. The existence of multiple toxins in freshwater can result in an increased risk of their bioaccumulation in humans from their ingestion through contaminated drinking water or recreational activities. This study, the first of its kind, was conducted to determine the occurrence of thirteen cyanotoxins namely; microcystins (-LA, -LF, -LR, -LY, -LW, -RR, -YR, -WR, dm MC-RR and dm MC-LR), anatoxin-a, nodularin and cylindrospermopsin in the freshwaters of Lake Victoria in Tanzania. A total of 23 sites were selected for water sampling. Samples were randomly collected from lakeshores (n = 54), wells (n = 66) and piped water (n = 18) in two phases, February (dry season) and December (rainy season) 2018. Samples (n = 138) were analysed using liquid chromatography mass spectrometry (UPLC-MS/MS). Cylindrospermopsin was the most abundant cyanotoxin detected in the lakeshores, with eight of the nine collection sites (89%) reporting cylindrospermopsin in phase I, compared to three out of nine (33%) in phase II. Microcystin congeners -RR, -LR and -YR were detected in phase I, with microcystins -RR and -LR detected in phase II. MC concentrations ranged from 0.003 to 0.007 μg/L for MC-RR, 0.01–0.013 μg/L for MC-LR and 0.004 to 0.01 μg/L for cylindrospermopsin, with nodularin reported once at a concentration of 0.01 μg/L. No cyanotoxins were detected in wells or in treated pipe water samples. The existence of multiple toxins in different collection sites may lead to synergistic effects and increase the toxicological risk to humans. This is the first study to report the presence of cylindrospermopsin and nodularin in the freshwaters of Lake Victoria.

A sensitive and accurate method for simultaneous analysis of algal toxins in freshwater using UPLC-MS/MS and 15N-microcystins as isotopically labelled internal standards

The development of analytical methods for the detection and accurate quantification of algal toxins is of importance to assess the health risk of exposure to algal toxins in freshwater sources. This study established a sensitive and accurate analytical method for the quantification of 13 algal toxins (microcystins and nodularin) based on solid phase extraction (SPE) coupled with UPLC-MS/MS, in which 15N-microcystins were used as surrogate/internal standards. SPE method was optimized to extract the target algal toxins in freshwater samples. Good SPE efficiencies (84–96%) were achieved for the overwhelming majority of the investigated algal toxins when SPE was performed using HLB (500 mg, 6 mL) under alkaline conditions (pH 11). An accurate quantitative analysis of the algal toxins in real freshwater samples was performed by using 15N-labelled microcystins as isotopically labelled internal standards (ILISs), which compensated for the loss of target toxins during the whole analytical process. In addition, ILISs also helped to correct the effects of environmental matrices and instrument fluctuation in UPLC-MS/MS analysis. The limit of method quantification (MQL) for the algal toxins was <2.0 ng/L that is sensitive enough to quantify extremely low levels of target toxins in freshwater samples.

Magnetic nanostructures for marine and freshwater toxins removal

Marine and freshwater toxins contaminate water resources, shellfish and aquaculture products, causing a broad range of toxic effects in humans and animals. Different core-shell nanoparticles were tested as a new sorbent for removing marine and freshwater toxins from liquid media. Water solutions were contaminated with 20 μg/L of marine toxins and up to 50 μg/L of freshwater toxins and subsequently treated with 250 or 125 mg/L of nanoparticles. Under these conditions, carbon nanoparticles removed around 70% of saxitoxins, spirolides, and azaspiracids, and up to 38% of diarrheic shellfish poisoning toxins. In the case of freshwater toxins, the 85% of microcystin LR was eliminated; other cyclic peptide toxins were also removed in a high percentage. Marine toxins were adsorbed in the first 5 min of contact, while for freshwater toxins it was necessary 60 min to reach the maximum adsorption. Toxins were recovered by extraction from nanoparticles with different solvents. Gymnodinium catenatum, Prorocentrum lima, and Microcystis aeruginosa cultures were employed to test the ability of nanoparticles to adsorb toxins in a real environment, and the same efficacy to remove toxins was observed in these conditions. These results suggest the possibility of using the nanotechnology in the treatment of contaminated water or in chemical analysis applications.

Quantification of cylindrospermopsin, anatoxin-a and homoanatoxin-a in cyanobacterial bloom freshwater using direct injection/SPE coupled with UPLC-MS/MS

Analytical methods based on direct injection (DI) and solid phase extraction (SPE) coupled with ultrahigh performance liquid chromatography-tandem mass spectrometry (UPLC- MS/MS) were developed for the determination of anatoxin-a (ATX-a), cylindrospermopsin (CYN), and homoanatoxin-a (HATX-a) in freshwater samples impacted with cyanobacterial blooms. The presence of CYN in freshwater samples was detected and quantified based on direct injection method, while ATX-a and HATX-a could be determined by both DI and SPE-based methods. Matrix effects (ME) on the signal intensity of the cyanotoxins were systematically evaluated for both direct injection and SPE extract samples. CYN, ATX-a, and HATX-a suffered a significant suppression during UPLC-MS/MS. The selection of internal standards (ISs) for compensating/correcting the losses of target cyanotoxins during sample preparation and matrix effects in UPLC-MS/MS analyses were systematically evaluated. Acetaminophen-d4 (an isotopically labelled acetaminophen) is a suitable internal standard for correcting the ME on the signal intensity of ATX-a and HATX-a, while the use of L-phenylalanine-d5 or caffeine-d9 as IS for correcting ME of these toxins was not efficient, as expected. The method detection limit (MDL) for the target cyanotoxins ranged from 0.6 to 15 ng/L, which is sensitive enough to detect the presence of these toxins in cyanobacterial bloom freshwater. The developed methods were successfully applied for routine monitoring of the occurrence of these cyanotoxins in a local water body. Monitoring results depicted that ATX-a, CYN and HATX-a were ubiquitously detected in water samples, at concentrations ranging from 70 to 24,600 ng/L.

Detection of free and bound microcystins in tilapia fish from Egyptian fishpond farms and its related public health risk assessment

Microcystins (MCs), the most common cyanobacterial toxins in freshwaters, can accumulate in aquatic animals in free and bound forms. MCs therefore pose a risk to human health upon consumption of contaminated fish tissues, as they cause severe liver damage and death with potential carcinogenic effects. While there have been extensive studies on free MC contents in fish tissues, the detection of bound MCs in fish is largely unexplored. In the present study, both free and bound MCs were monthly monitored in tilapia fish from three tropical fishponds in Egypt for one year. Fishpond waters contained high concentrations of MCs (18–44 µg/l). Free MCs were estimated in tilapia fish organs at levels up to 11.8 ng/g in intestines, 8.3 ng/g in livers and 0.38 ng/g in edible tissues. Concentrations of bound MCs in edible tissues as determined by Lemieux oxidation technique (15,000–19,000 ng/g fresh weight, FW) were several-folds higher than free MCs. The estimated daily intake (EDI) for free MCs (0.0006–0.002 μg/kg/day MCs) in edible tissues was lower than the WHO limit (0.04 µg/kg/day), while EDI of bound MCs exceeded this limit by a factor of 77–2396. Therefore, both free and bound MCs in fish tissues should be considered when fish are monitored for human consumption.

An Innovative Portable Biosensor System for the Rapid Detection of Freshwater Cyanobacterial Algal Bloom Toxins.

Harmful algal blooms in freshwater systems are increasingly common and present threats to drinking water systems, recreational waters, and ecosystems. A highly innovative simple to use, portable biosensor system (MBio) for the rapid and simultaneous detection of multiple cyanobacterial toxins in freshwater is demonstrated. The system utilizes a novel planar waveguide optical sensor that delivers quantitative fluorescent competitive immunoassay results in a disposable cartridge. Data are presented for the world's first duplex microcystin (MC)/cylindrospermopsin (CYN) assay cartridge using a combination of fluorophore-conjugated monoclonal antibodies as detector molecules. The on-cartridge detection limits of 20% inhibitory concentration (IC20) was 0.4 μg/L for MC and 0.7 μg/L for CYN. MC assay coverage of eight important MC congeners was demonstrated. Validation using 45 natural lake water samples from Colorado and Lake Erie showed quantitative correlation with commercially available laboratory-based enzyme linked immunosorbent assays. A novel cell lysis module was demonstrated using cyanobacteria cultures. Results show equivalent or better performance than the gold-standard but more tedious 3× freeze-thaw method, with >90% cell lysis for laboratory cultures. The MBio system holds promise as a versatile tool for multiplexed field-based cyanotoxin detection, with future analyte expansion including saxitoxin, anatoxin-a, and marine biotoxins.

Development of a two-step immunochromatographic assay for microcystin-LR based on fluorescent microspheres

Microcystins (MCs) are a class of toxins that are mainly produced by cyanobacteria. Among them, microcystin-leucine arginine (MC-LR) is one of the most toxic and harmful of the freshwater toxins, and it has caused many accidents and threats to human health. In the present study, we report a neoteric lateral flow fluorescent microsphere immunochromatographic assay (FM-ICA) combined with UV light detection to rapidly and quantitatively detect MC-LR in freshwater food, based on direct competitive immunoreactions on chromatographic strips. In the method, MC-LR artificial antigen, MC-LR-bovine serum albumin (MC-LR-BSA), and goat anti-rabbit immunoglobulin G (IgG) were labelled with europium (Eu) nanospheres that functioned as a luminescence tracer. Goat anti-mouse IgG and rabbit IgG were spread on a nitrocellulose (NC) membrane for the test (T) line and control (C) line, respectively. The optimal parameters were 1 mg/mL for the goat anti-mouse IgG and rabbit IgG, 20 μg of MC-LR-BSA conjugated with Eu nanospheres, 1:100 for the dilution of Eu-MC-LR-BSA, and a 1:30000 dilution of anti-MC-LR monoclonal antibody (mAb) with an assay time of 15 min. The working range of the MC-LR standard curve was 0.1–5.0 μg/L with a limit of detection (LOD) of 0.0542 μg/L and a 50% inhibitory concentration (IC50) of 0.5613 μg/L. The average recoveries of the FM-ICA for detecting MC-LR in real samples ranged from 90.1 to 109.3%, with coefficients of variation under 15.8%. The FM-ICA test strips for quantitative determination of MC-LR provide sensitive, simple, and rapid performance, and can be used to monitor freshwater samples.

Best Paper Award.

Best Paper Award.

Blurred lines: Multiple freshwater and marine algal toxins at the land-sea interface of San Francisco Bay, California

San Francisco Bay (SFB) is a eutrophic estuary that harbors both freshwater and marine toxigenic organisms that are responsible for harmful algal blooms. While there are few commercial fishery harvests within SFB, recreational and subsistence harvesting for shellfish is common. Coastal shellfish are monitored for domoic acid and paralytic shellfish toxins (PSTs), but within SFB there is no routine monitoring for either toxin. Dinophysis shellfish toxins (DSTs) and freshwater microcystins are also present within SFB, but not routinely monitored. Acute exposure to any of these toxin groups has severe consequences for marine organisms and humans, but chronic exposure to sub-lethal doses, or synergistic effects from multiple toxins, are poorly understood and rarely addressed. This study documents the occurrence of domoic acid and microcystins in SFB from 2011 to 2016, and identifies domoic acid, microcystins, DSTs, and PSTs in marine mussels within SFB in 2012, 2014, and 2015. At least one toxin was detected in 99% of mussel samples, and all four toxin suites were identified in 37% of mussels. The presence of these toxins in marine mussels indicates that wildlife and humans who consume them are exposed to toxins at both sub-lethal and acute levels. As such, there are potential deleterious impacts for marine organisms and humans and these effects are unlikely to be documented. These results demonstrate the need for regular monitoring of marine and freshwater toxins in SFB, and suggest that co-occurrence of multiple toxins is a potential threat in other ecosystems where freshwater and seawater mix.

Cyanobacterial Toxins in Freshwater and Food: Important Sources of Exposure to Humans.

A recent ecological study demonstrated a significant association between an increased risk of nonalcoholic liver disease mortality and freshwater cyanobacterial blooms. Moreover, previous epidemiology studies highlighted a relationship between cyanotoxins in drinking water with liver cancer and damage and colorectal cancer. These associations identified cyanobacterial blooms as a global public health and environmental problem, affecting freshwater bodies that are important sources for drinking water, agriculture, and aquafarms. Furthermore, as a result of climate change, it is expected that our freshwater environments will become more favorable for producing harmful blooms that produce various cyanotoxins. Food is an important source of cyanotoxin exposure to humans, but it has been less addressed. This paper synthesizes information from the studies that have investigated cyanotoxins in freshwater and food on a global scale. We also review and summarize the health effects and exposure routes of cyanotoxins and candidates for cyanotoxin treatment methods that can be applied to food.

Enhanced sensitivity and resolution for the analysis of paralytic shellfish poisoning toxins in water using capillary electrophoresis with amperometric detection and field-amplified sample injection.

The profiling of the most lethal paralytic shellfish poisoning toxins (PSTs) in freshwater has increased the need to establish an alternative analytical method with high sensitivity and resolution. In this paper, a coupling technique of field-amplified sample injection (FASI) and CE with end-column amperometric detection (CE-AD) was developed to improve the detection sensitivity and separation of PSTs by electrokinetically injecting a water plug of analytes to the capillary filled with a high-conductivity BGE. Parameters affecting FASI and CE process were carefully adjusted to achieve the highest response and resolution. Separation selectivity for PSTs, especially for the analogues and epimers, was greatly enhanced by using 40 mM Britton-Robinson buffer (pH 9.5) as BGE, which altered the EOF and mobility of the analytes that interacted with polyborate ions. Satisfactory linear relationship between peak current and concentration of toxins were gained over a wide range of 1.95-254 μg/L. The detection limits (S/N = 3) for five PSTs ranged from 0.63 to 3.11 μg/L, which are below the health alert level in drinking water. In comparison with the up-to-date reporting chromatographic methods, the FASI-CE-AD method was simple, low-cost, selective, and sensitive enough for direct quantification of PSTs at very low levels, implying a potential for screening and monitoring of PSTs in surface waters.

Monitoring of freshwater toxins in European environmental waters by using novel multi-detection methods.

Monitoring the quality of freshwater is an important issue for public health. In the context of the European project μAqua, 150 samples were collected from several waters in France, Germany, Ireland, Italy, and Turkey for 2 yr. These samples were analyzed using 2 multitoxin detection methods previously developed: a microsphere-based method coupled to flow-cytometry, and an ultra-performance liquid chromatography-tandem mass spectrometry (UPLC-MS/MS) method. The presence of microcystins, nodularin, domoic acid, cylindrospermopsin, and several analogues of anatoxin-a (ATX-a) was monitored. No traces of cylindrospermopsin or domoic acid were found in any of the environmental samples. Microcystin-LR and microcystin-RR were detected in 2 samples from Turkey and Germany. In the case of ATX-a derivatives, 75% of samples contained mainly H2 -ATX-a and small amounts of H2 -homoanatoxin-a, whereas ATX-a and homoanatoxin-a were found in only 1 sample. These results confirm the presence and wide distribution of dihydro derivatives of ATX-a toxins in European freshwaters. Environ Toxicol Chem 2017;36:645-654. © 2016 SETAC.

Toxicological Perspective on Climate Change: Aquatic Toxins.

In recent years, our group and several others have been describing the presence of new, not previously reported, toxins of high toxicity in vectors that may reach the human food chain. These include tetrodotoxin in gastropods in the South of Europe, ciguatoxin in fish in the South of Spain, palytoxin in mussels in the Mediterranean Sea, pinnatoxin all over Europe, and okadaic acid in the south of the U.S. There seem to be new marine toxins appearing in areas that are heavy producers of seafood, and this is a cause of concern as most of these new toxins are not included in current legislation and monitoring programs. Along with the new toxins, new chemical analogues are being reported. The same phenomenom is being recorded in freshwater toxins, such as the wide appearance of cylindrospermopsin and the large worldwide increase of microcystin. The problem that this phenomenon, which may be linked to climate warming, poses for toxicologists is very important not only because there is a lack of chronic studies and an incomplete comprehension of the mechanism driving the production of these toxins but also because the lack of a legal framework for them allows many of these toxins to reach the market. In some cases, it is very difficult to control these toxins because there are not enough standards available, they are not always certified, and there is an insufficient understanding of the toxic equivalency factors of the different analogues in each group. All of these factors have been revealed and grouped through the massive increase in the use of LC-MS as a monitoring tool, legally demanded, creating more toxicological problems.