Degradation Of microcystin-LR Research Articles

A Comparative Study of Microcystin-LR Degradation by UV-A, Solar and Visible Light Irradiation Using Bare and C/N/S-Modified Titania

In an endeavor to tackle environmental problems, the photodegradation of microcystin-LR (MC-LR), one of the most common and toxic cyanotoxins, produced by the cyanobacteria blooms, was examined using nanostructured TiO2 photocatalysts (anatase, brookite, anatase–brookite, and C/N/S co-modified anatase–brookite) under UV-A, solar and visible light irradiation. The tailoring of TiO2 properties to hinder the electron–hole recombination and improve MC-LR adsorption on TiO2 surface was achieved by altering the preparation pH value. The highest photocatalytic efficiency was 97% and 99% with degradation rate of 0.002 mmol L−1 min−1 and 0.0007 mmol L−1 min−1 under UV and solar irradiation, respectively, using a bare TiO2 photocatalyst prepared at pH 10 with anatase to brookite ratio of ca. 1:2.5. However, the bare TiO2 samples were hardly active under visible light irradiation (25%) due to a large band gap. Upon UV, solar and vis irradiation, the complete MC-LR degradation (100%) was obtained in the presence of C/N/S co-modified TiO2 with a degradation rate constant of 0.26 min−1, 0.11 min−1 and 0.04 min−1, respectively. It was proposed that the remarkable activity of co-modified TiO2 might originate from its mixed-phase composition, mesoporous structure, and non-metal co-modification.

Co-culturing of native bacteria from drinking water treatment plant with known degraders to accelerate microcystin-LR removal using biofilter

The biofilm-mediated bioremediation of drinking water source for Microcystin-LR degradation under various water quality parameters was investigated using sand filter with known Microcystin (MC)-degrading bacterial genera: Arthrobacter (A), Bacillus (B) and Sphingomonas (S), both under individual (A, B and S) as well as co-culture condition (A + X, B + X and S + X) with the native bacterial strains (Pseudomonas fragi and Chryseobacterium sp. = X). These native bacterial strains were isolated from the filtration unit of a drinking water treatment plant (DWTP). Before starting the filter operation, the biofilm-forming ability of MC-degraders was evaluated using a unique experimental set-up. The study showed that the MC-LR removal was enhanced by 38% using S + X filter as compared to the uninoculated filter (control). Except for Bacillus sp., MC-degraders in the form of Arthrobacter ramosus and Sphingomonas sp. enhanced the MC removal potential of the native bacterial strains (X) by 10% and 17%, respectively. The central composite design was used to obtain an optimized input parameter (pH, temperature, initial turbidity and retention time) for the filter operation. Various output parameters including dissolved organic carbon (DOC), total coliform, turbidity, dissolved oxygen, MC-LR toxicity and ammonia were analyzed to form a well-generalized model with a desirability index of 0.638. Overall, filter S + X achieved a non-detectable MCs concentration in some cycles and showed an average of >30% DOC and >80% of total coliform removal along with an under-regulated removal of nitrite, nitrate and ammonia. However, MC-LR breakthrough occurred after 8 weeks of filter operation. These studies demonstrated the effectiveness of inoculating MC-degraders in an existing filtration unit of a DWTP to remove the seasonal occurrence of MCs in the water source.

Degradation and mechanism of microcystin-LR by PbCrO4 nanorods driven by visible light

This work focuses on the photocatalytic removal of recalcitrant organic pollutants in water treatment. Based on facile precipitation reaction, we fabricated a photocatalyst (PbCrO4) in single crystals that present evident response to visible light and employed the catalyst in the photocatalytic decomposition of microcystin-LR (MC-LR). In the degradation test using the nanorods with prepared PbCrO4 photocatalyst, a 100% removal efficiency (27 min reaction) and a kinetics constant of 0.1356 min−1 were achieved. Such a high performance of PbCrO4 in photocatalytic conversion of MC-LR was ascribed to its high carrier separation efficiency, positive valence band (VB) position, and good delocalization of VB and conduction band (CB). The test of electron spin-resonance resonance (ESR) demonstrated that excessive free OH radicals were produced during the PbCrO4 photocatalysis of MC-LR. The density functional theory (DFT) and LC/MS/MS technology were employed to ascertain the intermediates during the MC-LR photocatalytic degradation. The major intermediates were resulted from the attack of hydroxyl radicals to the ADDA side chains of MC-LR structure. This study provides a proof-of-concept strategy to develop effective photocatalysts to efficiently produce OH radicals for the visible-light induced photocatalytic degradation of MC-LR in water.

Biodegradation kinetics of microcystins-LR crude extract by Lysinibacillus boronitolerans strain CQ5

As the most common variant of microcystins (MCs), microcystin-LR (MCLR) is a kind of toxins produced by some species of harmful cyanobacteria and more and more attention has been paid to it. Biodegradation has been extensively investigated and recognized to be a cost-efficient and environmentally benign method for MC clean-up. In order to further research the growth characteristics of strain and the biodegradation characteristics of MCLR, it is necessary to use the dynamic mathematical models as powerful and useful tools. In this study, strain CQ5 was screened and identified by morphological observation, physiological and biochemical tests, and 16S rDNA sequence analysis. The kinetic models of cell growth and MCLR degradation were established with the Gompertz model and revised Monod kinetic model. The results showed that strain CQ5 had the closest phylogenetic similarity to Lysinibacillus boronitolerans (T-10a, AB199591) in the phylogenetic tree, with 99% bootstrap support. Strain CQ5 could utilize MCLR as the carbon and nitrogen source for growth. When the initial pH value was 7 and the inoculation amount was 3%, strain CQ5 grew well in MSM, in which the MCLR crude extract was used as the carbon and nitrogen source of strain CQ5. Within 244 h, the MCLR concentration changed from 14.12 to 1.57 μg/L and its degradation rate could reach 88.88%. The growth curve fitted with the Gompertz growth model (Nt = 1.3119 * exp(−0.1237 * exp(−6.6341t)), R2 > 0.99). The process of MCLR degradation agreed with the first-order reaction kinetic equation (lnS = 2.64764 − 0.01537t, R2 > 0.99). The linkage relationship between MCLR concentration, cell density, and MCLR degradation rate was consistent with the revised Monod equation (V = 0.342S, R2 > 0.97) at low substrate concentration, where Vmax/ Ks was 0.342. The dynamic relationship in which strain CQ5 degraded MCLR and used it as the carbon and nitrogen source to promote its own growth could be explained by the equation S = 14.12 e− 0.342 Nt (N = 1.08). The growth of strain CQ5 and MCLR concentration in degradation system could be simulated and predicted by the dynamic mathematical models in this study. And the predicted results were very consistent. These results could provide theoretical reference for studying the mechanism of MCLR biodegradation and promote the engineering application of strain CQ5.

Microcystin-LR Degradation and Gene Regulation of Microcystin-Degrading Novosphingobium sp. THN1 at Different Carbon Concentrations.

The bacterium Novosphingobium sp. THN1 (THN1) is capable of degrading microcystin-LR (MC-LR). To study the ability of THN1 to degrade MC-LR and its possible mechanism(s) of regulation, we analyzed the effect of carbon concentrations on the degradation process. The MC-LR degradation rate peaked early and then declined during MC-LR biodegradation. Decreased levels of carbon in the medium caused the degradation peak to occur earlier. The expression of the functional gene mlrA, encoding a microcystinase, showed a similar trend to the MC-LR degradation rate at various carbon concentrations (r2 = 0.717, p < 0.05), suggesting that regulation of mlrA expression may play an important role in MC-LR degradation by THN1. The total bacterial biomass decreased when the carbon source was limited and did not correlate with the MC-LR degradation rate. Transcriptomic analysis showed that MC-LR degradation differentially regulated 62.16% (2597/4178) of THN1 genes. A considerable number of differentially expressed genes (DEGs) during MC-LR degradation encoded proteins related to carbon-, nitrogen-, and amino acid-related pathways. At 2 h of MC-LR degradation, most DEGs (29/33) involved in carbon and nitrogen metabolism were downregulated. This indicated that MC-LR may regulate carbon and nitrogen pathways of Novosphingobium sp. THN1. KEGG pathway analysis indicated that the upregulated DEGs during MC-LR degradation were mainly related to amino acid degradation and substrate metabolism pathways. Particularly, we detected increased expression of glutathione metabolism-related genes from transcriptomic data at 2 h of MC-LR degradation compared with the gene expression of 0 h, such as GST family protein, glutathione peroxidase, S-(hydroxymethyl) glutathione dehydrogenase, and glutathione-dependent disulfide-bond oxidoreductase that have been reported to be involved in microcystin degradation.

Degradation of cyanotoxin microcystin-LR in synthetic and natural waters by chemical-free UV/VUV radiation

This study investigated the capability of ultraviolet radiation at 254 nm and 185 nm (UV/VUV) to degrade cyanotoxin microcystin-LR (MC-LR). Results showed 70% toxin reduction solely by 254 nm direct photolysis (ε254 = 13,225 ± 814 M−1cm−1; Φ254 = 0.29 ± 0.03 mol/Einstein). The addition of 185 nm increased MC-LR degradation through advanced oxidation by •OH (k•OH,MC-LR = 2.25 ± 0.39 × 1010 M−1s−1). Alkalinity and organics (DOC) reduced MC-LR degradation by scavenging •OH (kobs,MilliQ = 0.117 cm2/mJ; kobs,50ppmAlk. = 0.0497 cm2/mJ; kobs,6ppmDOC = 0.019 cm2/mJ). Chloride absorbed 185 nm, impacting •OH formation and generating Cl•, while also scavenging •OH. However, Cl• is reactive and •OH scavenging is reversible, resulting in relatively low impact on MC-LR degradation (kobs,50ppmCl = 0.0939 cm2/mJ). In natural water, MC-LR could be degraded from a typical concentration (˜15 μg/L) to below detection (<0.5 μg/L) with a UV254 fluence of 200 mJ/cm2 using UV/VUV. The presence of cyanobacterial cells impeded MC-LR degradation; however, 90% MC-LR degradation could still be achieved. UV/VUV is a promising chemical-free technology capable of MC-LR degradation in a variety of water conditions, and a potentially suitable treatment option for small, remote communities.

Combining solar irradiation with chlorination enhances the photochemical decomposition of microcystin-LR

Microcystin-LR (MC-LR) generated by cyanobacteria is a potent toxin threatening human health. In this study the kinetics and mechanisms of MC-LR elimination from drinking water under solar irradiation with free chlorine (the solar/chlorine process) was evaluated. The rate of MC-LR degradation was dramatically enhanced in the solar/chlorine process (1.1 × 10−2 s−1) compared with chlorination alone (2.6 × 10−3 s−1) or solar irradiation alone (1.2 × 10−4 s−1) with a free chlorine dose of 42 μM (3.0 mg L−1 as Cl2). The enhancement was due to the presence of hydroxyl radicals, reactive chlorine species (RCS), and ozone during free chlorine photolysis. The second-order rate constants of Cl • and Cl2•- reacting with MC-LR were determined to be (2.25 ± 0.07) × 1010 and (5.58 ± 0.42) × 107 M−1s−1, respectively. Cl • was the major RCS contributing to MC-LR elimination. The highest MC-LR degradation rate was observed at pH 8.0. Free chlorine, HO •, Cl • and O3 together accounted for almost 95% of the MC-LR elimination. Hydroxyl- and chloro-MC-LR were generated in the process, followed by dechlorination, dehydration and cleavage of cyclic structures in MC-LR. Aldehyde- and ketone-MC-LR byproducts were also observed. The destruction of dienes led to a great reduction in MC-LR's toxicity. MC-LR removal in natural water samples under natural sunlight irradiation with free chlorine was demonstrated with limited formation of disinfection byproducts. The solar/chlorine process is an energy-efficient approach for MC-LR control, especially suitable for rural areas or where algal blooming threatens.

Removal of MC-LR using the stable and efficient MIL-100/MIL-53 (Fe) photocatalyst: The effect of coordinate immobilized layers

Microcystin-LR (MC-LR), which is produced from cyanobacteria, is the common microcystin with a serious threat to aquatic life and human beings. And the efficient removal method of MC-LR is urgent needed. In this work, the MIL-100/MIL-53 (Fe) photocatalysts, which were successfully prepared by the electrostatic interaction with each other, were applied for the photocatalytic degradation of MC-LR. The structure and optical properties of the MIL-100/MIL-53 (Fe) photocatalysts were characterized by using SEM, XRD, XPS, FT-IR and UV–vis DRS. The very low dosage of the MIL-100/MIL-53 (Fe) photocatalysts achieved the degradation of MC-LR, and the optimized loading was the 50% MIL-100/MIL-53 (Fe) photocatalyst. Compared to MIL-100 (Fe) and MIL-53 (Fe), the MC-LR degradation was up to 96.5% after 3 h under visible light illumination with the 50% MIL-100/MIL-53 (Fe) photocatalyst due to the pore-effect adsorption and the effective separation of photogenerated carriers. The effect of coordinate immobilized layers between MIL-100 (Fe) and MIL-53 (Fe) contributed to the stable and efficient removal of MC-LR for the 50% MIL-100/MIL-53 (Fe) photocatalyst. The MC-LR photocatalytic mechanism and degradation pathway, which the photogenerated holes (h+) were the main active species, were proposed by radical capture experiments and LC-MS analysis.

Photodegradation of Microcystin-LR Using Visible Light-Activated C/N-co-Modified Mesoporous TiO2 Photocatalyst

Microcystin-LR (MC-LR), a potent hepatotoxin produced by the cyanobacteria, is of increasing concern worldwide because of severe and persistent impacts on humans and animals by inhalation and consumption of contaminated waters and food. In this work, MC-LR was removed completely from aqueous solution using visible-light-active C/N-co-modified mesoporous anatase/brookite TiO2 photocatalyst. The co-modified TiO2 nanoparticles were synthesized by a one-pot hydrothermal process, and then calcined at different temperatures (300, 400, and 500 °C). All the obtained TiO2 powders were analyzed by X-ray diffraction (XRD), Raman spectroscopy, transmission electron microscope (TEM), specific surface area (SSA) measurements, ultraviolet-visible diffuse reflectance spectra (UV-vis DRS), X-ray photoelectron spectroscopy (XPS), Fourier transform infrared (FTIR) spectroscopy, and photoluminescence (PL) analysis. It was found that all samples contained mixed-phase TiO2 (anatase and brookite), and the content of brookite decreased with an increase in calcination temperature, as well as the specific surface area and the content of non-metal elements. The effects of initial pH value, the TiO2 content, and MC-LR concentration on the photocatalytic activity were also studied. It was found that the photocatalytic activity of the obtained TiO2 photocatalysts declined with increasing temperature. The complete degradation (100%) of MC-LR (10 mg L−1) was observed within 3 h, using as-synthesized co-modified TiO2 (0.4 g L−1) at pH 4 under visible light. Based on the obtained results, the mechanism of MC-LR degradation has been proposed.

Photoelectrocatalytic degradation of microcystin-LR using a dimensionally stable anode and the assessment of detoxification

Microcystins (MCs) pose a great threat to human health due to their toxicity. In this study, photoelectrocatalysis was applied as an effective technology to degrade MCs. The effects of different dimensionally stable anodes and cathodes were evaluated. Detoxification effects were investigated using a luminescence inhibition assay, a micronucleus assay of Vicia faba root tips and a single cell gel electrophoresis assay. The results show that RuO2-TiO2/Ti and stainless steel were the best among the six anodes and four cathodes tested for MCLR degradation. Compared to photodegradation, photocatalysis and electrocatalysis, photoelectrocatalysis obtained the highest efficiency on MCLR degradation, nearly 100% at 254 nm and 5.0 mA/cm2. The degradation kinetics agreed with the Langmuir-Hinshelwood kinetic model. When NaCl was used as an electrolyte, the degradation efficiency of MCLR reached 100% even under 0.002 mol/L, which was much better than that of Na2SO4, Na2HPO4 and NaNO3. The toxicity assays showed that although MCLR was completely degraded, acute toxicity still occurred in the solution at relative luminosities from 0 to 9.37%. However, the micronucleus efficiency and DNA damage of cells returned to normal levels at the end of the reaction. This indicates that genotoxicity and cytotoxicity were eliminated with the degradation of MCLR.

Rad]OH pre-treatment of algae blooms and degradation of microcystin-LR in a drinking water system of 480 m3/day: Comparison with ClO2

The widespread occurrence of harmful algae blooms in drinking water sources has resulted in significant challenges for safeguarding water bodies globally. During algae bloom outbreaks, an OH drinking water treatment system with a capacity of 480 m3/day, was built in the Xinglin water plant in Xiamen, China. The OH, which was produced using the strong ionization discharge combined with hydrodynamic cavitation effect, was applied in the pre-treatment of algae blooms and degradation of microcystin-LR (MC-LR). Results indicated that OH pre-treatment of 0.88 mg/L inactivated five species of algae from 35,180 to 220 cells/mL during conveying of algae bloom water within 9.8 s, subsequently all remaining living and dead algae were removed by the sand filtration. However, ClO2 pre-treatment existed alive and dead algae of 7830 cells/mL, which could pass through the sand filtration tank into pipe networks. Meanwhile, OH degraded the MC-LR from 14.4 μg/L to ND. Analysis of OH-degraded mechanism indicated that OH could mineralize MC-LR by key opening the benzene ring. With OH pre-treatment and ClO2 disinfection of 0.31 mg/L, no BrO3−, trihalomethanes and haloacetic acids were detected in this system, and all indexes of water quality and DBPs satisfied the Chinese Standards for Drinking Water. Therefore, this OH drinking water treatment system shows great promise for practical applications in the removal of algae blooms and degradation of MC-LR.

Oxidation and molecular properties of microcystin-LR, microcystin-RR and anatoxin-a using UV-light-emitting diodes at 255 nm in combination with H2O2

On the use of UV light emitting diodes (UV-LEDs), emitting at 260–290 nm, has attracted attention for treating cyanotoxins, although most previous studies related with UV/H2O2 process have been used conventional mercury UV lamp (λ = 254 nm). Therefore, the aim of the study was to investigate the UV-LEDs, having a wavelength of 255 nm, coupled with H2O2 process for the removal of microcystin-LR (MC-LR), microcystin-RR (MC-RR), and anatoxin-a (ANTX) and to verify the degradation kinetics, mechanism and impact of water quality parameters in relation to their molecular properties. Among three UV-LEDs (λ = 255, 266, and 280 nm), the shortest one was the most effective to remove MC-LR coincided with its decadic molar absorption coefficient. The degradation rate constants of MC-LR, MC-RR, and ANTX were 0.0644, 0.0241, and 0.0076 cm2 mJ−1, respectively, during the UV-LED/H2O2 process. For MC-LR and MC-RR degradation, reaction with OH is a major mechanism along with direct photolysis as a minor factor. ANTX degradation is predominantly attributed to OH. The second-order rate constant for ANTX is one order of magnitude lower than others because ANTX is recalcitrant to oxidation. The MC-LR degradation occurred at the diene and aromatic ring of Adda, Mdha, and amide bond and the main reactive oxidation site of MC-RR was the Adda chain. In contrast, photo-oxidation transformed ANTX to higher molecular weight compounds via polymerization instead of degradation. When MC-LR, MC-RR, and ANTX were co-present, lower concentration of dissolved organic carbon and higher acidity with bicarbonate was favorable to remove MC-LR and MC-RR according to their scavenging factors and reaction with CO−3. However, ANTX is relatively resistant to degradation at pH 3.2.

Construction of precious metal-loaded BiOI semiconductor materials with improved photocatalytic activity for microcystin-LR degradation

The composite photocatalyst of precious metal loaded on BiOI (M/BiOI, M = Pt, Au, Ag) was prepared by photochemical deposition and used for the photocatalytic degradation of microcystins (MC-LR). The material was characterized by X-ray powder diffraction (XRD), field emission scanning electron microscopy (FESEM), ultraviolet visible (UV-vis) diffuse reflectance spectroscopy, X-ray photoelectron spectroscopy (XPS), and photoluminescence spectra (PL). The effect of photodegradation of MC-LR and the possible mechanism were investigated. It turned out that, among precious metals of Pt, Au, and Ag, Ag had the most significant improvement for photocatalytic activity of BiOI and Au was the least. The Ag/BiOI catalyst was illuminated 2h under the simulated visible-light condition with the optimal load ratio of Ag catalyst (1.0wt%) and the 2-h illumination under simulated visible-light condition, the degradation rate of MC-LR was 61.26% ± 0.12%. In addition, through the experiment of trapping agent and the analysis of electron spin resonance (ESR), we could conclude that the main active species is O2- in the process of the degradation of MC-LR by three precious metal-loaded BiOI semiconductor materials.

Photocatalytic degradation of Microcystin-LR by visible light active and magnetic, ZnFe2O4-Ag/rGO nanocomposite and toxicity assessment of the intermediates

In this work, we aimed to study photocatalytic degradation of Microcystin-LR (MC-LR), a cyanotoxin known to cause acute as well as chronic toxicity and even mortality. The nanocomposite (NC) based on zinc ferrite (ZnFe2O4) was modified with graphene oxide (GO) and Ag nanoparticles (NPs) to enhance its photocatalytic properties under visible light. The so-formed ZnFe2O4-Ag/rGO NC exhibited superior performance in visible light allowing complete degradation of MC-LR within 120 min of treatment with pseudo rate constant, k = 0.0515 min−1, several times greater than other photocatalysts, TiO2 (k = 0.0009 min−1), ZnFe2O4 (k = 0.0021 min−1), ZnFe2O4-Ag (k = 0.0046 min−1) and ZnFe2O4/rGO (k = 0.007 min−1) respectively. The total organic carbon analysis revealed that only 22% of MC-LR was mineralized on 120 min of treatment time indicating presence of different intermediate by-products. The intermediates formed during photocatalytic treatment were identified using liquid chromatography–mass spectrometry (LCMS) based on which probable degradation pathways were proposed. The attack from OH radicals formed during the photocatalytic process resulted to hydroxylation and subsequent cleavage of diene bond. The toxicity assessment with Daphnia magna revealed that the degradation process has alleviated toxicity of the MC-LR and no toxic intermediates were formed during the treatment which is very important from eco-toxicological view point. Therefore, ZnFe2O4-Ag/rGO has a good potential in the field of environmental applications as visible light active and magnetic photocatalyst with enhanced performance.

Preparation of Ag3PO4/CNH and the performance for photocatalytic degradation of microcystin-LR under visible light

Preparation of Ag3PO4/CNH and the performance for photocatalytic degradation of microcystin-LR under visible light

Sono-Fenton hybrid process on the inactivation of Microcystis aeruginosa: Extracellular and intracellular oxidation

For the first time, the inactivation of Microcystis aeruginosa using sono-Fenton process at low frequency high intensity (20 kHz, 0.42 W/mL) and high frequency low intensity (800 kHz, 0.07 W/mL) was investigated, respectively. 20 kHz sono-Fenton treatment successfully reduced cyanobacterial cell number from 4.19 × 106 cells/mL to 0.45 × 106 cells/mL within 5 min treatment. Alternatively, efficient performance of 800 kHz sono-Fenton process was observed to decrease Microcystis cell number to 2.33 × 106 cells/mL after 5 min inactivation, with lower energy cost. It was found that powerful 20 kHz sonication induced pore formation on the cell wall, leading to extracellular damage, while 800 kHz irradiation with low intensity triggered intracellular uptake of chemicals, suggesting endocytosis effects. Furthermore, sono-Fenton Processes were found to be affected by the concentrations of Fenton’s reagent, and pre-sonication time. Although solo Fenton treatment released microcystins in water, the degradation of microcystin-LR were achieved using 20 and 800 kHz sono-Fenton processes, respectively. The results of this work showed that severe extracellular oxidation is the vital inactivation mechanism of 20 kHz sono-Fenton process, while the internal oxidation caused by intracellularly delivered Fenton reagents is suggested to be the main cause of 800 kHz sono-Fenton inactivation, leading to much lower energy cost. This work provides alternative methods to control harmful cyanobacteria in water towards effective treatment.

Further Understanding of Degradation Pathways of Microcystin-LR by an Indigenous Sphingopyxis sp. in Environmentally Relevant Pollution Concentrations.

Microcystin-LR (MC-LR) is the most widely distributed microcystin (MC) that is hazardous to environmental safety and public health, due to high toxicity. Microbial degradation is regarded as an effective and environment-friendly method to remove it, however, the performance of MC-degrading bacteria in environmentally relevant pollution concentrations of MC-LR and the degradation pathways remain unclear. In this study, one autochthonous bacterium, Sphingopyxis sp. m6 which exhibited high MC-LR degradation ability, was isolated from Lake Taihu, and the degrading characteristics in environmentally relevant pollution concentrations were demonstrated. In addition, degradation products were identified by utilizing the full scan mode of UPLC-MS/MS. The data illustrated that strain m6 could decompose MC-LR (1–50 μg/L) completely within 4 h. The degradation rates were significantly affected by temperatures, pH and MC-LR concentrations. Moreover, except for the typical degradation products of MC-LR (linearized MC-LR, tetrapeptide, and Adda), there were 8 different products identified, namely, three tripeptides (Adda-Glu-Mdha, Glu-Mdha-Ala, and Leu-MeAsp-Arg), three dipeptides (Glu-Mdha, Mdha-Ala, and MeAsp-Arg) and two amino acids (Leu, and Arg). To our knowledge, this is the first report of Mdha-Ala, MeAsp-Arg, and Leu as MC-LR metabolites. This study expanded microbial degradation pathways of MC-LR, which lays a foundation for exploring degradation mechanisms and eliminating the pollution of microcystins (MCs).

Isolation and Characterization of Lake Erie Bacteria that Degrade the Cyanobacterial Microcystin Toxin MC-LR.

Microcystin-LR (MC-LR) is a cyclic hepatotoxin produced by cyanobacteria, including Microcystis sp. and Planktothrix sp. Harmful algal blooms (HABs) in Lake Erie have become a major human health concern in recent years, highlighted by the August 2014 city of Toledo, Ohio, municipal water "do not drink" order that affected nearly 500,000 residents for 3 days. Given that microcystin degrading bacteria have been reported from HAB-affected waters around the world, we hypothesized that MC-LR degrading bacteria could be isolated from Lake Erie. To test this hypothesis, 13 water samples were collected from various Lake Erie locations during the summers of 2014 and 2015, MC-LR was continuously added to each water sample for 3 to 5 weeks to enrich for MC-LR-degrading bacteria, and MC-LR was quantitated over time. Whereas MC-LR was relatively stable in sterile-filtered lake water, robust MC-LR degradation (up to 19 ppb/day) was observed in some water samples. Following the MC-LR selection process, 67 individual bacterial isolates were isolated from MC-LR degrading water samples and genotyped to exclude potential human pathogens, and MC-LR degradation by smaller groups of bacterial isolates (e.g., groups of 22 isolates, groups of 11 isolates, etc.) was examined. Of those smaller groups, selected groups of four to five bacterial isolates were found to degrade MC-LR into non-toxic forms and form robust biofilms on siliconized glass tubes. Taken together, these studies support the potential use of isolated bacterial isolates to remove MC-LR from drinking water.

Novel fluidized-bed biofilm reactor for concomitant removal of microcystin-LR and organics

Fluidized bed biofilm reactor (FBBR) was evaluated for the removal of microcystin-LR (MC-LR) from drinking water-sludge (0.3% w/v). Biofilm formed inside the solid media carriers (biocarriers) were studied for the MC-LR degradation in FBBRs via known MC-LR degraders: Arthrobacter ramosus (reactor A: RA) and Bacillus sp. (reactor B: RB), along with the heterogeneous bacterial community (HBC) present in the sedimentation-unit sludge as a background matrix. Their ability to form biofilm inside the immobilized biocarriers was periodically quantified for over 300 days to determine the duration of mature biofilm growth, sloughing event and then re-maturation. The bioreactor performance was mainly evaluated in terms of MC-LR, nitrate, nitrite, ammonia removal, and soluble-chemical oxygen demand (s-COD) removal. Biological degradation of MC-LR showed significant role over the physical adsorption, as the removal efficiency increased by around 30% and 26% for RA and RB respectively, as compared to the control bioreactor RD (without any bacterial cells) and an increase by over 15% and 11% when compared to reactor RC (contained only HBC). Mass spectra analysis for RA, RB, and RC strengthen the possibility of a toxic-free degradation mechanism. Overall, RA showed the best MC-LR removal efficiency of around 93.7%, which comprised no MC-LR in the supernatant phase and around 3 µg/L in the sludge-mixture phase. Toxicity assessment of biodegraded sample (using bioindicator) further revealed the toxic-free nature by RA with >80% removal for ammonia, nitrate, and nitrite. Scale-up of laboratory scale FBBR (2 L) is also proposed to handle 200 m3 of feed water per day based on a similar volumetric mass transfer coefficient (kLa) to study the feasible process economics.

Elimination kinetics and detoxification mechanisms of microcystin-LR during UV/Chlorine process

Microcystin-LR (MC-LR), a toxin produced by cyanobacteria, is very toxic and poses a threat to public health when entering water treatment works. In this study, UV/chlorine process, as an advanced oxidation process (AOP), has been demonstrated for effective elimination of MC-LR levels and associated toxicity. At a chlorine dose of 3.0 mg L−1 and UV fluence of 125 mJ cm−2, MC-LR (initial concentration 1.0 μM) was reduced by 92.5%, which was much higher than 20.3% removal under UV irradiation alone and 65.1% removal during dark chlorination. Enhanced degradation was attributed by hydroxyl radicals (HO) and reactive chlorine species (RCS), mainly Cl2- and ClO. Increasing chlorine doses or lowering pH favored MC-LR removal. Increased bicarbonate and natural organic matter concentrations inhibited MC-LR removal, but bromide ions enhanced MC-LR removal instead. MC-LR elimination rates in natural waters were roughly two times smaller than those in ultrapure water. The reactive radicals promoted hydroxylation of both diene of Adda moiety and double bond of Mdha moiety in MC-LR. UV exposure enhanced the dechlorination of chloro-MC-LR via the cleavage of CCl bond. The toxicity was evaluated by a protein phosphatase (PP2A) inhibition assay. At a chlorine dose of 3.0 mg L−1 and UV fluence of 125 mJ cm−2, the toxicity of the treated water was reduced by 75.0%, which was also higher than 25.7% and 46.7% removal under UV irradiation alone and during dark chlorination, respectively. These results highlight UV/chlorine is an efficient AOP for MC-LR degradation and detoxification.