Beata Bober

Cyanobacterial blue color formation during lysis under natural conditions.

ABSTRACT Cyanobacteria produce numerous volatile organic compounds (VOCs), such as β-cyclocitral, geosmin, and 2-methylisoborneol, which show lytic activity against cyanobacteria. Among these compounds, only β-cyclocitral causes a characteristic color change from green to blue (blue color formation) in the culture broth during the lysis process. In August 2008 and September 2010, the lysis of cyanobacteria involving blue color formation was observed at Lake Tsukui in northern Kanagawa Prefecture, Japan. We collected lake water containing the cyanobacteria and investigated the VOCs, such as β-cyclocitral, β-ionone, 1-propanol, 3-methyl-1-butanol, and 2-phenylethanol, as well as the number of cyanobacterial cells and their damage and pH changes. As a result, the following results were confirmed: the detection of several VOCs, including β-cyclocitral and its oxidation product, 2,2,6-trimethylcyclohexene-1-carboxylic acid; the identification of phycocyanin based on its visible spectrum; the lower pH (6.7 and 5.4) of the lysed samples; and characteristic morphological change in the damaged cyanobacterial cells. We also encountered the same phenomenon on 6 September 2013 in Lake Sagami in northern Kanagawa Prefecture and obtained almost the same results, such as blue color formation, decreasing pH, damaged cells, and detection of VOCs, including the oxidation products of β-cyclocitral. β-Cyclocitral derived from Microcystis has lytic activity against Microcystis itself but has stronger inhibitory activity against other cyanobacteria and algae, suggesting that the VOCs play an important role in the ecology of aquatic environments.

Determination of some cyanopeptides synthesized by Woronichinia naegeliana (Chroococcales, Cyanophyceae)

Nineteen compounds isolated from field samples of cyanobacteria Woronichinia naegeliana (Unger) Elenkin were identified. They fell into four classes of peptides: cyanopeptolins (cyanopeptolin B, cyanopeptolin C, cyanopeptolin D, cyanopeptolin 880, micropeptin 88D, micropeptin 478‐B, micropeptin SD999, micropeptin T2, planktopeptin BL1061), microginins (microginin 478, microginin 757, microginin 51A, microginin 91E, microginin FR3, microginin FR4), anabaenopeptins (oscillamide B) and possibly microcystins (trace amounts of microcystin‐LR) showing respectively fragment patterns in their electrospray ion source‐MS spectra. The molecular masses of the determined peptides range from 700 to 1100 Da. These results confirm the remarkable ability of cyanobacteria to synthesize a wide array of peptides.

Phytoremediation of anatoxin-a by aquatic macrophyte Lemna trisulca L.

The neurotoxin anatoxin-a (ANTX-a), one of the most common cyanotoxin, poses a health risk to people and can be lethal to aquatic organisms. This paper presents results on its bioremediation by the aquatic macrophyte Lemna trisulca. We show that the plant is resistant to the harmful impact of toxin and is capable of removing ANTX-a from water. Some of the ANTX-a concentrations which were used in our experiments were much higher than those found in natural conditions. The exposition of L. trisulca to 2.5 μg ANTX-a/mL did not affect its biomass accumulation within 24 d. Significant decreases in biomass content by 21% and 30% were demonstrated in samples cultivated in media containing 12.5 μg ANTX-a/mL after 18 and 24 day of experiment, respectively. One gram of fresh weight (f.w.) of L. trisulca cultured for 14 d in the media containing 50 μg ANTX-a removed 95% of the initial toxin concentration; for media with 250 μg ANTX-a, 86% was removed. In tests of ANTX-a binding stability and degradation we transferred the macrophyte to fresh media without added toxin; within 14 d the content of accumulated ANTX-a in the macrophyte decreased by 76% (from initial 19.3 μg ANTX-a/gf.w.), 71% (from 37.3 μg ANTX-a/g f.w.) and 47% (from 63.7 μg ANTX-a/g f.w.). The quantity of ANTX-a released to media was minimal: from 3.5% to 5.1% of the initial bioaccumulated value. The data show that part of the ANTX-a was degraded. Mass spectra analyses did not indicate transformation of ANTX-a to already known forms. These findings suggest that L. trisulca has much potential as a phytoremediation agent for stabilization of aquatic environments.

Degradation of microcystin-LR by ozone in the presence of Fenton reagent

In this study the effectiveness and feasibility of the degradation of microcystin-LR (MC-LR) using a combined method ozone/Fenton reagent was investigated. The decomposition of the toxin was determined by the chromatographic technique. The effect of the Fenton reaction on the ozonation was observed at various concentrations of ozone at pH 3.0 and 6.8. A low concentration of ozone (0.01 mg/L) given simultaneously with Fenton reagent was more effective in MC-LR degradation than ozone or Fenton reagent treatment individually regardless of the pH. At higher concentrations of ozone the use together with Fenton reagent at pH 6.8 was less efficient in MC-LR degradation than treatment with ozone alone, whereas at pH 3.0 Fenton process turned out to be more effective. The mixture of ozone and hydrogen peroxide was more striking than using ozone with Fenton reagent regardless of the pH. The complete degradation of MC-LR was achieved using ozone alone at a concentration of 0.10 mg/L, whereas the same result using ozonation with Fenton reagent required a dose of ozone of 0.20 mg/L at pH 6.8. In acidic pH the total removal of MC-LR was achieved using ozone alone at a concentration of 0.20 mg/L and the same result was obtained for the combined method of ozone/Fenton reagent.

Characteristic oxidation behavior of β-cyclocitral from the cyanobacterium Microcystis

The cyanobacterium Microcystis produces volatile organic compounds such as β-cyclocitral and 3-methyl-1-butanol. The lysis of cyanobacteria involving the blue color formation has been occasionally observed in a natural environment. In this study, we focused on the oxidation behavior of β-cyclocitral that contributed to the blue color formation in a natural environment and compared β-cyclocitral with a structurally related compound concerning its oxidation, acidification, and lytic behavior. The oxidation products of β-cyclocitral were identified by the addition of β-cyclocitral in water, in which 2,2,6-trimethylcyclohex-1-ene-1-yl formate and 2,2,6-trimethylcyclohexanone were structurally characterized. That is, β-cyclocitral was easily oxidized to produce the corresponding carboxylic acid and the enol ester in water without an oxidizing reagent, suggesting that this oxidation proceeded according to the Baeyer-Villiger oxidation. The oxidation behavior of β-cyclocitral in a laboratory was different from that in the natural environment, in which 2,2,6- trimethylcyclohexanone was detected at the highest amount in the natural environment, whereas the highest amount in the laboratory was β-cyclocitric acid. A comparison of β-cyclocitral with structurally similar aldehydes concerning the lytic behavior of a Microcystis strain and the acidification process indicated that only β-cyclocitral was easily oxidized. Furthermore, it was found that a blue color formation occurred between pH 5.5 and 6.5, suggesting that chlorophyll a and β-carotene are unstable and decomposed, whereas phycocyanin was stable to some extent in this range. The obtained results of the characteristic oxidation behavior of β-cyclocitral would contribute to a better understanding of the cyanobacterial life cycle.

Mycosporine-Like Amino Acids: Potential Health and Beauty Ingredients

Human skin is constantly exposed to damaging ultraviolet radiation (UVR), which induces a number of acute and chronic disorders. To reduce the risk of UV-induced skin injury, people apply an additional external protection in the form of cosmetic products containing sunscreens. Nowadays, because of the use of some chemical filters raises a lot of controversies, research focuses on exploring novel, fully safe and highly efficient natural UV-absorbing compounds that could be used as active ingredients in sun care products. A promising alternative is the application of multifunctional mycosporine-like amino acids (MAAs), which can effectively compete with commercially available filters. Here, we outline a complete characterization of these compounds and discuss their enormous biotechnological potential with special emphasis on their use as sunscreens, activators of cells proliferation, anti-cancer agents, anti-photoaging molecules, stimulators of skin renewal, and functional ingredients of UV-protective biomaterials.

Cylindrospermopsin: cyanobacterial secondary metabolite. Biological aspects and potential risk for human health and life

Cylindrospermopsin (CYN) is a cytotoxin produced by several species of cyanobacteria, which occur all over the world. It was demonstrated that CYN has a wide spectrum of biological activity in animal cells, involving hepatotoxicity, genotoxicity, cytotoxicity and carcinogenic potential, and is considered as one of the factors that caused human poisoning in Palm Island (Australia) and in Caruaru (Brazil). This compound may be introduced into organism by several ways, including consumption of water, fishes and seafood as well as accidental swallowing or aerosol spray inhalation during recreational using of reservoirs covered by cyanobacterial blooms. The information about the CYN impact on environment and its degradation processes under natural conditions is scant. Taking this into consideration CYN should be regarded as a potential threat to human health and life. This review presents physicochemical characteristic and biological activity of CYN, occurrence in freshwaters and its sensitivity to the influence of some environmental factors.

Stability of some microginins synthesized by the cyanobacterium Woronichinia naegeliana (Unger) Elenkin

Microginins are linear oligopeptides synthesized by cyanobacteria. The literature data on their characteristics are scant. This study examined the influence of abiotic factors including pH, temperature, visible and ultraviolet radiation on the stability of the microginins FR3 (MG‐FR3), FR4 (MG‐FR4) and 757 (MG‐757) synthesized by Woronichinia naegeliana. In alkaline conditions (pH 9) only the concentration of MG‐757 was reduced significantly, by 14.3%. The tested microginins were stable at room temperature (half‐life 7–17 weeks). Boiling for one hour caused 26.1% decomposition of MG‐FR4 and 26.8% decomposition of MG‐757; MG‐FR3 was not significantly affected. Under visible radiation the initial content of MG‐FR4 declined 23.0%, but MG‐FR3 and MG‐757 proved insensitive to it. Treatment with a high dose of UV radiation (36 μmol m−2 s−1) caused the tested microginins to degrade by 13.8% to 21.4%. The study showed these microginins to be oligopeptides of high stability, the most stable of them being MG‐FR3.

Densification of cyanobacteria from a lake leading to production of β-cyclocitral and related volatile organic compounds and species change: Densification of cyanobacteria

The purpose of the present study was to demonstrate that the lysis with the blue color formation was caused by densification of the cyanobacteria, and related events of the species change in the cyanobacteria were induced by the resulting volatile organic compounds (VOCs), particularly β‐cyclocitral. In order to obtain a high cell density of cyanobacteria in the laboratory, a concentration technique (graduated cylinder method) using the buoyancy of the gas vesicles was successfully used. The collected scum contained mainly Dolichospermum spp. and Microcystis, and the dispersed cyanobacteria were concentrated in the surface layer after several hours and the concentration ratio became approximately 10. The concentrated cyanobacteria were gradually lysed, while some of the cyanobacteria sank to the bottom, which finally died and disappeared. This method has the additional advantage that it is possible to visualize the entire lysis process. During the concentration process, β‐cyclocitral and its oxidation products together with β‐ionone were significantly detected. Because β‐cyclocitral was easily oxidized to the corresponding carboxylic acid, the pH of the water in the graduated cylinder decreased to approximately 6. Under favorable conditions, lysis with the blue color from phycocyanin could be observed due to the acid stress. Overall, the results of the present study were consistent with the hypothesis that VOCs were produced when the cyanobacteria are highly dense, and that the lysis with the blue color formation occurs due to the higher density.