Ferric Addition Research Articles

Dynamic Response of Sulfate-Reducing and Methanogenic Activities of Anaerobic Sewer Biofilms to Ferric Dosing

AbstractA recent study showed that, in addition to precipitating sulfides, Fe3+ addition to sewers reduces the sulfate-reducing and methanogenic activities of anaerobic sewer biofilms. The dynamic response of these activities to the commencement and termination of ferric dosage is investigated in this study. Both the sulfate-reduction and methane-production rates of anaerobic sewer biofilms decreased upon the addition of ferric ions, with a maximum inhibition of approximately 50% achieved after 3 and 7 days, respectively. In comparison, the sulfate-reducing activity of suspended biomass in the Fe3+ receiving reactor was completely inhibited. The volatile solids-to-total solids (VS/TS) ratio of sewer biofilms decreased from 91±3% before Fe3+ addition to 54±6% after a full adaptation of the biofilms to Fe3+ addition. Energy-dispersive spectroscopy profiles showed higher iron and sulfur contents in biofilms adapted to Fe3+ addition, suggesting FeS deposition in biofilms. We hypothesize that FeS precipitation...

Persulfate oxidation for the aniline degradation in aqueous systems

Ferrous catalyzed persulfate oxidation of dissolved aniline was investigated in aqueous systems under a variety of ferrous ion concentrations and temperature. Result showed that the addition of ferrous ions accelerated the degradation of aniline by persulfate. For the thermally activated persulfate oxidation experiment, the optimum persulfate/aniline concentration ratio at 30˚C was at 5.4 mM or 20/1. This ratio gave the highest aniline removal of 45%. For the ferrous ion catalyzed persulfate oxidation experiment, there was marginal difference in the result for the various ferrous ion/oxidant molar ratios. Thus, another series of experiment was conducted to determine the optimum ratio and a ferrous ion/persulfate molar ratio of 1.25/1 showed the highest removal efficiency.

In situ oxidation of petroleum-hydrocarbon contaminated groundwater using passive ISCO system

Groundwater contamination by gasoline spill is a worldwide environmental problem. Gasoline contains methyl tertiary-butyl ether (MTBE) (a fuel oxygenates) and benzene, which are the chemicals of concerns among the gasoline components. In this study, an in situ chemical oxidation (ISCO) barrier system was developed to evaluate the feasibility of applying this passive system on the control of MTBE and benzene plume in aquifer. The developed ISCO barrier contained oxidant-releasing materials, which could release oxidants (e.g., persulfate) when contact with water for the contaminants’ oxidation in groundwater. In this study, laboratory-scale fill-and-draw experiments were conducted to determine the component ratios of the oxidant-releasing materials and evaluate the persulfate release rates. Results indicate that the average persulfate-releasing rate of 7.26 mg S 2O 8 2−/d/g was obtained when the mass ratio of sodium persulfate/cement/sand/water was 1/1.4/0.24/0.7. The column study was conducted to evaluate the efficiency of in situ application of the developed ISCO barrier system on MTBE and benzene oxidation. Results from the column study indicate that approximately 86–92% of MTBE and 95–99% of benzene could be removed during the early persulfate-releasing stage (before 48 pore volumes of groundwater pumping). The removal efficiencies for MTBE and benzene dropped to approximately 40–56% and 85–93%, respectively, during the latter part of the releasing period due to the decreased persulfate-releasing rate. Results reveal that acetone, byproduct of MTBE, was observed and then further oxidized completely. Results suggest that the addition of ferrous ion would activate the persulfate oxidation. However, excess ferrous ion would compete with organic contaminants for persulfate, and thus, cause the decrease in contaminant oxidation rates. The proposed treatment scheme would be expected to provide a more cost-effective alternative to remediate MTBE, benzene, and other petroleum-hydrocarbon contaminated aquifers. Results from this study will be useful in designing a scale-up system for field application.

Mechanism of enargite pressure leaching in the presence of pyrite

Hydrometallurgy is a promising alternative to treat copper concentrates that contain large amounts of enargite (Cu 3AsS 4). However, leaching of enargite is difficult due to its slow dissolution rate in acidic solutions. The pressure leaching of an enargite concentrate containing about 40% pyrite was carried out in sulfuric acid/oxygen at temperatures in the range of 160 to 200 °C and oxygen partial pressure of 345 to 1034 kPa. The results showed that the dissolution of enargite in the presence of pyrite was considerably faster than the dissolution of pure enargite. By leaching an enargite–pyrite concentrate sample of particle size −75 + 53 μm at 200 °C and 689 kPa O 2, all the copper was extracted in 15 min. It was also found that temperature, oxygen partial pressure and particle size had a significant influence on the rate of enargite dissolution from the enargite–pyrite concentrate, while the sulfuric acid concentration had little effect. Ferric ions produced in the leaching were responsible for the enhanced dissolution of enargite in the presence of pyrite and pure enargite leaching was similarly enhanced by the addition of ferrous ions. Analysis of the data for the enargite–pyrite concentrate showed linear kinetics for the dissolution of pyrite, whilst the rate of dissolution of enargite increased substantially with time as ferric ions build up in solution.

Coordination chemistry approach for the end-to-end assembly of gold nanorods

Gold nanorods synthesized by radiolysis were selectively end-functionalized by a fully conjugated thiol bearing a pendant terpyridine group; addition of ferrous ions led to the end-to-end 1D self-assembly of the nanorods. Similar results have been obtained when the preformed [(HStpy)Fe(tpySH)] 2+ dithiol complex was directly added to the gold nanorods.

Effectiveness of Potassium Ferrate (K2FeO4) for Simultaneous Removal of Heavy Metals and Natural Organic Matters from River Water

This study has investigated how to simultaneously remove both heavy metals (Cu, Mn, and Zn) and natural organic matters (NOM; humic acid and fulvic acid) from river water using potassium ferrate (K2FeO4), a multipurpose chemical acting as oxidant, disinfectant, and coagulant. In water sample including each 0.1 mM heavy metal, its removal efficiency ranged 28–99% for Cu, 22–73% for Mn, and 18–100% for Zn at the ferrate(VI) doses of 0.03–0.7 mM (as Fe). The removal efficiency of each heavy metal increased with increasing pH, whereas an overall temperature did not make any special effect on the reaction between the heavy metal and ferrate(VI). A high efficiency was achieved on the simultaneous treatment of heavy metals (0.1 mM) and NOM (10 mg/l) at the ferrate(VI) doses of 0.03–0.7 mM (as Fe): 87–100% (Cu), 31–81% (Mn), 11–100% (Zn), and 33–86% (NOM). In the single heavy metal solution, the optimum ferrate dose for treating 0.1 mM Cu or Mn was 0.1 mM (as Fe), while that for treating 0.1 mM Zn was 0.3 mM (as Fe). In the mixture of three heavy metals and NOM, on the other hand, 0.5 mM (as Fe) ferrate(VI) was determined as an optimum dose for removing both 0.1 mM heavy metals (Cu, Mn, and Zn) and 10 mg/l NOM. Prior to the addition of ferrate(VI) into the solution of heavy metals and NOM (HA or FA), complexes were formed by the reaction between divalent cations of heavy metals and negatively charged functional groups of NOM, enhancing the removal of both heavy metals and NOM by ferrate(VI).

Lactobacilli prevent hydroxy radical production and inhibitEscherichia coliandEnterococcusgrowth in system mimicking colon fermentation

To explore the effect of Lactobacillus on redox state of colon chyme. Nine Lactobacillus strains were studied for the inhibition of lipid peroxide formation in Fe(2+)/ascorbate system and for their ability to chelate 'free' ferrous ion. The result shows both properties were strain specific and no relationship between them was found. Both properties of Lactobacillus paracasei Fn032, Lactobacillus rhamnosus GG (LGG) and Lactobacillus sp. Fn001 were successively decreasing. LGG and Fn032 significantly decreased hydroxyl radicals (P < 0.01) in colonic fermentation model, in which considerable hydroxyl radicals occurred spontaneously. Addition of ferrous ion induced the production of hydroxyl radicals, which could be significantly inhibited by LGG, Fn032 (P < 0.01) and Fn001 (P < 0.05). Ferrous ion significantly induced the growth of Enterococcus and Escherichia coli, which could be inhibited by all three Lactobacillus strains. Escherichia coli and Enterococcus show significantly positive correlation with hydroxyl radicals with R of 0.96 (P = 0.0002) and 0.91 (P = 0.0017), respectively. Antioxidative Lactobacillus could modulate redox state in colonic fermentation system, which is related to their free radical-scavenging ability or antibacterial effect. This study proves that Lactobacillus strain could influence the redox state of gut chyme. Evaluation of antioxidative ability might be a powerful method for screening probiotic Lactobacillus strains.

Electrochemical Production of Ferrate (Iron VI): Application to the Wastewater Treatment on a Laboratory Scale and Comparison with Iron (III) Coagulant

This paper presents a comparative study of the performance of ferrate(VI), FeO 4 2− , and ferric, Fe(III), towards wastewater treatment. The ferrate(VI) was produced by electrochemical synthesis, using steel electrodes in a 16 M NaOH solution. Domestic wastewater collected from Hailsham North Wastewater Treatment Works was treated with ferrate(VI) and ferric sulphate (Fe(III)). Samples were analysed for suspended solids, chemical oxygen demand (COD), biochemical oxygen demand (BOD) and P removal. Results for low doses of Fe(VI) were validated via a reproducibility study. Removal of phosphorous reached 40% with a Fe(VI) dose as low as 0.01 mg/L compared to 25% removal with 10 mg/L of Fe(III). For lower doses (<1 mg/L as Fe), Fe(VI) can achieve between 60% and 80% removals of SS and COD, but Fe(III) performed even not as well as the control sample where no iron chemical was dosed. The ferrate solution was found to be stable for a maximum of 50 min, beyond which Fe(VI) is reduced to less oxidant species. This provided the maximum allowed storage time of the electrochemically produced ferrate(VI) solution. Results demonstrated that low addition of ferrate(VI) leads to good removal of P, BOD, COD and suspended solids from wastewater compared to ferric addition and further studies could bring an optimisation of the dosage and treatment.

Iron Is an Essential Cause of Fishy Aftertaste Formation in Wine and Seafood Pairing

Fishy aftertaste is sometimes perceived in wine with fish and seafood pairing. However, what component of wine clashes with seafood or what compound contributes to the unpleasant fishy aftertaste in the mouth remains an open problem. First, intensities of unpleasant fishy aftertaste of wine and dried scallop pairings were rated by sensory analysis. Second, components of the wines were analyzed. Strong positive correlations were found between the intensity of fishy aftertaste and the concentration of both total iron and ferrous ion. Moreover, the intensity of fishy aftertaste was increased by the addition of ferrous ion in model wine and suppressed by the chelation of ferrous ion in red wine. Third, potent volatile compounds of fishy aftertaste, such as hexanal, heptanal, 1-octen-3-one, (E,Z)-2,4-heptadienal, nonanal, and decanal, were determined by gas chromatography-olfactometry and gas chromatography-mass spectrometry in dried scallop soaked in red wine. The formations of these compounds depended on the dose of ferrous ion in the model wine. These results suggest that ferrous ion is a key compound of the formation of fishy aftertaste in wine and seafood pairing within the concentration range commonly found in wine.

Methyl Tert‐Butyl Ether (MTBE) Degradation by Ferrous Ion‐Activated Persulfate Oxidation: Feasibility and Kinetics Studies

The objective of this study was to evaluate the feasibility of using ferrous ion-activated persulfate oxidation to remediate groundwater contaminated with methyl tert-butyl ether (MTBE). In this study, batch experiments were conducted to evaluate the effects of various factors on the efficiency of MTBE degradation including persulfate concentrations, ferrous ion concentrations, and persulfate coupled with hydrogen peroxide. Results show that ferrous ion-activated persulfate oxidation was capable of degrading MTBE efficiently. Persulfate and ferrous ion concentrations correlated with MTBE degradation rates. However, excess addition of ferrous ion resulted in decreased MTBE degrading rates most likely because of competition for sulfate free radicals between ferrous ion and MTBE. Two main byproducts of MTBE degradation, tert-butyl formate and tert-butyl alcohol, were detected in the experiments; both were, however, subsequently degraded. Results of sulfate analysis show that proper addition of ferrous ion could prevent unnecessary persulfate decomposition.

Enhancing the electrochemical oxidation of acid-yellow 36 azo dye using boron-doped diamond electrodes by addition of ferrous ion

This work shows preliminary results on the electrochemical oxidation process (EOP) using boron-doped diamond (BDD) electrode for acidic yellow 36 oxidation, a common azo dye used in textile industry. The study is centred in the synergetic effect of ferrous ions and hydroxyl free radicals for improving discoloration of azo dye. The assays were carried out in a typical glass cell under potentiostatic conditions. On experimental conditions, the EOP was able to partially remove the dye from the reaction mixture. The reaction rate increased significantly by addition of Fe 2+ (1 mM as ferrous sulphate) to the system and by (assumed) generation of ferrate ion [Fe(VI)] over BDD electrode. Ferrate is considered as a highly oxidizing reagent capable of removing the colorant from the reaction mixture, in synergistic action with the hydroxyl radicals produced on the BDD surface. Further increases in the Fe 2+ concentration lead to depletion of the reaction rate probably due to the hydroxyl radical scavenging effect of Fe 2+ excess in the system.

Candida albicans, Cryptococcus neoformans or Aspergillus fumigatus Induces an Antifungal Activity in Mouse Serum, which is Different from Transferrin

It has been reported that administration of Candida albicans into mouse induces an antifungal activity in serum, which has been identified as transferrin. In the present study, we show that not only C. albicans, but also other fungus such as Cryptococcus neoformans or Aspergillus fumigatus similarly can induce an antifungal activity in mouse serum. This antifungal activity was inhibited by the addition of ferrous ion, indicating that the growth inhibition of C. albicans was due to deficiency of ferrous ion, which may be caused by transferrin. Indeed, addition of transferrin in an in vitro assay system using RPMI1640 culture medium inhibited the growth of C. albicans, C. neoformans or A. fumigatus. However, when C. albicans was grown in RPMI1640 medium with 10% fetal bovine serum (FBS), transferrin was unable to inhibit the growth of C. albicans, in sharp contrast, when C. albicans treated mouse serum was added instead of FBS, the growth of the organism was inhibited. Similar results were obtained when C. neoformans or A. fumigatus was used. Taken together, the results suggest that antifungal activity induced by C. albicans, C. neoformans or A. fumigatus was not due to transferrin but likely due to other unknown serum proteins, which may cut off the source of iron for the growth of these fungi.

Transformation of Dinitrosyl Iron Complexes [(NO)2Fe(SR)2]− (R = Et, Ph) into [4Fe-4S] Clusters [Fe4S4(SPh)4]2−: Relevance to the Repair of the Nitric Oxide-Modified Ferredoxin [4Fe-4S] Clusters

Transformation of dinitrosyl iron complexes (DNICs) [(NO)(2)Fe(SR)(2)](-) (R = Et, Ph) into [4Fe-4S] clusters [Fe(4)S(4)(SPh)(4)](2-) in the presence of [Fe(SPh)(4)](2-/1-) and S-donor species S(8) via the reassembling process ([(NO)(2)Fe(SR)(2)](-) --> [Fe(4)S(3)(NO)(7)](-) (1)/[Fe(4)S(3)(NO)(7)](2-) (2) --> [Fe(4)S(4)(NO)(4)](2-) (3) --> [Fe(4)S(4)(SPh)(4)](2-) (5)) was demonstrated. Reaction of [(NO)(2)Fe(SR)(2)](-) (R = Et, Ph) with S(8) in THF, followed by the addition of HBF(4) into the mixture solution, yielded complex [Fe(4)S(3)(NO)(7)](-) (1). Complex [Fe(4)S(3)(NO)(7)](2-) (2), obtained from reduction of complex 1 by [Na][biphenyl], was converted into complex [Fe(4)S(4)(NO)(4)](2-) (3) along with byproduct [(NO)(2)Fe(SR)(2)](-) via the proposed [Fe(4)S(3)(SPh)(NO)(4)](2-) intermediate upon treating complex 2 with 1.5 equiv of [Fe(SPh)(4)](2-) and the subsequent addition of 1/8 equiv of S(8) in CH(3)CN at ambient temperature. Complex 3 was characterized by IR, UV-vis, and single-crystal X-ray diffraction. Upon addition of complex 3 to the CH(3)CN solution of [Fe(SPh)(4)](-) in a 1:2 molar ratio at ambient temperature, the rapid NO radical-thiyl radical exchange reaction between complex 3 and the biomimetic oxidized form of rubredoxin [Fe(SPh)(4)](-) occurred, leading to the simultaneous formation of [4Fe-4S] cluster [Fe(4)S(4)(SPh)(4)](2-) (5) and DNIC [(NO)(2)Fe(SPh)(2)](-). This result demonstrates a successful biomimetic reassembly of [4Fe-4S] cluster [Fe(4)S(4)(SPh)(4)](2-) from NO-modified [Fe-S] clusters, relevant to the repair of DNICs derived from nitrosylation of [4Fe-4S] clusters of endonuclease III back to [4Fe-4S] clusters upon addition of ferrous ion, cysteine, and IscS.

Influence of ferrous iron on the granularity of a UASB reactor

The effect of ferrous ion addition on the granularity of an upflow anaerobic sludge blanket (UASB) reactor was investigated. Two UASB reactors (R1 and R2) (35 °C; pH 7) were operated for 3 months at a 20-h hydraulic retention time (HRT) at organic loads from 1.4 to 10.0 g COD L−1 d−1. Ferrous iron was fed only to reactor R1 in a range of load from 0.014 to 0.100 g Fe2+ L−1 d−1. The addition of ferrous iron induced a stable and excellent COD conversion rate. The enhancement of the performance of reactor R1 may be accredited to the mean granule diameter increase as well as to the sludge bed porosity decrease. The addition of iron to reactor R1 had a pronounced effect on the quality of the granular sludge, increasing the characteristic settling velocities. The formation of ferrous sulphide was mainly responsible for the promotion of sludge granulation.

Immobilization of peptides by ozone activation to promote the osteoconductivity of PLLA substrates

In this study, ozone treatment was applied to modify poly(L-lactic acid) (PLLA) with the intermediate reagent acryl-N-succinimide (ASI). Then, P15, the peptide related to the attachment and differentiation of osteoblastic cells, was reacted with ASI. Ozone activation successfully created peroxides on the surface of PLLA, which was quantitatively determined by the iodide method. By changing the activation temperature, oxygen flow rate, reaction bath, reaction temperature or addition of ferrous ions, the amount of peroxides was controlled and the effects of these variables were explored in this research. The immobilizations of ASI and P15 were confirmed and quantitative analyzed by FT-IR spectroscopy, elementary analysis and amino-acid analysis. Also, the optimization for ozone activation and ASI grafting were performed. From in vitro experiments, the cultured ROS cells expressed significantly higher ALPase activity and calcium deposition after P15 immobilization. The results demonstrated that the ROS cells expressed osteoblastic phenotypes more significantly when cultured with the substrate modified with P15. In this study, PLLA was successfully modified with P15 by ozone activation and the modification promoted the osteoconductivity of PLLA substrates, which could be helpful in bone tissue engineering.

Preparation and Properties of Recombinant Rat and Human Procholecystokinin57 –95

Recombinant human progastrin(6-80) binds two ferric ions with an apparent dissociation constant of 2.2 +/- 0.1 microM [Baldwin (2004) Protein J 23:65-70]. The aims of the present study were to express fragments of recombinant procholecystokinin and to determine whether or not they bound ferric ions. Recombinant rat and human procholecystokinin(57-95) were expressed as glutathione S-transferase fusion proteins in E. coli. The fusion proteins were bound to glutathione-agarose, cleaved with thrombin, and purified by reverse phase HPLC. Recombinant procholecystokinin(57-95) did not bind to either the CCK1 or CCK2 receptor with high affinity. No change in absorption spectrum was observed on addition of ferric ions, and analysis of the quenching of tryptophan fluorescence observed in the presence of ferric ions indicated that binding to procholecystokinin(57-95) was at least 40-fold weaker than the binding of ferric ions to progastrin(6-80).

Gentisate 1,2-Dioxygenase fromXanthobacter polyaromaticivorans127W

A putative gentisate 1,2-dioxygenase was encoded in the dibenzothiophene degradation gene cluster (dbd) from Xanthobacter polyaromaticivorans 127W. The deduced amino acid sequence showed high sequence similarity with gentisate dioxygenases from Pseudomonas alcaligenes (AAD49427, 65% identical), Bradyrhizobium japonicum (NP_766750, 64%), and P. aeruginosa (ZP_00135722, 54%), and moderate similarity with 1-hydroxy-2-naphthoate dioxygenase from Nocardioides sp. KP7 (BAA31235, 33%) and salicylate dioxygenase from Pseudaminobacter salicylatoxidans (AAQ91293, 33%). The enzyme, GDOxp, was heterologously produced in Escherichia coli and purified to homogeneity. GDOxp formed a tetramer and exhibited high dioxygenase activity against 1,4-dihydroxy 2-naphthoate as well as gentisate, suggesting unusually broad substrate specificity. GDOxp easily released ferrous ion under unfavorable temperature and pH conditions to become an inactive monomer protein. An inactive monomer protein can reconstitute a tetramer structure and restore enzyme activity in a cooperative manner upon the addition of ferrous ion. Chymotryptic digestion and protein truncation experiments suggested that the N-terminal region is important for the tetramerization of GDOxp.

Effect of ferrous ion on the biological activity in a UASB reactor: Mathematical modeling and verification

The effect of ferrous ion on the biological activity in a upflow anaerobic sludge blanket (UASB) reactor was studied. A mathematical model was developed and validated in order to simulate the dynamic behavior of a UASB reactor. This model took into consideration of all the biological and physicochemical reactions. The model was able to simulate the accumulation of iron in the sludge bed and its effect on the biological activity of the anaerobic sludge. A significant increase in the maximum uptake rate of methanogens and acidogens was revealed when iron was supplemented to the UASB reactor. The addition of ferrous iron induced a stable and excellent COD conversion rate. The model can be a useful tool for the prediction of process performance in the future and can be used to assist in the operation of biogas plants. The ferrous ion addition proved to enhance the biological activity of UASB sludge. Thus, the model can be used for the design of treatment plants that will take advantage of the benefits of iron addition.

Influence of the addition of sulphate and ferric ions in a methanogenic anaerobic packed-bed reactor treating gasoline-contaminated water

Benzene, toluene and xylene (BTX) are relatively soluble aromatic compounds of gasoline. Gasoline storage tank leakages generally lead to an extensive contamination of groundwater. In the natural environment for instance, these compounds might be biodegraded under a variety of reducing potentials. The objective of this work was to examine the influence of the addition of sulphate and Fe(OH)3 in a methanogenic horizontal-flow anaerobic immobilized-biomass reactor treating gasoline-contaminated water. Three different conditions were evaluated: methanogenic, sulphidogenic and sulphidogenic with the addition of ferric ions. Methanogenic condition showed the higher BTX degradation rates and the addition of sulphate negatively affected BTX removal rates with the production of H2S. However, the addition of ferric ions resulted in the precipitation of sulphur, improving BTX degradation by the consortium. Metanosphaera sp., Methanosarcina barkeri and Methanosaeta concilii were identified in the consortium by means of 16S and directly related to the addition of ferric ions.

Reduced Adsorption of Ametryn in Clay, Humic Acid, and Soil by Interaction with Ferric Ion Under Fenton Treatment Conditions

Previous work in our laboratory indicated a weak interaction between ferric ion and several triazine/triazinone herbicides during a Fenton treatment process, and the intensity of the interaction was calculated. To further support the existence of this weak interaction, the adsorption of ametryn, a triazine herbicide, was investigated in kaolinite clay, humic acid, and soil under pseudo-Fenton conditions. At a low addition rate of ferric ion, the adsorption of ametryn in clay, humic acid, and soil was enhanced due to the decreased pH resulting from the hydrolysis of ferric ion. But the pH effect was totally neutralized and the adsorption of ametryn was significantly reduced by further addition of ferric ion, demonstrating the existence of the weak interaction between ametryn and ferric acid. Further study showed that the adsorption-reduction effect of ferric ion existed not only with ametryn but also with several other triazine/triazinone herbicides. This weak interaction may accelerate the desorption process during the remediation of triazine/triazinone herbicide-contaminated soil using a Fenton/Fenton-like treatment, but it may also impede the degradation of these herbicides.