Organic mercury solid phase chemoselective capture for proteomic identification of S-nitrosated proteins and peptides.

Cysteine S-nitrosation mediates NO signaling and protein function under pathophysiological conditions. Herein, we provide a detailed protocol regarding the organic mercury chemoselective enrichment of S-nitrosated proteins and peptides. We discuss key aspects of the enrichment strategy and provide technical tips for the best performance of the experimental protocol.

Simultaneous removal of nitrate/phosphate with bimetallic nanoparticles of Fe coupled with copper or nickel supported on chelating resin.

Given the prevalence of nitrate and phosphate in surface and groundwater, it is important to develop technology for the simultaneous removal of nitrate and phosphate. In this study, we prepared the bimetallic nanoparticles of Fe coupled with copper or nickel supported on chelating resin DOW 3N (D-Fe/Ni and D-Fe/Cu) for removing nitrate and phosphate simultaneously. XPS profiles revealed that Cu has better ability than Ni to increase the stability of Fe nanoparticles and prevent nZVI from oxidation. The results showed that nitrate removal efficiencies by D-Fe/Ni and D-Fe/Cu were 98.7% and 95.5%, respectively and the phosphate removal efficiencies of D-Fe/Cu and D-Fe/Ni were 99.0% and 93.0%, respectively. Besides adsorption and coprecipitation as reported in previous studies, the mechanism of phosphate removal also includes the adsorption of the newly formed polymeric ligand exchanger (PLE). Moreover, in previous studies, the presence of phosphate had significant negative effects on the reduction of nitrate. However, in this study, the removal efficiency of nitrate was less affected with the increasing concentration of phosphate for D-Fe/Cu. This was mainly because D-Fe/Cu had higher adsorption capacity of phosphate due to the newly formed PLE according to the XPS depth profile analysis.

Effect of zero-valent iron/starch nanoparticle on nitrate removal using MD simulation.

In this study, the efficacy of zero-valent iron nanostructure modified by starch for removal of nitrate was investigated. Effect of zero-valent iron/starch nanoparticle in the presence of Thiobacillus dinitrificans for removal of nitrate was simulated via material studio software. Thermodynamic principles and proper equations were used via molecular dynamic (MD) simulation. The results of software predictions were demonstrated by radial distribution function (RDF), density, potential energy and temperature graphs. According to the graphs, the simultaneous in the presence of zero-valent iron/starch nanoparticle and Thiobacillus dinitrificans increase the removal efficiency of nitrate reached 91% and in the absence of nanoparticle was 44.44%.

[Characteristic of Nitrate Adsorption in Aqueous Solution by Iron and Manganese Oxide/Biochar Composites].

In this study, we synthesized Fe/Mn bimetallic oxide coated biochar sorbents by pyrolysis of wheat straw impregnated with ferric chloride and potassium permanganate and investigated their potential to adsorb nitrate in water. X-ray photoelectron spectroscopy and scanning electron microscopy analysis suggests that Fe(Ⅲ)/Mn(Ⅳ) bimetallic oxide particles emerge on the sorbents. The optimized sorbent could achieve a specific surface area of 153.116 m2·g-1 and a point of zero charge of 9.76. Batch nitrate adsorption experiments were carried out to investigate the influence of various factors, such as sorbent dosage, initial solution pH, and co-existing anions. Results show that the sorbent maintained a high adsorption capacity of 75.40%-78.70% over a wide range of pH from 1.00 to 9.05, and the sorption mechanism was interpreted as ligand exchange. The effects of co-existing anions on the nitrate sorption followed the decreasing order of Cl- > SO42- > PO43-. Furthermore, the adsorption isotherms were well described by the Langmuir model, and the sorbent could exhibit a quite competitively high capacity of 37.3613 mg·g-1 for nitrate removal. In addition, the accordance of sorption kinetics with the pseudo-second order model implied that the sorption could be a multi-stage controlled chemical process. In addition, the thermodynamic parameters suggested that the sorption reaction could be a spontaneous and endothermic process. The results demonstrated that the Fe/Mn bimetallic oxide coated biochar could serve as a promising agent for nitrate removal from water.

Enhanced nitrate-nitrogen removal by modified attapulgite-supported nanoscale zero-valent iron treating simulated groundwater.

Attapulgite (or palygorskite) is a magnesium aluminium phyllosilicate. Modified attapulgite-supported nanoscale zero-valent iron (NZVI) was created by a liquid-phase reduction method and then applied for nitrate-nitrogen (NO3-N) removal (transformation) in simulated groundwater. Nanoscale zero-valent iron was sufficiently dispersed on the surface of thermally modified attapulgite. The NO3-N removal efficiency reached up to approximately 83.8% with an initial pH values of 7.0. The corresponding thermally modified attapulgite-supported nanoscale zero-valent iron (TATP-NZVI) and NO3-N concentrations were 2.0 g/L and 20 mg/L respectively. Moreover, 72.1% of the water column NO3-N was converted to ammonium-nitrogen (NH4-N) within 6 h. The influence of environmental boundary conditions including dissolved oxygen (DO) concentration, light illumination and water temperature on NO3-N removal was also investigated with batch experiments. The results indicated that the DO concentration greatly impacted on NO3-N removal in the TATP-NZVI-contained solution, and the NO3-N removal efficiencies were 58.5% and 83.3% with the corresponding DO concentrations of 9.0 and 0.3 mg/L after 6 h of treatment, respectively. Compared to DO concentrations, no significant (p > 0.05) effect of light illumination on NO3-N removal and NH4-N generation was detected. The water temperature also has great importance concerning NO3-N reduction, and the removal efficiency of NO3-N at 25 °C was 1.25 times than that at 15 °C. For groundwater, therefore, environmental factors such as water temperature, anaerobic conditions and darkness could influence the NO3-N removal efficiency when TATP-NZVI is present. This study also demonstrated that TATP-NZVI has the potential to be developed as a suitable material for direct remediation of NO3-N-contaminated groundwater.

Impact of electro-stimulation on denitrifying bacterial growth and analysis of bacterial growth kinetics using a modified Gompertz model in a bio-electrochemical denitrification reactor.

This study aimed to investigate the effect of electro-stimulation on denitrifying bacterial growth in a bio-electrochemical reactor, and the growth were modeled using modified Gompertz model under different current densities at three C/Ns. It was found that the similar optimum current density of 250mA/m2 was obtained at C/N=0.75, 1.00 and 1.25, correspondingly the maximum nitrate removal efficiencies were 98.0%, 99.2% and 99.9%. Moreover, ATP content and cell membrane permeability of denitrifying bacteria were significantly increased at optimum current density. Furthermore, modified Gompertz model fitted well with the microbial growth curves, and the highest maximum growth rates (µmax) and shorter lag time were obtained at the optimum current density for all C/Ns. This study demonstrated that the modified Gompertz model could be used for describing microbial growth under different current densities and C/Ns in a bio-electrochemical denitrification reactor, and it provided an alternative for improving the performance of denitrification process.

Kinetic Study of Nitrate Removal from Aqueous Solutions Using Copper-Coated Iron Nanoparticles.

Nitrates are considered hazard compounds for human health due to their tendency to be reduced to nitrites, in particular in reducing environment. Nano zero valent iron (nZVI) represents an efficient and low-cost adsorbent/reductive agent for nitrate removal from groundwater and wastewaters and a little addition of a second metal species (Cu, Pd, Ni, Ag) has proven to increase process effectiveness, by enhancing stability and oxidation resistance of nanoparticles. In this work Cu/Fe nanoparticles were loaded in a NO3- solution (100 mg L-1) and the removal efficiency was tested by monitoring nitrate concentration at selected time intervals. Results showed that the nitrate removal process involves both reduction and adsorption processes: the removal mechanism has been investigated, and the pseudo-first-order and pseudo-second-order-adsorption kinetic models were successfully tested.

[Performance Recoverability of Denitrifying Granular Sludge Under the Stressing Effect of Nanoscale Zero-valent Iron].

To explore the potential stressing effect of nanoscale zero-valent iron (nZVI) on denitrifying granular sludge (DGS), the evolution of DGS denitrifying performance under different C/N ratios was investigated in this study, by carrying out batch tests of eight successive periods with the nZVI shock-loading. The results showed that the specific denitrification rate of µ value decreased when the nZVI dosage was higher than 5 mg · L⁻¹. Meanwhile, a positive correlation between the inhibition ratio (IR) of µ value and substrate C/N ratios or nZVI dosage was observed. When the nZVI dosage reached 100 mg · L⁻¹, both extracellular protein and polysaccharides concentrations decreased obviously. It would be beneficial to promote the recovery of DGS denitrifying activity and reduce the COD demanding to remove unit mass of nitrate, by increasing external carbon source with C/N ratios of higher than 4. On the basis of Freundlich and Langmuir adsorption isotherms, when higher C/N ratio was provided, stronger bioadsorption of nZVI would be achieved. During the recovery period, a significant improvement of DCS denitrifying performance under the high C/N ratio was expected, due to the continuous washout of total iron in sludge phase (Qe), while the µ value would reach or approach the one of the control group when Qe was lower than 0.4 mg · g⁻¹.

Efficient recovery of nitrate and phosphate from wastewater by an amine-grafted adsorbent for cyanobacterial biomass production.

Various types of wastewater have been widely utilized in microalgae and cyanobacteria cultivation for environmental and economic reasons. However, the problems of low cell growth and biomass contamination due to direct use of wastewater remain unresolved. In the present study, nitrate and phosphate were separated from wastewater by adsorption and subsequently used for cyanobacterial biomass production. To this end, an amine-grafted magnetic absorbent was synthesized. The synthesized absorbent recovered ca. 78% nitrate and 93% phosphate from wastewater. Regenerated medium was prepared using recovered nutrients as nitrogen and phosphate sources, which were efficiently assimilated by cyanobacterial culture. Compared to synthetic medium, there was no difference in growth and nutrient removal using regenerated medium. The proposed indirect method of wastewater utilization would prevent contamination of the produced biomass by unfavorable substances, which will broaden its potential applications.

Effect of electro-stimulation on activity of heterotrophic denitrifying bacteria and denitrification performance.

The effects of electro-stimulation on heterotrophic denitrifying bacterial activity and nitrate removal were investigated using a bench-scale bio-electrochemical reactor in this study. Results showed that the maximum nitrate removal efficiency was 100% at the optimum current density of 200mA/m(2), at which low nitrite production and high ATP aggregate level were obtained. The activity of denitrifying bacteria was highest at the range densities of 200-250mA/m(2), although the terminative pH increased to 8.62 at 200mA/m(2) and 9.63 at 250mA/m(2). This demonstrates that suitable current densities could improve the activity of denitrifying bacteria. Therefore, this study provides a number of useful information to improve the bio-electrochemical reactor designs and promote the removal efficiency of pollutants.

An endophytic bacterium Acinetobacter calcoaceticus Sasm3-enhanced phytoremediation of nitrate-cadmium compound polluted soil by intercropping Sedum alfredii with oilseed rape.

Intensive agricultural system with high input of fertilizer results in high agricultural output. However, excessive fertilization in intensive agricultural system has great potential to cause nitrate and heavy metal accumulation in soil, which is adverse to human health. The main objective of the present study was to observe the effects of intercropping and inoculation of endophytic bacterium Acinetobacter calcoaceticus Sasm3 on phytoremediation of combined contaminated soil in oilseed rape (Brassica napus L.). The results showed that with Sasm3 inoculation, the biomass of rape was increased by 10-20% for shoot, 64% for root, and 23-29% for seeds while the nitrate accumulation in rape was decreased by 14% in root and by 12% in shoot. The cadmium concentration in rape increased significantly with mono-inoculating treatment, whereas it decreased significantly after intercropping treatment. By denaturing gradient gel electrophoresis (DGGE) and real-time quantitative PCR analysis, the diversity of bacterial community and the number of nirS and nirK gene copies increased significantly with inoculation or/and intercropping treatment. In conclusion, the endophytic bacterium Sasm3-inoculated intercropping system not only improved the efficiency of clearing cadmium from soil without obstructing crop production, but also improved the quality of crop.

Heterotrophic nitrogen removal by Acinetobacter sp. Y1 isolated from coke plant wastewater.

A strain of Acinetobacter sp. Y1, which exhibited an amazing ability to remove ammonium, nitrite and nitrate, was isolated from the activated sludge of a coking wastewater treatment plant. The aim of this work was to study the ability, influence factors and possible pathway of nitrogen removal by Acinetobacter sp. Y1. Results showed that maximum removal rate of NH4(+)-N by the strain was 10.28 mg-N/L/h. Carbon source had significant influence on the growth and ammonium removal efficiencies of strain Y1. Pyruvate, citrate and acetate were favourable carbon sources for the strain. Temperature, pH value and shaking speed could affect the growth and nitrogen removal ability. Nitrate or nitrite could be used as a sole nitrogen source for the growth and removed efficiently by the strain. N2 levels increased to 53.74%, 50.21% and 55.13% within 36 h when 100 mg/L NH4(+)-N, NO2(-)-N or NO3(-) -N was used as sole nitrogen source in the gas detection experiment. The activities of hydroxylamine oxidoreductase (HAO), nitrate reductase (NR) and nitrite reductase (NiR), which are key enzymes in heterotrophic nitrification and aerobic denitrification, were all detectable in the strain. Consequently, a possible pathway for ammonium removal by the strain was also suggested.

Mixed sulfur-iron particles packed reactor for simultaneous advanced removal of nitrogen and phosphorus from secondary effluent.

A mixed sulfur-iron particles packed reactor (SFe reactor) was developed to simultaneously remove total nitrogen (TN) and total phosphorus (TP) of the secondary effluent from municipal wastewater treatment plants. Low effluent TN (<1.5 mg/L) and TP (<0.3 mg/L) concentrations were simultaneously obtained, and high TN removal rate [1.03 g N/(L·d)] and TP removal rate [0.29 g P/(L·d)] were achieved at the hydraulic retention time (HRT) of 0.13 h. Kinetic models describing denitrification were experimentally obtained, which predicted a higher denitrification rate [1.98 g N/(L·d)] of SFe reactor than that [1.58 g N/(L·d)] of sulfur alone packed reactor due to the mutual enhancement between sulfur-based autotrophic denitrification and iron-based chemical denitrification. A high TP removal obtained in SFe reactor was attributed to chemical precipitation of iron particles. Microbial community analysis based on 16S rRNA revealed that autotrophic denitrifying bacteria Thiobacillus and Sulfuricella were the dominant genus, indicating that autotrophic denitrification played important role in nitrate removal. These results indicate that sulfur and iron particles can be packed together in a single reactor to effectively remove nitrate and phosphorus.

Nitrate reduction by mixed iron(II-III) hydroxycarbonate green rust in the presence of phosphate anions: the key parameters influencing the ammonium selectivity.

The reduction of nitrate anions by a mixed Fe(II)-Fe(III) carbonated green rust (GR) in aqueous medium is studied as a function of the initial pH and the initial concentrations of iron, phosphate and nitrate. The influence of these parameters on the fraction of nitrate removed and the production of ammonium is investigated by the help of statistical experimental designs. The goal is to determine experimental conditions that maximize the fraction of NO3(-) removed and concomitantly minimize the production of NH4(+). Increasing the phosphate concentration relatively to the initial Fe(II) concentration inhibits the reduction of nitrate probably due to a surface saturation of the lateral sites of the GR crystals. The kinetics of the reaction is greatly enhanced by increasing the initial pH at 10.5, however it leads to a global increase of the NH4(+) production. A partial saturation of the surface sites by phosphate leads to a global decrease of selectivity of the reaction towards ammonium. The evolution of the ratio of the NH4(+) concentration to the Fe(II) concentration confirms that the NO3(-) species are only partially transformed into ammonium. Interestingly at an initial pH of 7.5, the selectivity of the reaction towards NH4(+) is often lower than ∼30%. The reduction of nitrate by carbonated GR differs from the behavior of other GRs incorporating Cl(-), F(-) and SO4(2-) anions that fully transform nitrate into ammonium. Finally, if GR is intended to be used during a passive water denitrification process, complementary dephosphatation and ammonium treatments should be considered.

Influence of zero-valent iron nanoparticles on nitrate removal by Paracoccus sp.

Nitrate contamination in drinking water is a major threat to public health. This study investigated the efficiency of denitrification of aqueous solutions in the co-presence of synthesized nanoscale zero-valent iron (nZVI; diameter: 20-80 nm) and a previously isolated Paracoccus sp. strain YF1. Various influencing factors were studied, such as oxygen, pH, temperature, and anaerobic corrosion products (Fe(2+), Fe(3+) and Fe3O4). With slight toxicity to the strain, nZVI promoted denitrification efficiency by providing additional electron sources under aerobic conditions. For example, 50 mg L(-1) nZVI increased the nitrate removal efficiency from 66.9% to 85.2%. However, a high concentration of nZVI could lead to increased production of Fe(2+), a toxic ion which could compromise the removal efficiency. Kinetic studies suggest that denitrification by both free cells, and nZVI-amended cells fitted well to the zero-order model. Temperature and pH are the major factors affecting nitrate removal and cell growth, with or without the presence of nZVI. In this study, nitrate removal and cell growth increased in the pH range of 6.5-8.0, and temperature range of 25-35 °C. These conditions favor the growth of the strain, which dominated denitrification in all scenarios involved. As for anaerobic corrosion products, compared with Fe(2+) and Fe(3+), Fe3O4 promoted denitrification by serving as an electron donor. Finally, scanning electron microscopy (SEM), energy dispersive spectroscopy (EDS) and X-ray diffraction (XRD) confirmed attachments of nZVI on the surface of the cell, and the formation of iron oxides. This study indicated that, as an electron donor source with minimal cellular toxicity, nZVI could be used to promote denitrification efficiency under biotic conditions.

Copper, zinc superoxide dismutase and nitrate reductase coimmobilized bienzymatic biosensor for the simultaneous determination of nitrite and nitrate.

This work presents a novel bienzymatic biosensor for the simultaneous determination of nitrite (NO2(-)) and nitrate (NO3(-)) ions using copper, zinc superoxide dismutase (SOD1) and nitrate reductase (NaR) coimmobilized on carbon nanotubes (CNT)-polypyrrole (PPy) nanocomposite modified platinum electrode. Morphological changes of the PPy and CNT modified electrodes were investigated using scanning electron microscopy. The electrochemical behavior of the bienzymatic electrode (NaR-SOD1-CNT-PPy-Pt) was characterized by cyclic voltammetry exhibiting quasi-reversible redox peak at +0.06 V and reversible redox peaks at -0.76 and -0.62V vs. Ag/AgCl, for the immobilized SOD1 and NaR respectively. The electrocatalytic activity of SOD1 towards NO2(-) oxidation observed at +0.8 V was linear from 100 nM to 1mM with a detection limit of 50 nM and sensitivity of 98.5 ± 1.7 nA µM(-1)cm(-2). Similarly, the coimmobilized NaR showed its electrocatalytic activity towards NO3(-) reduction at -0.76 V exhibiting linear response from 500 nM to 10mM NO3(-) with a detection limit of 200 nM and sensitivity of 84.5 ± 1.56 nA µM(-1)cm(-2). Further, the present bienzymatic biosensor coated with cellulose acetate membrane for the removal of non-specific proteins was used for the sensitive and selective determinations of NO2(-) and NO3(-) present in human plasma, whole blood and saliva samples.

Bio-desulfurization and denitrification by anaerobic-anoxic process for the treatment of wastewater from flue gas washing.

For amine-based carbon dioxide capture, nitrogen oxides and sulfur oxides were the main pollutants that had a negative effect on the regeneration of solvent. Before carbon dioxide capture, the sulfur oxides in flue gas should be removed by the method of calcium salt, and then washed by alkaline solution to eliminate the residual nitrogen oxides and sulfur oxides. The washing wastewater containing sulfate and nitrate needs to be treated. In this study, a novel anaerobic-anoxic process was built up for the treatment of this washing wastewater. Nitrate was reduced to nitrogen by denitrifying bacteria. Sulfate was firstly reduced to sulfide by sulfate reducing bacteria, and then selectively oxidized to element sulfur by sulfide oxidizing bacteria. The treated liquid could be reused as absorption after the adjustment of pH value. The performances of this bioprocess were investigated under various pH values and S/N ratios. It was found that the optimal pH value of influent was 6.0, the percentages of denitrification and sulfate reducing could reach 90 and 89%, respectively. Seventy-six percent of sulfate was transformed into element sulfur. Nitrate significantly had a negative effect on sulfate reduction above 10 mM. As 20 mM nitrate, the sulfate reducing percentage would drop to 67%. These results showed that the anaerobic-anoxic process was feasible for the treatment of flue gas washing wastewater. It would be prospectively applied to other wastewater with the higher ratio of SO4(2-)/NO3(-).

Pilot-scale demonstration of the hybrid zero-valent iron process for treating flue-gas-desulfurization wastewater: part II.

The hybrid zero-valent-iron (hZVI) process is a novel chemical treatment process that has shown promise for removing heavy metals and nutrients from industrial wastewaters. In this study, a pilot-scale demonstration was conducted to continuously treat 3.8-7.6 L/min (1-2 gpm) of the flue-gas-desulfurization (FGD) wastewater at a coal-fired power plant for 5 months. In this paper, a spike test was conducted to evaluate performance of the hZVI process for removing selected toxic metals at artificially elevated concentrations. The results showed that a multiple-stage hZVI process could decrease selenate-Se from 22 mg/L to ~10 µg/L and dissolved Hg(2+) from 1.15 mg/L to ~10 ng/L. In addition, the process simultaneously removed a broad spectrum of heavy metals such as As(III), As(V), Cr(VI), Cd(II), Pb(II) and Cu(II) from mg/L to near or sub-ppb (µg/L) level after a single-stage treatment. The process consumed about 0.3 kg ZVI per 1 m(3) FGD wastewater treated at a cost of about US$0.6/m(3). Solid waste production and energy consumption were reasonably low. The successful pilot study demonstrated that the hZVI technology can be a low-cost, high-performance treatment platform for solving some of the toughest heavy metal water problems.

Effect of pH on nitrate and selenate reduction in flue gas desulfurization brine using the H2-based membrane biofilm reactor (MBfR).

Increased tightening of air regulations is leading more electric utilities to install flue gas desulfurization (FGD) systems. These systems produce brine containing high concentrations of nitrate, nitrite, and selenate which must be removed before discharge. The H2-based membrane biofilm reactor (MBfR) was shown to consistently remove nitrate, nitrite, and selenate at high efficiencies. The maximum selenate removal flux reached 362 mgSe m(-2)d(-1) and was higher than that observed in earlier research, which shows continual improvement of the biofilm for selenate reduction. A low pH of 6.8 inhibited precipitation when treating actual FGD brine, yet did not inhibit removal. SO4(2-) was not removed and therefore did not compete with nitrate, nitrite, and selenate reduction for the available H2.

Removal of nitrate and ammonium ions from livestock wastewater by hybrid systems composed of zero-valent iron and adsorbents.

The feasibility of hybrid systems for simultaneous removal of nitrate (NO3-) and ammonium ions (NH4+) from livestock wastewater was examined in batch experiments. As a part of efforts to remove nitrate and ammonium simultaneously, Fe0 and adsorbents including coconut-based granular activated carbon (GAC), sepiolite and filtralite were used. Various parameters such as adsorbent dosages and temperature were studied. Removal of NO3- increased with increase in temperature. Maximum NO3- removal (85.3%) was observed for the Fe0-filtralite hybrid system at 45 degrees C for a 24 h reaction time. Increase in GAC and sepiolite dosages had significant (P < 0.01) effect on the NH4+ removal efficiency, which was primarily due to the net negative surface charge of the adsorbents. The efficiency of hybrid systems for the removal of NO3- was in the order of filtralite > sepiolite > GAC, and the order of the removal of NH4+ was GAC > sepiolite > filtralite. The results of the present study suggest that the use of hybrid systems could be a promising innovative technology for achieving simultaneous removal of NO3- and NH4 from livestock wastewater.