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1.
Chemosphere ; 254: 126899, 2020 Sep.
Artigo em Inglês | MEDLINE | ID: mdl-32957294

RESUMO

In this study, the reduction of iron-carbon internal electrolysis was reinforced by persulfate for p-nitrophenol removal. The effects of persulfate dosage, initial pH and iron-carbon mass ratio were comprehensively studied in batch experiments. In the system of iron-carbon internal electrolysis coupled with persulfate, the iron-carbon internal electrolysis and persulfate had a significant mutual influence, exhibiting a wide range of pH in the treatment process. Moreover, the coupled system also showed the remarkable removal and degradation efficiency of p-nitrophenol according to the contrast experiments. The satisfactory results should be attributed to the potential reduction of iron-carbon internal electrolysis, which was stimulated by persulfate to transform the nitro group to the amine group, accompanying the subsequent oxidation. Furthermore, persulfate possessed the ability that the dynamically destructive effect on external and internal of Fe0 and the scavenging action on activated carbon, effectively strengthening the potential energy for release and transfer of reductive substances. Both HO• and SO4•- as the main free radicals were formed to mineralize the intermediates in the coupled system. These findings indicate that the system of iron-carbon internal electrolysis coupled with persulfate can be a promising strategy for the treatment of the toxic and refractory wastewater.


Assuntos
Carvão Vegetal/química , Eletrólise/métodos , Ferro/química , Nitrofenóis/análise , Sulfatos/química , Poluentes Químicos da Água/análise , Purificação da Água/métodos , Modelos Teóricos , Nitrofenóis/química , Oxirredução , Águas Residuárias/química , Poluentes Químicos da Água/química
2.
Chemosphere ; 254: 126909, 2020 Sep.
Artigo em Inglês | MEDLINE | ID: mdl-32957299

RESUMO

Soil contamination by heavy metals (HMs) is an environmental problem, and nanoremediation by using zero-valent iron nanoparticles (nZVI) has attracted increasing interest. We used ecotoxicological test and global transcriptome analysis with DNA microarrays to assess the suitability of C. elegans as a useful bioindicator to evaluate such strategy of nanoremediation in a highly polluted soil with Pb, Cd and Zn. The HMs produced devastating effect on C. elegans. nZVI treatment reversed this deleterious effect up to day 30 after application, but the reduction in the relative toxicity of HMs was lower at day 120. We stablished gene expression profile in C. elegans exposed to the polluted soil, treated and untreated with nZVI. The percentage of differentially expressed genes after treatment decreases with exposure time. After application of nZVI we found decreased toxicity, but increased biosynthesis of defensive enzymes responsive to oxidative stress. At day 14, when a decrease in toxicity has occurred, genes related to specific heavy metal detoxification mechanisms or to response to metal stress, were down regulated: gst-genes, encoding for glutathione-S-transferase, htm-1 (heavy metal tolerance factor), and pgp-5 and pgp-7, related to stress response to metals. At day 120, we found increased HMs toxicity compared to day 14, whereas the transcriptional oxidative and metal-induced responses were attenuated. These findings indicate that the profiled gene expression in C. elegans may be considered as an indicator of stress response that allows a reliable evaluation of the nanoremediation strategy.


Assuntos
Caenorhabditis elegans/efeitos dos fármacos , Ferro/química , Metais Pesados/toxicidade , Nanopartículas/química , Estresse Oxidativo/efeitos dos fármacos , Poluentes do Solo/toxicidade , Transcrição Genética/efeitos dos fármacos , Animais , Caenorhabditis elegans/genética , Proteínas de Caenorhabditis elegans/genética , Ecotoxicologia , Nanopartículas Metálicas , Metais Pesados/análise , Estresse Oxidativo/genética , Solo/química , Microbiologia do Solo , Poluentes do Solo/análise , Toxicogenética
3.
Ecotoxicol Environ Saf ; 202: 110921, 2020 Oct 01.
Artigo em Inglês | MEDLINE | ID: mdl-32800256

RESUMO

Jarosite is one of the iron oxyhydroxysulfate minerals that are commonly found in acid mine drainage (AMD) systems. In natural environments, phosphate and sulfate reducing bacteria (SRB) may be coupled to jarosite reduction and transformation. In this research, the effect of phosphate on jarosite reduction by SRB and the associated secondary mineral formation was studied using batch experiments. The results indicated that Fe3+ is mainly reduced by biogenic S2- in this experiment. The effect of PO43- on jarosite reduction by SRB involved not only a physico-chemical factor but also a microbial factor. Phosphate is an essential nutrient, which can support the activity of SRB. In the low PO43- treatment, the production of total Fe2+ was found to be slightly larger than that in the zero PO43- treatment. Sorption of PO43- effectively elevated jarosite stability via the formation of inner sphere complexes, which, therefore, inhibited the reductive dissolution of jarosite. At the end of the experiment, the amounts of total Fe2+ accumulation were determined to be 4.54 ± 0.17a mM, 4.66 ± 0.22a mM, 3.91 ± 0.04b mM and 2.51 ± 0.10c mM (p < 0.05) in the zero, low, medium and high PO43- treatments, respectively, following the order of low PO43- treatment > zero PO43- treatment > medium PO43- treatment > high PO43- treatment. PO43- loading modified the transformation pathways for the jarosite mineral, as well. In the zero PO43- treatment, the jarosite diffraction lines disappeared, and mackinawite dominated at the end of the experiment. Compared to PO43--free conditions, vivianite was found to become increasingly important at higher PO43- loading conditions. These findings indicate that PO43- loading can influence the broader biogeochemical functioning of AMD systems by impacting the reactivity and mineralization of jarosite mineral.


Assuntos
Bactérias/metabolismo , Compostos Férricos/química , Fosfatos/química , Sulfatos/química , Adsorção , Biodegradação Ambiental , Compostos Ferrosos , Ferro/química , Compostos de Ferro/química , Minerais , Mineração , Oxirredução
4.
Ecotoxicol Environ Saf ; 204: 111066, 2020 Nov.
Artigo em Inglês | MEDLINE | ID: mdl-32781344

RESUMO

In this study, an iron-doped metal-organic framework (MOF) Fe/ZIF-8 was synthesized from ZIF-8 at room temperature. Direct carbonization of Fe/ZIF-8 under a nitrogen atmosphere produced nanoporous nitrogen doped carbon nanoparticles decorated with Fe component (Fe/NC). The Fe/NC exhibited a large surface area (1221.185 m2 g-1) and narrow pore-size distribution (3-5 nm). The nanoporous Fe/NC components along with Nafion were used to modify a glassy carbon electrode for the electrochemical determination of chloramphenicol and metronidazole via linear sweep voltammetry. Under optimal conditions, the reduction peak currents (observed at -0.237 V and -0.071 V vs. Ag/AgCl) of these analytes increased linearly with increasing chloramphenicol and metronidazole concentrations in the range of 0.1-100 µM and 0.5-30 µM, with the detection limits estimated to be 31 nM and 165 nM, respectively. This result was attributed to the large surface area, porous structure, high nitrogen content, and as well as the electrocatalytic effect of Fe atoms embeded in the carbon support. The proposed sensor was used for chloramphenicol and metronidazole analysis in samples, providing satisfactory results.


Assuntos
Carbono/química , Cloranfenicol/análise , Técnicas Eletroquímicas/métodos , Ferro/química , Estruturas Metalorgânicas/química , Metronidazol/análise , Nitrogênio/química , Animais , Cloranfenicol/urina , Eletrodos , Humanos , Limite de Detecção , Metronidazol/urina , Leite/química , Nanoporos , Soluções Oftálmicas/química , Porosidade , Comprimidos/química
5.
Ecotoxicol Environ Saf ; 202: 110893, 2020 Oct 01.
Artigo em Inglês | MEDLINE | ID: mdl-32615495

RESUMO

Leaching of the hazardous electric arc furnace (EAF) dust containing mainly zinc ferrite and zinc oxide, accompanied by minor concentrations of arsenic compounds, was investigated using sulfuric acid. In order to reach the maximum recovery of zinc, the leaching solution was adjusted to recover both iron and zinc at their maximum possible values. To obtain a high recovery value of zinc and iron, analyzed by AAS, the optimum leaching condition was found to be the temperature of 90 °C, the sulfuric acid concentration of 3 M, the particle size of 75 µm, the S/L ratio of 1:10 g/mL and the leaching time of 2 h. The percentages of the zinc and iron recovery under the optimum condition were ca. 98.6% and 99.1% respectively, which were verified by a confirmation test and were very close to the predicted values of 100% based on the optimized model, obtained through the software. From the thermodynamics' point of view, it has been found that Zn2+ is the predominant species (90%) under the leaching condition applied. Moreover, the predominant species of iron are FeSO4+, FeHSO42+, Fe(SO4)2- and Fe3+ in the magnitudes of 65.8%, 25.6%, 4.4% and 4.0%, respectively. According to the kinetic results, the controlling step in the leaching was the chemical reaction at the most of the operating temperatures and times. In order to purify the zinc solution for electrowinning, iron and arsenic were removed through the jarosite formation process as confirmed by the XRD results. The speciation of arsenic in the precipitated jarosite was explored by XPS. Finally, the low concentrations of arsenic (less than 0.1 ppm) and iron (less than 50 ppm) were determined by the ICP analysis.


Assuntos
Compostos Férricos/química , Metalurgia/métodos , Reciclagem , Sulfatos/química , Zinco/análise , Poeira/análise , Eletricidade , Ferro/química , Tamanho da Partícula , Ácidos Sulfúricos , Temperatura , Óxido de Zinco
6.
Int J Mol Sci ; 21(15)2020 Jul 23.
Artigo em Inglês | MEDLINE | ID: mdl-32717853

RESUMO

As SARS-CoV-2 is spreading rapidly around the globe, adopting proper actions for confronting and protecting against this virus is an essential and unmet task. Reactive oxygen species (ROS) promoting molecules such as peroxides are detrimental to many viruses, including coronaviruses. In this paper, metal decorated single-wall carbon nanotubes (SWCNTs) were evaluated for hydrogen peroxide (H2O2) adsorption for potential use for designing viral inactivation surfaces. We employed first-principles methods based on the density functional theory (DFT) to investigate the capture of an individual H2O2 molecule on pristine and metal (Pt, Pd, Ni, Cu, Rh, or Ru) decorated SWCNTs. Although the single H2O2 molecule is weakly physisorbed on pristine SWCNT, a significant improvement on its adsorption energy was found by utilizing metal functionalized SWCNT as the adsorbent. It was revealed that Rh-SWCNT and Ru-SWCNT systems demonstrate outstanding performance for H2O2 adsorption. Furthermore, we discovered through calculations that Pt- and Cu-decorated SWNCT-H2O2 systems show high potential for filters for virus removal and inactivation with a very long shelf-life (2.2 × 1012 and 1.9 × 108 years, respectively). The strong adsorption of metal decorated SWCNTs and the long shelf-life of these nanomaterials suggest they are exceptional candidates for designing personal protection equipment against viruses.


Assuntos
Betacoronavirus/efeitos dos fármacos , Desinfetantes/farmacologia , Peróxido de Hidrogênio/análise , Nanotubos de Carbono/química , Adsorção , Infecções por Coronavirus/prevenção & controle , Teoria da Densidade Funcional , Desinfetantes/química , Estabilidade de Medicamentos , Humanos , Ferro/química , Ferro/farmacologia , Pandemias/prevenção & controle , Equipamento de Proteção Individual , Platina/química , Platina/farmacologia , Pneumonia Viral/prevenção & controle , Ródio/química , Ródio/farmacologia , Rutênio/química , Rutênio/farmacologia , Inativação de Vírus
7.
Chemosphere ; 259: 127395, 2020 Nov.
Artigo em Inglês | MEDLINE | ID: mdl-32623200

RESUMO

In this work, iron (oxyhydr)oxide nanoparticle-doped expanded graphite (IO/EG-1 and IO/EG-2) was prepared via a hydrothermal reaction and applied for the phosphorus adsorption in the aqueous solutions. The analysis of scanning electron microscopy (SEM) and X-ray diffraction (XRD) verified the successful fabrication of IO/EGs, and iron (oxyhydr)oxide nanoparticles became more crystalized according to the calcination at high temperature (IO/EG-2). The maximum adsorption capacity of IO/EG-1 was considerably higher (7.30 mg/g) than that of IO/EG-2 (0.70 mg/g) mainly due to the electrostatic interaction between the negatively charged phosphate ions with iron (oxyhydr)oxides. At the neutral pH, IO/EG-1 exhibited more positively charged than IO/EG-2, which the iso-electric points (IEP) were pH of 9.1 and 6.0, respectively. The thermodynamic study also suggested that the phosphorus adsorption energy of IO/EG-1was considerably favorable (-12.13 kJ/mol) than that of IO/EG-2 (-7.43 kJ/mol). The regeneration of IO/EG-1 were efficiently achieved by a simple extraction using an alkaline solution such as NaOH. Overall, our study suggested that the prepared IO/EGs could be used as good adsorbents for the phosphorus recovery from aqueous solutions.


Assuntos
Grafite/química , Fósforo/química , Poluentes Químicos da Água/química , Adsorção , Concentração de Íons de Hidrogênio , Ferro/química , Nanopartículas , Óxidos , Fosfatos , Termodinâmica , Difração de Raios X
8.
Chemosphere ; 260: 127574, 2020 Dec.
Artigo em Inglês | MEDLINE | ID: mdl-32688316

RESUMO

Artisanal and small-scale gold mining (ASGM) operations are major contributors to the Philippines' annual gold (Au) output (at least 60%). Unfortunately, these ASGM activities lacked adequate tailings management strategies, so contamination of the environment is prevalent. In this study, soil contamination with copper (Cu), lead (Pb), zinc (Zn) and arsenic (As) due to ASGM activities in Nabunturan, Davao de Oro, Philippines was investigated. The results showed that ASGM-impacted soils had Cu, Pb, Zn and As up to 3.6, 83, 73 and 68 times higher than background levels, respectively and were classified as 'extremely' polluted (CD = 30-228; PLI = 5.5-34.8). Minerals typically found in porphyry copper-gold ores like pyrite, chalcopyrite, malachite, galena, sphalerite and goethite were identified by XRD and SEM-EDS analyses. Furthermore, sequential extraction results indicate substantial Cu (up to 90%), Pb (up to 50%), Zn (up to 65%) and As (up to 48%) partitioned with strongly adsorbed, weak acid soluble, reducible and oxidisable fractions, which are considered as 'geochemically mobile' phases in the environment. Although very high Pb and Zn were found in ASGM-impacted soils, they were relatively immobile under oxidising conditions around pH 8.5 because of their retention via adsorption to hydrous ferric oxides (HFOs), montmorillonite and kaolinite. In contrast, Cu and As release from the historic ASGM site samples exceeded the environmental limits for Class A and Class C effluents, which could be attributed to the removal of calcite and dolomite by weathering. The enhanced desorption of As at around pH 8.5 also likely contributed to its release from these soils.


Assuntos
Mineração , Poluentes do Solo/análise , Poluentes do Solo/química , Solo/química , Arsênico/análise , Arsênico/química , Cobre/análise , Cobre/química , Ouro/análise , Ferro/química , Compostos de Ferro/química , Chumbo/análise , Chumbo/química , Minerais/química , Filipinas , Sulfetos/química , Difração de Raios X , Zinco/análise , Zinco/química
9.
Nucleic Acids Res ; 48(15): 8663-8674, 2020 09 04.
Artigo em Inglês | MEDLINE | ID: mdl-32663277

RESUMO

Divalent metal cations are essential to the structure and function of the ribosome. Previous characterizations of the ribosome performed under standard laboratory conditions have implicated Mg2+ as a primary mediator of ribosomal structure and function. Possible contributions of Fe2+ as a ribosomal cofactor have been largely overlooked, despite the ribosome's early evolution in a high Fe2+ environment, and the continued use of Fe2+ by obligate anaerobes inhabiting high Fe2+ niches. Here, we show that (i) Fe2+ cleaves RNA by in-line cleavage, a non-oxidative mechanism that has not previously been shown experimentally for this metal, (ii) the first-order in-line rate constant with respect to divalent cations is >200 times greater with Fe2+ than with Mg2+, (iii) functional ribosomes are associated with Fe2+ after purification from cells grown under low O2 and high Fe2+ and (iv) a small fraction of Fe2+ that is associated with the ribosome is not exchangeable with surrounding divalent cations, presumably because those ions are tightly coordinated by rRNA and deeply buried in the ribosome. In total, these results expand the ancient role of iron in biochemistry and highlight a possible new mechanism of iron toxicity.


Assuntos
Cátions Bivalentes/metabolismo , Ferro/metabolismo , Clivagem do RNA/genética , Ribossomos/genética , Sítios de Ligação , Cátions Bivalentes/química , Ferro/química , Magnésio/química , Magnésio/metabolismo , Metais/química , Metais/metabolismo , Oxirredução/efeitos dos fármacos , Ribossomos/química
10.
Ecotoxicol Environ Saf ; 203: 110945, 2020 Oct 15.
Artigo em Inglês | MEDLINE | ID: mdl-32684517

RESUMO

The high-concentration wastewater produced in the industrial reverse osmosis (RO) process contains a large amount of refractory organic matters, which will have serious impacts on the natural environment and human health. Among them, contaminants can be transformed by humus-reducing bacteria based on humus. In this study, O3- assisted UV-Fenton method was applied as pretreatment. Biological activated carbon (BAC) technology in which humus-reducing bacteria were the dominant bacteria, enhanced by electron donor and Fe3+, was used to dispose of RO concentrate (ROC). The results showed that water treatment process combining oxidation with biological filtration had a positive effect on the removal of stubborn contaminants in ROC. The system was strengthened by adding electron donor and Fe3+, and the chemical oxygen demand (COD) removal efficiency was up to 80.1%. However, when the removal efficiency of UV254 absorbing pollutants reached optimal value (87.3%), that means only Fe3+ was added.


Assuntos
Carvão Vegetal/análise , Compostos Férricos/química , Substâncias Húmicas , Poluentes Químicos da Água/análise , Purificação da Água/métodos , Análise da Demanda Biológica de Oxigênio , Filtração/métodos , Substâncias Húmicas/análise , Substâncias Húmicas/microbiologia , Hidrocarbonetos Halogenados/análise , Peróxido de Hidrogênio/química , Ferro/química , Osmose , Oxirredução , Ozônio/química , Raios Ultravioleta , Águas Residuárias/análise , Águas Residuárias/microbiologia
11.
Chemosphere ; 259: 127466, 2020 Nov.
Artigo em Inglês | MEDLINE | ID: mdl-32615456

RESUMO

This work addresses the mineralization of the widely used Methyl Orange (MO) azo dye by technologies based on H2O2 electrogeneration at a 3D-like air-diffusion cathode. These include two Fe2+-catalyzed processes such as electro-Fenton (EF) and photoelectro-Fenton (PEF). Bulk electrolyses were performed in a recirculation flow plant, in which the Eco-Cell filter-press electrochemical reactor was connected in series with a UVA photoreactor. The former reactor was equipped with a Ti|Ir-Sn-Sb oxide plate anode alongside a 3D-like air-diffusion cathode made from graphite felt and hydrophobized carbon cloth, aimed at electrogenerating H2O2 on site. The influence of current density (j), volumetric flow rate (Q) and initial MO concentration was examined. The greatest oxidation power corresponded to PEF process. The best operation conditions to treat 30 mg L-1 of total organic carbon of MO in a 50 mM Na2SO4 solution by PEF were found at 0.50 mM Fe2+, pH 3.0, j = 20 mA cm-2 and Q = 2.0 L min-1, obtaining 100% and 94% of color and TOC removals at 30 and 240-300 min, respectively. This accounted for 35% of mineralization current efficiency and 0.12 kWh (g TOC)-1 of energy consumption at the end of the electrolysis. The oxidation power of EF and PEF was compared with that of anodic oxidation (AO), and the sequence obtained was: PEF > EF > AO. The dye was gradually degraded, yielding non-toxic short carboxylic acids, like maleic, fumaric, formic, oxalic and oxamic, whose Fe(III) complexes were rapidly photolyzed.


Assuntos
Compostos Azo/química , Poluentes Químicos da Água/química , Carbono , Ácidos Carboxílicos , Difusão , Eletrodos , Eletrólise , Compostos Ferrosos , Peróxido de Hidrogênio/química , Ferro/química , Oxirredução , Fotólise
12.
Chemosphere ; 260: 127617, 2020 Dec.
Artigo em Inglês | MEDLINE | ID: mdl-32683031

RESUMO

In this study, poly dimethyl diallyl ammonium chloride (PDADMAC) and polyacrylamide (PAM) were applied to substitute ferric trichloride (FeCl3) and lime conditioning for advanced dewatering of landfill sludge (LS). Four response surface methodology (RSM) models were constructed for FeCl3-lime, FeCl3-PAM, PDADMAC-lime and PDADMAC-PAM, and identical dosages, namely 29.86, 57.91, 5.73 and 2.99 mg/g dry solids (DS) for FeCl3, lime, PDADMAC and PAM, were obtained by solving the system of four RSM equations at water content of 60% to investigate conditioning mechanisms. Compared to FeCl3-lime, PDADMAC-PAM conditioning had strong charge neutralization and bridging performance, and obtained conditioned LS with large flocs size, strong network structure and rapid dewatering rate. By integrating RSM with nonlinear programming for optimization, the total cost of PDADMAC-PAM route was saved by 7.9% and close to FeCl3-lime, and the optimized condition with dosages of 1.93 and 3.47 kg/t DS was further confirmed by pilot-scale experiments. The results indicated that PDADMAC-PAM was a feasible substitute for FeCl3-lime in sludge conditioning, and showed more advantage if dewatered sludge was further treated by incineration.


Assuntos
Eliminação de Resíduos Líquidos/métodos , Resinas Acrílicas , Compostos de Cálcio , Floculação , Ferro/química , Óxidos , Polímeros , Esgotos/química , Instalações de Eliminação de Resíduos , Água
13.
Chemosphere ; 260: 127629, 2020 Dec.
Artigo em Inglês | MEDLINE | ID: mdl-32698117

RESUMO

Polychlorinated biphenyls are synthetic industrial organic substances. These persistent pollutants occur in nature causing high ecological risks and damage to human health. Magnetoferritin nanoparticles composed of apoferritin protein shell surrounding synthetically prepared iron-based nanoparticles seem to be a promising candidate for polychlorinated biphenyls elimination. Properties of magnetoferritin, as a redox activity, a biocompatible character, high application possibilities and a close relationship with the human body promoted ours in vitro investigation of the magnetoferritin catalytic activity in the presence of representative 2,4,4'-trichlorobiphenyl. Basic physico-chemical properties of magnetoferritin were determined by ultraviolet and visible spectrophotometry, dynamic light scattering, zeta potential measurements, superconducting quantum interference device magnetometry and atomic force microscopy. The remediation effect of magnetoferritin on 2,4,4'-trichlorobiphenyl was demonstrated by the use of gas chromatography in combination with infrared spectroscopy.


Assuntos
Apoferritinas/química , Ferro/química , Óxidos/química , Bifenilos Policlorados/química , Poluentes Ambientais , Humanos , Nanopartículas/química
14.
Ecotoxicol Environ Saf ; 201: 110868, 2020 Sep 15.
Artigo em Inglês | MEDLINE | ID: mdl-32563163

RESUMO

Technologies based on zero-valent iron (Fe0) are increasingly being used to immobilize metals in soils and remove metals and nitrate from waters. However, the impact of nitrate reduction on metal immobilization in metal contaminated soils has been poorly investigated so far. Here, different concentrations of Fe0 filings (1%, 2% and 5%; wt%) were applied to a metal contaminated soil. The resulting nitrate reduction and metal (Cd and Zn) immobilization was investigated using a column leaching experiment for 12 weeks. Corrosion of Fe0 filings and precipitation of Fe oxyhydroxydes (FeOOH) on the surfaces of the filings were observed using SEM-EDS and EMPA-WDS at the end of the experiment. Compared to the untreated soil, total nitrate amounts released were lowered by 47%, 59% and 87% in the presence of 1%, 2% and 5% of Fe0, respectively. Concomitantly with nitrate reduction, Cd and Zn concentrations in leachates were strongly alleviated in the presence of Fe0, which was partly attributed to the rise of soil pH subsequent to nitrate reduction. More importantly, biotests with Lupinus albus L. revealed that the mechanisms involved in metal immobilization are stable to root-induced acidification. However, Fe0 was not efficient to reduce Cd concentration in Lolium multiflorum Lam., indicating that root processes other than acidification may re-mobilize metals.


Assuntos
Ferro/química , Metais Pesados/análise , Nitratos/análise , Poluentes do Solo/análise , Recuperação e Remediação Ambiental , Lolium/química , Solo/química
15.
Nat Commun ; 11(1): 2738, 2020 06 01.
Artigo em Inglês | MEDLINE | ID: mdl-32483131

RESUMO

Almost half of all enzymes utilize a metal cofactor. However, the features that dictate the metal utilized by metalloenzymes are poorly understood, limiting our ability to manipulate these enzymes for industrial and health-associated applications. The ubiquitous iron/manganese superoxide dismutase (SOD) family exemplifies this deficit, as the specific metal used by any family member cannot be predicted. Biochemical, structural and paramagnetic analysis of two evolutionarily related SODs with different metal specificity produced by the pathogenic bacterium Staphylococcus aureus identifies two positions that control metal specificity. These residues make no direct contacts with the metal-coordinating ligands but control the metal's redox properties, demonstrating that subtle architectural changes can dramatically alter metal utilization. Introducing these mutations into S. aureus alters the ability of the bacterium to resist superoxide stress when metal starved by the host, revealing that small changes in metal-dependent activity can drive the evolution of metalloenzymes with new cofactor specificity.


Assuntos
Proteínas de Bactérias/metabolismo , Ferro/metabolismo , Manganês/metabolismo , Metaloproteínas/metabolismo , Staphylococcus aureus/enzimologia , Superóxido Dismutase/metabolismo , Sequência de Aminoácidos , Proteínas de Bactérias/química , Proteínas de Bactérias/genética , Domínio Catalítico , Evolução Molecular , Ferro/química , Isoenzimas/classificação , Isoenzimas/genética , Isoenzimas/metabolismo , Manganês/química , Metaloproteínas/química , Metaloproteínas/genética , Mutação , Oxirredução , Filogenia , Homologia de Sequência de Aminoácidos , Staphylococcus aureus/genética , Superóxido Dismutase/química , Superóxido Dismutase/genética , Superóxidos/metabolismo
16.
PLoS One ; 15(6): e0234136, 2020.
Artigo em Inglês | MEDLINE | ID: mdl-32520947

RESUMO

Groundwater treatment sludge is a Fe/Mn-bearing waste that is mass produced in groundwater treatment plant. In this study, sludge was converted to a magnetic adsorbent (MA) by adding ascorbate. The sludge was weakly magnetised in the amorphous form with Fe and Mn contents of 28.8% and 8.1%, respectively. After hydrothermal treatment, Fe/Mn oxides in the sludge was recrystallised to siderite and rhodochrosite, with jacobsite as the intermediate in the presence of ascorbate. With an increment in ascorbate dosage, the obtained magnetic adsorbent had a significant increase in chromate adsorption but a decrease in magnetisation. When the Mascorbate/MFe molar ratio was 10, the produced MA-10 was a dumbbell-shaped nanorod with a length of 2-5 µm and a diameter of 0.5-1 µm. This MA-10 showed 183.2 mg/g of chromate adsorption capacity and 2.81 emu/g of magnetisation. The mechanism of chromate adsorption was surface coprecipitation of the generated Cr3+ and Fe3+/Mn4+ from redox reaction between chromate and siderite/rhodochrosite on MA-10, separately. This study demonstrated an efficient recycling route of waste sludge from groundwater treatment to produce MA for treating chromate-bearing wastewater.


Assuntos
Cromatos/química , Magnetismo , Nanotubos/química , Esgotos/química , Eliminação de Resíduos Líquidos/métodos , Poluentes Químicos da Água/química , Adsorção , Carbonatos/química , Compostos Férricos/química , Ferro/química , Cinética , Manganês/química , Oxirredução , Óxidos/química
17.
Chemosphere ; 257: 127209, 2020 Oct.
Artigo em Inglês | MEDLINE | ID: mdl-32502736

RESUMO

An effective method for increasing the utilization efficiency of active components in heterogeneous Fenton-like catalysts was provided. 1.5 at.% Fe-Cu bimetal on 1D sepiolite (Sep) (D-FeCu@Sep) with high dispersion and reduced chemical valence was prepared via complexation-carbonization process of glutathione. 93% of ofloxacin (OFX, a typical antibiotic of emerging concern) was degraded over D-FeCu@Sep without any extra energy input at the optimum conditions (100 mL 10 mg/L OFX, pH 5.0, 3.0 g/L catalyst and 0.03 M H2O2), which was enhanced by 2.3, 3.0 and 1.7 times compared with aggregated Fe-Cu on Sep (A-FeCu@Sep), monometallic Fe on Sep (D-Fe@Sep) and Fe-Cu on blocky Celite (D-FeCu@Celite), respectively. Moreover, it exhibited an excellent performance at a wide working pH range from acidic to neutral conditions (pH 3.2-7.2) with a satisfied stability. Based on the characterizations of X-ray photoelectron spectroscopy (XPS), inductively coupled plasma mass spectrometry (ICP-MS), transmission electron microscopy (TEM), hydrogen temperature-programmed reduction (H2-TPR) and electrochemical impedance spectroscopy (EIS), the proposed complexation-carbonization process of glutathione played an important role in the good Fenton performance of D-FeCu@Sep. The complexation of Fe and Cu ion by glutathione favors the high dispersion of Fe-Cu active component, afterward the reduced chemical valence results from carbonization process of glutathione. Moreover, the 1D nanofibrous structure of D-FeCu@Sep could greatly increase the surface electron transfer efficiency compared with D-FeCu@Celite. This study provides a method alternative to the heterogeneous Fenton chemistry by increasing the utilization efficiency of active components.


Assuntos
Ofloxacino/química , Antibacterianos , Carbono/química , Catálise , Cobre/química , Peróxido de Hidrogênio/química , Ferro/química , Silicatos de Magnésio , Modelos Químicos
18.
Chemosphere ; 258: 127370, 2020 Nov.
Artigo em Inglês | MEDLINE | ID: mdl-32554019

RESUMO

Porous luffa plant fibre (LF) was grafted with Fe and Zr, and the ability of the fabricated adsorbents to remove arsenate (As(V)) from water was investigated in batch and column adsorption experiments. The Langmuir adsorption capacity (mg g-1) at pH 7 of LF was found to be 0.035, which increased to 2.55 and 2.89 after being grafted with Fe (FLF-3) and Zr (ZLF-3), respectively. Grafting with Fe and Zr increased the zeta potential and zero point of charge (ZPC) of LF (from pH 3.9 to 7.4 for Fe grafting and to 7.6 for Zr grafting), due to chemical bonding of the metals, possibly with the hydroxyl and carboxylic groups in LF as indicated in FTIR peaks. Zeta potential and ZPC decreased after As adsorption owing to inner-sphere complexation mechanism of adsorption. The increase of pH from 3 to 10 progressively reduced the adsorbents' adsorption capacity. Co-existing anions weakened the As(V) removal efficiency in the order, PO43- > SiO32- > CO32- > SO42-. Adsorption kinetics data fitted well to the Weber and Morris model, which revealed initial fast and subsequent slow rates of intra-particle As diffusion into the bigger pores and smaller pores, respectively. Column adsorption data fitted well to the Thomas model with the predicted adsorption capacities in the same order as in the batch adsorption experiment (ZLF-3 > FLF-3 > LF).


Assuntos
Arseniatos/análise , Água Potável/química , Ferro/química , Luffa/química , Poluentes Químicos da Água/análise , Purificação da Água/métodos , Zircônio/química , Adsorção , Água Potável/normas , Concentração de Íons de Hidrogênio , Cinética
19.
Food Chem ; 328: 127124, 2020 Oct 30.
Artigo em Inglês | MEDLINE | ID: mdl-32485585

RESUMO

This work demonstrates the challenges for selenium (Se) determination in bean samples using high-resolution continuum source Graphite Furnace Atomic Absorption Spectrometry (HR-CS-GF-AAS) and line source Graphite Furnace Atomic Absorption Spectrometry (LS-GF-AAS). Different chemical modifiers were optimized namely; Ir, Ru, and Pd/Mg nitrates. At selenium contents <5 ng g-1, it cannot be quantified accurately. Spectral interferences of the molecular bands of PO and NO as well as the iron lines with Se line at 196.026 were demonstrated. The noticeable low energy of the continuum source of the HR-CS-GF-AAS at 196.026 nm gives high values of the limits of detection and quantification. The Se limits of detection were found to be 24, 33, and 29 ng g-1 for Ir, Ru, and Pd/Mg modifiers, respectively. In situ trapping hydride generation LS-GF-AAS gives better limits of detection and it reached 30 pg g-1 with Ir modifier.


Assuntos
Fabaceae/química , Selênio/análise , Grafite/química , Ferro/química , Espectrofotometria Atômica
20.
Chemosphere ; 258: 127265, 2020 Nov.
Artigo em Inglês | MEDLINE | ID: mdl-32540534

RESUMO

Ferrate (Fe(VI)) is usually effective for oxidizing a variety of organic pollutants within a few seconds, but some recalcitrant asorganophosphorus pesticides such as dimethoate require higher dose of Fe(VI) and inorganic phosphorus produced by mineralization is difficult to remove. In this study, acid-activated ferrate (Fe(VI)) was firstly used to degrade organophosphorus pesticides dimethoate and simultaneously remove total phosphorus (TP) from solution under simulated sunlight. At a Fe(VI):dimethoate molar radio of 15:1, dimethoate was almost completely removed within 20 min and 47% of TP in the solution was removed by the reduction product of Fe(VI) within 240 min. Electron paramagnetic resonance (EPR) and terephthalic acid (TA) fluorescence experiments showed that •OH radicals were continuously generated in the system, and •OH formation pathway was proposed. Importantly, the involvement of •OH in acid-activated Fe(VI) process was confirmed for the first time by EPR. In the acid-activated Fe(VI)/simulated sunlight system, the removal of dimethoate and TP gradually increased with the decrement of activation pH, whereas the increase of molar ratio of Fe(VI):dimethoate enhanced the removal of dimethoate and TP. The addition of inorganic anions (HCO3- and NO2-) had obvious inhibitory effects on dimethoate and TP removal. Eight degradation products including O,O,S-trimethylphosphorothiate, omethoate and 2-S-methyl-(N-methyl) acetamide were determined by gas chromatography mass spectrometry (GC-MS) analysis, and two possible degradation pathways were proposed. The insights gained from this study open a new avenue to simultaneously degrade and remove organic contaminants.


Assuntos
Dimetoato/análise , Ferro/química , Praguicidas/análise , Ácidos Ftálicos/química , Luz Solar , Poluentes Químicos da Água/análise , Ferro/efeitos da radiação , Modelos Teóricos , Oxirredução , Purificação da Água/métodos
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