Photocatalytic degradation of microcystin-LR by modified high-energy {001} titanium dioxide: Kinetics and mechanism study of HF8

Background: Uniquely synthesised titanium dioxide (TiO2) with high-energy {001} exposed facets denoted HF8 was used for the photocatalytic degradation of microcystin-LR (MC-LR) under ultraviolet irradiation at 365 nm. Methods: The influence of various conditions including environmental pH, nutrient anions, TiO2 dose, and MC-LR concentration was studied, and concentration of MC-LR measured using liquid chromatography-tandem mass spectrometry. Results: Within 120 min, 72.6% of an environmentally relevant MC-LR concentration (120 µg/L) was degraded under pH conditions ranging from 3 to 11. Stability tests revealed no loss of TiO2 activity after four applications of the same dose, indicating its stability, reusability, and potential to be re-used for sustainable remediation of MC-LR in eutrophic waters. Mechanism studies suggested that the reaction obeyed the pseudo-first-order equation and that hydroxyl radicals are the major reactive intermediate contributing to the reaction. The structure elucidation of intermediates suggested that hydroxylation and bond cleavage between the Adda chain and Mdha site could be the initiation of reactions in the degradation of MC-LR by HF8 TiO2. Conclusion: The results present a fast, sustainable, and practical method using modified TiO2 to improve MC-LR remediation.Peer reviewe

Factors Affecting Temporal and Spatial Variations of Microcystins in Gonghu Bay of Lake Taihu, with Potential Risk of Microcystin Contamination to Human Health

A field survey of the seasonal variation of microcystin (MC) concentration was performed in Gonghu Bay (a total of 15 sampling sites) of Lake Taihu from January to December 2008. Microcystis spp. biomass and intra-/extracellular MCs were significantly correlated with water temperature, suggesting the importance of temperature in cyanobacterial blooming in the lake. Higher MC concentration was found in summer and autumn, and peaks of Microcystis biomass and intra-/extracellular MC concentrations were all present in October. Spatially, risk of MCs was higher in littoral zones than in the pelagic area. There were significant correlations between N or P concentrations, and Microcystis biomass or MC content, suggesting that N and P levels affected MC production through influencing Microcystis biomass. Intra-/extracellular MCs and Microcystis biomass had negative exponential relationships with TN:TP, and the maximum values all occurred when TN:TP was <25. Multivariate analyses by PCCA indicated that intra- and extracellular MC concentrations had better correlations with biological factors (such as Microcystis biomass and chl-a) than with physicochemical factors. The maximum MC concentration reached up to 17 mu g/L MC-LReq, considerably higher than the drinking water safety standard (1 mu g/L) recommended by the WHO. So it is necessary to take measures to reduce the exposure risk of cyanobacterial toxins to human beings

Use of a Generalized Additive Model to Investigate Key Abiotic Factors Affecting Microcystin Cellular Quotas in Heavy Bloom Areas of Lake Taihu

Lake Taihu is the third largest freshwater lake in China and is suffering from serious cyanobacterial blooms with the associated drinking water contamination by microcystin (MC) for millions of citizens. So far, most studies on MCs have been limited to two small bays, while systematic research on the whole lake is lacking. To explain the variations in MC concentrations during cyanobacterial bloom, a large-scale survey at 30 sites across the lake was conducted monthly in 2008. The health risks of MC exposure were high, especially in the northern area. Both Microcystis abundance and MC cellular quotas presented positive correlations with MC concentration in the bloom seasons, suggesting that the toxic risks during Microcystis proliferations were affected by variations in both Microcystis density and MC production per Microcystis cell. Use of a powerful predictive modeling tool named generalized additive model (GAM) helped visualize significant effects of abiotic factors related to carbon fixation and proliferation of Microcystis (conductivity, dissolved inorganic carbon (DIC), water temperature and pH) on MC cellular quotas from recruitment period of Microcystis to the bloom seasons, suggesting the possible use of these factors, in addition to Microcystis abundance, as warning signs to predict toxic events in the future. The interesting relationship between macrophytes and MC cellular quotas of Microcystis (i.e., high MC cellular quotas in the presence of macrophytes) needs further investigation

Quantitative analysis of glutathione and cysteine S-conjugates of microcystin-LR in the liver, kidney and muscle of common carp (Cyprinus carpio) in Lake Taihu

Tissue distribution of microcystin (MC)-LR-GSH, MC-LR-Cys and MC-LR of omnivorous fish in Lake Taihu was investigated. MC-LR and MC-LR-Cys were detected in liver, kidney and muscle. The concentration of MC-LR in liver and kidney was 0.052 mu g g(-1) DW and 0.067 mu g g(-1) DW, respectively. MC-LR-Cys appeared to be an important metabolite with average contents of 1.104 mu g g(-1) DW and 0.724 mu g g(-1) DW in liver and kidney, and the MC-LR-Cys/MC-LR ratio in liver and kidney reaching as high as 21.4 and 10.8. High MC-LR-Cys/MC-LR ratio and a significant correlation between MC-LR-Cys and MC-LR concentration in liver, suggest that liver is more active in detoxification of MC-LR by formation of MC-LR-Cys for omnivorous fish. Furthermore, there might be a balance between the accumulation and depuration/metabolism of MC-LR-Cys in kidney. The MC-LR-Cys can be formed in kidney directly, or transported from liver or other tissues, while the MC-LR-Cys in kidney might be dissociated to MC-LR or excreted. Although MC-LR and its metabolites were scarcely detected in muscle, it is necessary to investigate the distribution of toxic metabolites in edible muscle

Photocatalytic Degradation of Microcystins-LR over Mesoporous graphitic Carbon Nitride (mpg-CN)

Mesoporous graphitic carbon nitrides (mpg-CN) were synthesized by a templating method using Ludox (SiO2) as hard template and guanidine hydrochloride (GndCl) as precursor, and were used as metal-free photocatalysts for microcystin-LR (MC-LR) degradation in aqueous solution. By tuning the mass ratio of SiO2 to GndCl, mpg-CN with varied surface areas and condensation degrees were obtained. Catalytic results showed that sample prepared at mass ratio equals 0.4, i.e., mpg-CN(0.4), exhibits the best activity, with above 98% MC-LR conversion obtained at 120 min. Mechanism studies suggested that the reaction obeys the pseudo first-order equation and the produced superoxide anion radicals (&bull;O2&minus;) is the major reactive intermediates contributing to the reaction. Stability tests showed that no appreciable loss of activity is observed even the catalyst is recycled for five times, indicating that the material is stable in the reaction

Factors Affecting Temporal and Spatial Variations of Microcystins in Gonghu Bay of Lake Taihu, with Potential Risk of Microcystin Contamination to Human Health

A field survey of the seasonal variation of microcystin (MC) concentration was performed in Gonghu Bay (a total of 15 sampling sites) of Lake Taihu from January to December 2008. Microcystis spp. biomass and intra-/extracellular MCs were significantly correlated with water temperature, suggesting the importance of temperature in cyanobacterial blooming in the lake. Higher MC concentration was found in summer and autumn, and peaks of Microcystis biomass and intra-/extracellular MC concentrations were all present in October. Spatially, risk of MCs was higher in littoral zones than in the pelagic area. There were significant correlations between N or P concentrations, and Microcystis biomass or MC content, suggesting that N and P levels affected MC production through influencing Microcystis biomass. Intra-/extracellular MCs and Microcystis biomass had negative exponential relationships with TN:TP, and the maximum values all occurred when TN:TP was <25. Multivariate analyses by pcca indicated that intra- and extracellular MC concentrations had better correlations with biological factors (such as Microcystis biomass and chl-a) than physicochemical factors. The maximum concentration reached up to 17 µg/L MC-Lreq, considerably higher drinking water safety standard (1 µg/L) recommended who. So it is necessary take measures reduce exposure risk of cyanobacterial toxins human beings

Metabolic Response to Oral Microcystin-LR Exposure in the Rat by NMR-Based Metabonomic Study

Microcystin-LR (MCLR), a potent hepatotoxin, is causing increased risks to public health. Although the liver is the main target organ of MCLR, the metabolic profiling of liver in response to MCLR in vivo remains unknown. Here, we comprehensively analyzed the metabolic change of liver and ileal flushes in rat orally gavaged with MCLR by ¹H nuclear magnetic resonance (NMR). Quantification of hepatic MCLR and its glutathione and cysteine conjugates by liquid chromatography–electrospray ionization–mass spectrometry (LC-ESI-MS) was conducted. Metabonomics results revealed significant associations of MCLR-induced disruption of hepatic metabolisms with inhibition of nutrient absorption, as evidenced by a severe decrease of 12 amino acids in the liver and their corresponding elevation in ileal flushes. The hepatic metabolism signature of MCLR was characterized by significant inhibition of tyrosine anabolism and catabolism, three disrupted pathways of choline metabolism, glutathione exhaustion, and disturbed nucleotide synthesis. Notably, substantial alterations of hepatic metabolism were observable even at the low MCLR-treated group (0.04 mg/kg MCLR), although no apparent histological changes in liver were observed in the low- and medium-dosed groups. These observations offered novel insights into the microcystin hepatotoxic mechanism at a functional level, thereby facilitating further assessment and clarification of human health risk from MCs exposure

Spatial distribution of <i>Microcystis</i> density, MC concentration and MC cellular quotas in A) spring (May), B) summer (August) and C) autumn (November) of Lake Taihu.

<p>Spatial distribution of <i>Microcystis</i> density, MC concentration and MC cellular quotas in A) spring (May), B) summer (August) and C) autumn (November) of Lake Taihu.</p

Temporal variation of phytoplankton density composition in the northern area of Lake Taihu.

<p>Temporal variation of phytoplankton density composition in the northern area of Lake Taihu.</p