Characterization of an efficient catalytic and organic solvent-tolerant azoreductase toward methyl red from Shewanella oneidensis MR-1

The acyl carrier protein (ACP) phosphodiesterase gene (SO 4396) of Shewanella oneidensis MR-1 which was analyzed to have azoreductase activity was heterologously expressed in Escherichia coli. The ACP phosphodiesterase was found to reach maximum enzyme velocity 220.59 U/mg, named azoreductase in this study. The azoreductase had highest specific activity (153.16 U/mg) at pH 6.5, which showed a preference for nicotinamide adenine dinucleotide (NADH) as electron donor. The phylogenetic tree analysis indicated that the azoreductase had preference for NADH and dependence for flavin mononucleotide (FMN). However, the azoreductase from S. oneidensis MR-1 still had high enzyme activity in the absence of FMN. The Mg²⁺ had a positive influence on the enzyme activity with 25 mM concentration, whereas Cr³⁺, Cd²⁺ usually had significantly negative effect on enzyme activity. The purified azoreductase retained nearly 100 % activity after incubating in 30 % dimethyl sulfoxide (DMSO), 30 % acetone, 30 % methanol, 20 % ethanol, 20 % isopropanol, and 10 % propanol.     

Occurrence, distribution, and sources of six phenolic endocrine disrupting chemicals in the 22 river estuaries around Dianchi Lake in China

The objectives of this study are to track the occurrence, distribution, and sources of phenolic endocrine disrupting compounds (EDCs) in the 22 rivers around Dianchi Lake in China, to estimate the input and output amounts of phenolic EDCs in the water system, and to provide more comprehensive fundamental data for risk assessment and contamination control of phenolic EDCs in aquatic environment. Six phenolic EDCs were systematically evaluated in water and surface sediment in the estuaries of those rivers. The water and sediment samples were preconcentrated by solid-phase extraction system and microwave-assisted extraction system, respectively. Phenolic EDCs were analyzed by GC-MS (Thermo Fisher Scientific, USA) after derivatization. Phenolic EDCs were found ubiquitously in the aquatic environment. The total concentrations ranged from 248 to 4,650 ng/L in water, and 113 to 3,576 ng/g dry weight in surface sediment. The residue amount of phenolic EDCs in Dianchi Lake was 258 kg/a. Concentrations of the phenolic EDCs in the Lake decreased with increase in distance to the estuaries of those rivers which run through urban and industrial areas. The rivers seriously contaminated by phenolic EDCs were Xin River, Yunliang River, Chuanfang River, Cailian River, Jinjia River, Zhengda River, and Daqing River which run through the old area of Kunming City. Satisfying correlations were observed between the concentrations of the target compounds in water and in surface sediment. NP1EO, NP2EO, and BPA were identified as the three predominant phenolic EDCs. There were significant correlations between phenolic EDCs and many basic water quality parameters. Urban and industrial areas are the major contributors for phenolic EDCs, especially in Kunming City. Compositional profiles of phenolic EDCs in surface sediment were similar to those in river water. The concentrations of phenolic EDCs in the rivers located in the northwest part of the valley were very high, and posed a potential risk to aquatic organisms and even human. The concentrations of NP2EO, NP1EO, and BPA were at moderate levels of other areas. The basic water quality parameters (TOC, TN, DO, and pH) play important roles on the distribution, fate, and behavior of phenolic EDCs in the valley.     

Photodegradation of the antimicrobial triclocarban in aqueous systems under ultraviolet radiation

This work aimed to investigate the effectiveness of ultraviolet (UV) radiation on the degradation of the antimicrobial triclocarban (TCC). We investigated the effects of several operational parameters, including solution pH, initial TCC concentration, photocatalyst TiO₂ loading, presence of natural organic matter, and most common anions in surface waters (e.g., bicarbonate, nitrate, and sulfate). The results showed that UV radiation was very effective for TCC photodegradation and that the photolysis followed pseudo-first-order kinetics. The TCC photolysis rate was pH dependent and favored at high pH. A higher TCC photolysis rate was observed by direct photolysis than TiO₂ photocatalysis. The presence of the inorganic ions bicarbonate, nitrate, and sulfate hindered TCC photolysis. Negative effects on TCC photolysis were also observed by the addition of humic acid due to competitive UV absorbance. The main degradation products of TCC were tentatively identified by gas chromatograph with mass spectrometer, and a possible degradation pathway of TCC was also proposed.     

Understanding the patterns and mechanisms of urban water ecosystem degradation: phytoplankton community structure and water quality in the Qinhuai River, Nanjing City, China

The temporal and spatial distribution characteristics of environmental parameters and the phytoplankton community were investigated in October 2010 and January 2011 in the Qinhuai River, Nanjing, China. Results showed that the water quality in the study area was generally poor, and the main parameters exceeding standards (level V) were nitrogen and phosphorus. The observed average concentrations of the total nitrogen (TN) were 4.90 mg?L^?1 in autumn and 9.29 mg?L^?1 in winter, and those of the total phosphorus (TP) were 0.24 mg?L^?1 in autumn and 0.88 mg?L^?1 in winter, respectively. Thirty-seven species, 30 genera, and four phyla of phytoplankton were detected in the river. Cyanophyta and Bacillariophyta were the dominant phyla in autumn, with average abundance and biomass of 221.5?×?10⁴?cells?L^?1 and 4.41 mg?L^?1, respectively. The dominant population in winter was Bacillariophyta, and the average abundance and biomass were 153.4?×?10⁴?cells?L^?1 and 6.58 mg?L^?1, respectively. The results of canonical correspondence analysis (CCA) between environmental parameters and phytoplankton communities showed that Chlorophyta could tolerate the higher concentrations of the permanganate index, nitrogen, and phosphorus in eutrophic water; Bacillariophyta could adapt well to changing water environments; and the TN/TP ratio had obvious impacts on the distributions of Cyanophyta, Euglenophyta, and some species of Chlorophyta. CCA analyses for autumn and winter data revealed that the main environmental parameters influencing phytoplankton distribution were water temperature, conductivity, and total nitrogen, and the secondary factors were dissolved oxygen, NH₄ ⁺–N, NO₃–N, TN, COD_Mn, TN/TP ratio, and oxidation-reduction potential.     

Sedimentary record of polycyclic aromatic hydrocarbons and DDTs in Dianchi Lake, an urban lake in Southwest China

Unique time trends of polycyclic aromatic hydrocarbons (PAHs) and dichlorodiphenyltrichloroethanes (DDTs) were found in a dated sediment core from Dianchi Lake (DC), an urban lake in Southwest China. The temporal trend of PAHs in DC was not only different from those in China's coastline and remote lakes of China, but also different from those in more developed countries. Identification of sources suggested that PAHs in DC originated primarily from domestic combustion of coal and biomass. However, a change of source from low- and moderate-temperature combustion to high-temperature combustion processes was observed. Different from those in China's coastline and some developed countries, the temporal trend of DDTs in DC mirrored the historical usage of DDTs in China, with erosion of soils and surface runoff from its drainage area the most likely routes of DDT introduction to the lake. Rapid urbanization and industrialization in its catchment, effective interception of point-source pollution, and changes in sources of energy during the last few decades have significantly influenced the vertical profiles of PAHs in DC.     

Adsorption behavior of light green anionic dye using cationic surfactant-modified wheat straw in batch and column mode

An agricultural by-product, natural wheat straw (NWS), was soaked in 1 % cationic surfactant (hexadecylpyridinium bromide, CPB) solution for 24 h (at 293 K), and modified wheat straw (MWS) was obtained. Analysis of FTIR, XFR, and nitrogen element showed that CPB was adsorbed onto surface of NWS. Then, MWS was used as adsorbent for the removal of light green dye (LG, anionic dye) from aqueous solution. The experiment was performed in batch and column mode at room temperature (293 K). Sodium chloride (up to 0.1 mol/L) existed in solution was not favor of LG dye adsorption. The equilibrium data were better described by Langmuir isotherm, and adsorption capacity of q _m from Langmuir model was 70.01?±?3.39 mg/g. In fixed-bed column adsorption mode, the effects of initial LG concentration (30, 50, 70 mg/L) and flow rate (6.5, 9.0, 14.5 mL/min) on adsorption were presented. Thomas and modified dose–response models were used to predict the breakthrough curves using nonlinear analysis method, and both models can fit the breakthrough curves. Theoretical and experimental breakthrough curves were drawn and compared. The results implied that MWS can be used as adsorbent material to remove LG from aqueous solution.     

Effect of silicate supplementation on the alleviation of arsenite toxicity in 93-11 (Oryza sativa L. indica)

Chronic exposure to arsenic (As) in rice has raised many health and environmental problems. As reported, great variation exists among different rice genotypes in As uptake, translocation, and accumulation. Under hydroponic culture, we find that the Chinese wild rice (Oryza rufipogon; acc. 104624) takes up the most arsenic among tested genotypes. Of the cultivated rice, the indica cv. 93-11 has the lowest arsenic translocation factor value but accumulates the maximum concentration of arsenic followed by Nipponbare, Minghui 86, and Zhonghua 11. Higher level of arsenite concentration (50 μM) can induce extensive photosynthesis and root growth inhibition, and cause severe oxidative stress. Interestingly, external silicate (Si) supplementation has significantly increased the net photosynthetic rate, and promoted root elongation, as well as strongly ameliorated the oxidative stress by increasing the activities of antioxidant enzymes superoxide dismutase, ascorbate peroxidase, and peroxidase in roots and/or leaves of 93-11 seedlings. Notably, 1.873 mM concentration of Si considerably decreases the total As uptake and As content in roots, but significantly increases the As translocation from roots to shoots. In contrast, Si supplementation with 1.0 mM concentration significantly increases the total As uptake and As concentrations in roots and shoots of 93-11 seedlings after 50 μM arsenite treatment for 6 days.     

Effects of nitrogen application rate and a nitrification inhibitor dicyandiamide on methanotroph abundance and methane uptake in a grazed pasture soil

Methane-oxidizing bacteria (methanotrophs) in the soil are a unique group of methylotrophic bacteria that utilize methane (CH₄) as their sole source of carbon and energy which limit the flux of methane to the atmosphere from soils and consume atmospheric methane. A field experiment was conducted to determine the effect of nitrogen application rates and the nitrification inhibitor dicyandiamide (DCD) on the abundance of methanotrophs and on methane flux in a grazed pasture soil. Nitrogen (N) was applied at four different rates, with urea applied at 50 and 100 kg N ha^?1 and animal urine at 300 and 600 kg N ha^?1. DCD was applied at 10 kg ha^?1. The results showed that both the DNA and selected mRNA copy numbers of the methanotroph pmoA gene were not affected by the application of urea, urine or DCD. The methanotroph DNA and mRNA pmoA gene copy numbers were low in this soil, below 7.13?×?10³ g^?1 soil and 3.75?×?10³ μg^?1 RNA, respectively. Daily CH₄ flux varied slightly among different treatments during the experimental period, ranging from ?12.89 g CH₄ ha^?1 day^?1 to ?0.83 g CH₄ ha^?1 day^?1, but no significant treatment effect was found. This study suggests that the application of urea fertilizer, animal urine returns and the use of the nitrification inhibitor DCD do not significantly affect soil methanotroph abundance or daily CH₄ fluxes in grazed grassland soils.     

Effect of biochars on adsorption of Cu(II), Pb(II) and Cd(II) by three variable charge soils from southern China

The purpose of this study is to compare the relative contribution of different mechanisms to the enhanced adsorption of Cu(II), Pb(II) and Cd(II) by variable charge soils due to incorporation of biochars derived from crop straws. The biochars were prepared from the straws of canola and peanut using an oxygen-limited pyrolysis method at 350 °C. The effect of biochars on adsorption and desorption of Cu(II), Pb(II) and Cd(II) by and from three variable charge soils from southern China was investigated with batch experiments. Based on the desorption of pre-adsorbed heavy metals, the electrostatic and non-electrostatic adsorptions were separated. EDTA was used to replace the heavy metals complexed with biochars and to evaluate the complexing ability of the biochars with the metals. The incorporation of biochars increased the adsorption of Cu(II), Pb(II) and Cd(II) by the soil; peanut straw char induced a greater increase in the adsorption of the three metals. The increased percentage of Cd(II) adsorption induced by biochars was much greater than that for the adsorption of Cu(II) and Pb(II). Cu(II) adsorption on three variable charge soils was enhanced by the two biochars mainly through a non-electrostatic mechanism, while both electrostatic and non-electrostatic mechanisms contributed to the enhanced adsorption of Pb(II) and Cd(II) due to the biochars. Peanut straw char had a greater specific adsorption capacity than canola straw char and thus induced more non-electrostatic adsorption of Cu(II), Pb(II) and Cd(II) by the soils than did the canola straw char. The complexing ability of the biochars with Cu(II) and Pb(II) was much stronger than that with Cd(II) and thus induced more specific adsorption of Cu(II) and Pb(II) by the soils than that of Cd(II). Biochars increased heavy metal adsorption by the variable charge soils through electrostatic and non-electrostatic mechanisms, and the relative contribution of the two mechanisms varied with metals and biochars.     

Presence of bacteria in aqueous solution influences virus adsorption on nanoparticles

Virus contamination in wastewater is usually accompanied by the existence of various bacteria. Nanoparticles (NPs) have been shown to efficiently remove virus. In this study, bacterial cells, supernatants, and cultures were harvested separately from three strains at the culture ages of 6 and 24 h, corresponding to the log and stationary phases, respectively. The aim is to investigate how their presence affects virus adsorption on the three Fe and Al oxide NPs (α-Fe₂O₃, γ-Fe₂O₃-B, and Al₂O₃) and how these effects change with bacterial growth phase. Bacteriophage phiX174 was used as a virus model. Results showed that bacterial cells, supernatants, and cultures harvested at 6 h generally reduced virus adsorption by an average of 0.75?±?0.84, 7.7?±?9.0, and 10.3?±?8.6 %, respectively, while those harvested at 24 h reduced virus adsorption by an average of 2.1?±?0.93, 21.5?±?6.6, and 24.6?±?6.9 %, respectively. Among the NPs, α-Fe₂O₃ showed more sensitivity to bacteria than the other two, probably because of its relatively higher value of point of zero charge. It was found that cell-induced and supernatant-induced reductions were combined to achieve added results, in which the supernatants contributed much more than the cells, implying that the bacterial exudates might be more crucial in the reduced virus adsorption than the bacterial cells. These results strongly demonstrated that the bacteria-induced reduction in virus adsorption became more significant with culture age. It is suggested that studies conducted in the absence of bacteria may not accurately evaluate the potential of virus removal efficiency of the NPs in bacteria-containing environments.